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CHEMISTRY
FOR JEE MAIN & ADVANCED
SECOND
EDITION

Exhaustive Theory
(Now Revised)

Formula Sheet
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Electrochemistry
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17. ELECTROCHEMISTRY

1. INTRODUCTION
Electrochemistry is a branch of chemistry which deals with inter-conversion of chemical energies and electrical
energy. We’ll discuss electrolytic reactions (reactions that occur when electricity passes through solutions) as well
as electromagnetic reaction (reactions that produce electric energy). Some examples of electrolytic reactions are
electrolysis, electroplating, electro refining of metals, etc. Some examples of electro genetic reactions are reactions
occurring in cells or batteries.

2. TERMINOLOGIES IN ELECTROCHEMISTY
Some important terms used in Electrochemistry are as follows:
(a) Electrical Conductors: Materials that allow flow of electrons are known as conductors. There are broadly two
types of conductors-Electronic/Metallic and Electrolytic/Solution.

Table 17.1: Difference between Electronic Conductor and Electrolytic Conductors

Electronic Conductors or Metallic Conductors Electrolytic Conductors or Solution Conductors

1. Passage of current by movement of electrons in the Passage of current by ions in molten state or in aqueous solution
metallic lattice, e.g., Cu, Ag, etc. of electrolytes, e.g., NaCl (aq) or NaCl (fused).
2. Passage of current brings in only physical changes. Passage of current brings in physical as well as chemical changes.
3. It generally shows no transfer of matter. It involves transfer of matter in the form of ions.
4. It generally shows an increase in resistance during the It generally shows a decrease in resistance due to decrease in
passage of current due to increase in temperature. viscosity of the medium and degree of hydration of ions with
Thermal motion of metal ions hindering the flow of increase in temperature.
electrons increases with increase in temperature.
5. The conducting power of metals is usually high. The conducting power of electrolytic conductors is relatively low.

(b) Insulators: Those materials which don’t allow the passage of electrons are known as Insulators. For e.g. wood,
wool, plastic, silk, etc.
(c) Electrolytes: The substance that in solution or in the molten state, conducts electric current and is
simultaneously decomposed is called an electrolyte.The extent or degree of dissociation of different electrolytes
in solution is different. Electrolytes can be broadly categorized into two: Strong and Weak Electrolytes.
(d) Strong Electrolytes: Substances which are largely dissociated and form a highly conducting liquid in water
are strong electrolytes, e.g., All salts (except CdBr2, HgCl2), mineral acids like HCl, H2SO4, HNO3, etc. and
bases like NaOH, KOH, etc. are strong electrolytes. The strong electrolytes are almost 100% ionized at
normal dilution.
1 7 . 2 | Electrochemistr y

(e) Weak Electrolytes: Substances which dissociate only to a small extent in aqueous solution forming low
conducting liquid are weak electrolytes, e.g., All organic acids (except sulphonic acids), inorganic acids
like HCN, H3BO3, etc. and bases like NH3, amines, etc. are weak electrolytes.
(f) Electrodes: In order to pass the current through an electrolytic conductor, two rods or plates are always
needed which are connected with the terminals of a battery. These rods/plates are called Electrodes. The
electrode where oxidation reaction takes place is anode and electrode where reduction takes place is cathode.

3. ELECTROLYSIS
The phenomenon in which passage of current through an electrolyte (molten or solution) brings in chemical
changes involving electronation (reduction) as well as de-electronation (oxidation) of ions is known as electrolysis.

3.1 Preferential Discharge Theory


If an electrolytic solution consists of more than two ions and the electrolysis is done, it is observed that all the
ions are not discharged from the electrodes simultaneously but certain ions are liberated from the electrodes in
preference to others. This is explained by preferential discharge theory. It states that if more than one type of
ions are attracted towards a particular electrode, then the one discharged is the ion which requires least energy.
The potential at which the ion is discharged or deposited on the appropriate electrode is termed the discharge
potential or deposition potential. The values of discharge potential are different for different ions.

Table 17.2: Examples of preferential discharge theory

Electrolyte Electrode Cathodic reaction Anodic reaction


Aqueous acidified Pt 2Cl− → Cl2 + 2e−
CuCl2 solution
Cu2+ + 2e− → Cu
Molten PbBr2 Pt 2Br − → Br2 + 2e−
Pb2+ + 2e− → Pb
Sodium chloride Hg 2Cl− → Cl2 + 2e−
solution
2Na+ + 2e− → 2Na
Silver nitrate solution Pt
Ag+ + e− → Ag 1
2OH− → O2 + H2O + 2e−
2
Sodium nitrate Pt
2H+ + 2e− → H2 1
solution 2OH− → O2 + H2O + 2e−
2

Illustration 1: Find the charge in coulomb on 1 g-ion of N3− .  (JEE MAIN)

Sol: First determine charge on one ions of this can be calculated as product of number of electron and charge of
electron. According to Avogadro’s law one g of ion contains 6.02 × 1023 ions. So, charge on one g-ion of N3− can be
calculated by multiplying charge.
Charge on one ions of N3− into Avogadro number.
3− −19
Charge on one ions of N =3 × 1.6 × 10 coulomb One g-ion = 6.02 × 1023 ions

Thus, charge on one g-ion of N3− =3 × 1.6 × 10 −19 × 6.02 × 1023 = 2.89 × 105 coulomb

Illustration 2: Explain the reaction: (a) 2KI + Cl2 → 2KCl + I2 , (b) 2KClO3 + I2 → 2KIO3 + Cl2

Sol: Compound which undergoes oxidation acts as a reducing agent and compound which undergoes reduction
acts as an oxidizing agent.
Chem i str y | 17.3

(a) Cl2 acts as oxidizing agent: 2e− + Cl2 → 2Cl− ; 2I − → I2 + 2e−
(b) I2 acts as reducing agent: 2Cl5+ + 10e− → Cl ; I02 → 2I5+ + 10e−
2

PLANCESS CONCEPTS

Misconception: Electrolysis does not mean breaking up of an ionic compound into ions. An ionic
compound even on dissolution in water furnishes ions.
Note: During electrolysis, oxidation-reduction occurs simultaneously. Oxidation occurs at anode whereas
reduction occurs at cathode.
Nikhil Khandelwal (JEE 2009 AIR 94)

3.2 Faraday’s Law of Electrolysis


The relationship between the quantity of electric charge passed through an electrolyte and the amount of the
substance deposited at the electrodes was presented as the ‘laws of electrolysis’ by Faraday in 1834.

3.2.1 Faraday’s First Law


When an electric current is passed through an electrolyte, the amount of substance deposited is proportional to
the quantity of electric charge passed through the electrolyte.
If W be the mass of the substance deposited by passing Q coulomb of charge, then according to the law, we have
the relation: W ∝ Q
Q = current in amperes × time in seconds = I × t
So, W ∝ I × t or W = Z×I×t
Where Z is a constant, known as electrochemical equivalent and is characteristic of the substance deposited.
When a current of one ampere is passed for one second, i.e., one coulomb (Q = 1), then W = Z.
Definition of electrochemical equivalent: Mass of the substance deposited by one coulomb of charge or one
ampere current for one second.

3.2.2 Faraday’s Second Law


When the same quantity of charge is passed through different electrolytes, then the masses of different substances
deposited at the respective electrodes will be in the ratio of their equivalent masses. Again according to first law,
W= Z × Q
When, Q = 96500 coulomb, W becomes gram equivalent mass (E).
E Z1 E1
Thus, E= Z × 96500 or Z = ; =
96500 Z 2 E2

3.2.3 Faraday’s Law for Gaseous Electrolytic Product


ItVe
For the gases, we use V =
96500
Where, V = Volume of gas evolved at STP at an electrode
Ve = Equivalent volume = Volume of gas evolved at an electrode at STP by 1 faraday charge
1 7 . 4 | Electrochemistr y

Example: A 40.0 amp current flowed through molten iron (III) chloride for 10.0 hours (36,000 s). Determine the
mass of iron and the volume of chlorine gas (measured at 25ºC and 1 atm) that is produced during this time.

Sol:
 1. Write the half-reaction that take place at the anode and at the cathode.
Anode (oxidation): 2Cl− → Cl2 (g) + 2e− Cathode (reduction): Fe3+ + 3e− → Fe(s)
 2. Calculate the number of moles of electrons.

1.44 × 106 C
40.0amps × 36,000s =
1F 1mole e−
1.44 × 106 C × 14.9F ; 14.9F ×
= 14.9mole e−
=
96, 485C 1F

 3. Calculate the moles of iron and of chlorine produced using the number of moles of electrons calculated and
the stoichiometry from the balanced half-reactions. According to the equations, three moles of electrons
produce one mole of iron and 2 moles of electrons produce 1 mole of chlorine gas.

1mole Fe 1mole Cl2


14.9mole
= e− × e− ×
4.97mole Fe; 14.9mole= 7.45mole Cl2

3mole e 2mole e−
 4. Calculate the mass of iron using the molar mass and calculate the volume of chlorine gas using the ideal gas
law (PV = nRT).

55.847 gFe (7.45moleCl2 )(0.0821atm L / mole K)(298K)


=
4.97mole Fe × 278gFe; = 182L Cl2
1mole Fe 1atm

Calculating the Time required


To determine the quantity of time required to produce a known quantity of a substance given the amount of
current that flowed:
(i) Find the quantity of substance produced/consumed in moles.
(ii) Write the balanced half-reaction involved.
(iii) Calculate the number of moles of electrons required.
(iv) Convert the moles of electrons into coulombs.
(v) Calculate the time required.

Example: How long must a 20.0 amp current flow through a solution of ZnSO 4 in order to produce 25.00 g of Zn
metal?
Sol:
(i) Convert the mass of Zn produced into moles using the molar mass of Zn.
1mole Zn
25.00gZn × 0.3823mole Zn
=
65.39gZn

(ii) Write the half-reaction for the production of Zn at the cathode. Zn2+ (aq) + 2e− → Zn(s)
(iii) Calculate the moles of e- required to produce the moles of Zn using the stoichiometry of the balanced half-
reaction. According to the equation, 2 moles of electrons will produce one mole of zinc.
2mole e−
0.3823mole Zn × 0.7646mole e−
=
1mole Zn
Chem i str y | 17.5

(iv) Convert the moles of electrons into coulombs of charge using Faraday’s constant.
1F 96, 485C
0.76mole e− × = 0.7646F; 0.7646F × = 73,770C
1molee − 1F

(v) Calculate the time using the current and the coulombs of charge.


20.0amps
= × t 73,770C;
= t 3,688s or 1.03h

Calculating the Current required


To determine the amount of current necessary to produce a known quantity of substance in a given amount of
time:
(i) Find the quantity of substance produced/or consumed in moles.
(ii) Write the equation for the half-reaction taking place.
(iii) Calculate the number of moles of electrons required.
(iv) Convert the moles of electrons into coulombs of charge.
(v) Calculate the current required.
Example: What amount of current is required to produce 400.0 L of hydrogen gas, measured at STP, from the
electrolysis of water in 1 hour (3600 s)?

Sol:
(i) Calculate the number of moles of H2. (Remember, at STP, 1 mole of any gas occupies 22.4 L)
1mole H2
400.0L H2 × = 17.9mole H2
22.4L H2

(ii) Write the equation for the half-reaction that takes place.
Hydrogen is produced during the reduction of water at the cathode. The equation for this half-reaction is:

4e− + 4H2O(I) → 2H2 (g) + 4OH− (aq)


(iii) Calculate the number of moles of electrons. According to the stoichiometry of the equation, 4 mole of e− are
required to produce 2 moles of hydrogen gas, or 2 moles of e− s for every one mole of hydrogen gas.
2mole e−
17.9mole H2 × 35.8mole e−
=
1mole H2

(iv) Convert the moles of electrons into coulombs of charge.


1F 96, 485C
35.8mole e− × 35.8F; 35.8F ×
= 3.45 106 C

1mole e − 1F

(v) Calculate the current required. I × 3600s =3.45 × 106 C; I =958C / s =958amps

PLANCESS CONCEPTS

As one faraday (96500 coulombs) deposits one gram equivalent of the substance, hence electrochemical
equivalent can be calculated from the equivalent weight,
Eq. wt. of the substance
i.e., Z =
96500
Note: Knowing the weight of the substance deposited (W gram) on passing a definite quantity of electricity
W
(Q coulombs), the equivalent weight of the substance can be calculated, i.e., Eq. wt.
= × 96500
Q
1 7 . 6 | Electrochemistr y

PLANCESS CONCEPTS

Tip: The quantity of electricity actually passed is calculated from the current and time as follows:
Quantity of electricity in columbs = Current amperes × time in seconds
Thus, knowing the quantity of electricity passed, the amount of substance deposited can be calculated.
Faraday’s first law and second law can be combined to give a mathematical relation as follows:-
E Q Q M C×t M
W = ZQ = ×Q = ×E = × = ×
F F F z F z
z = Electrochemical equivalent; Q = Quantity of electricity passed, E = Eq. wt. of the metal,
F = 1 Faraday, M = Atomic mass of the metal; z = Valency of the metal; C = Current passed,
t = Time for which current is passed.
Saurabh Gupta (JEE 2010 AIR 443)

Illustration 3: Electric current of 100 ampere is passed through a molten liquid of sodium chloride for 5 hours.
Calculate the volume of chlorine gas liberated at the electrode at NTP.  (JEE MAIN)

Sol: Here current and time is given so from this first calculate quantity of electricity passed (charge) and from this
calculate the amount of chlorine liberated. Volume of Cl2 liberated at NTP can be determined by multiplying the
amount of chlorine liberated by 22.4 L

The reaction taking place at anode is: 2Cl− → Cl2 + 2e− Q = I × t = 100 × 5 × 60 × 60 coulomb
71.0 g 71.0 g 2×96500 coulomb
1mole

The amount of chlorine liberated by passing 100 × 5 × 60 × 60 coulomb of electric charge


1
= × 100 × 5 × =
60 × 60 9.3264 mole Volume of Cl2 liberated at NTP= 9.3264 × 22.4= 201L
2 × 96500

Illustration 4: How much electric charge is required to oxidize (a) 1 mole of H2O toO2 and
(b) 1 mole of FeO to Fe2O3 ? (JEE MAIN)

Sol: Charge = No of electrons involved in the reaction x faradays constant


So first find out the no of electron reaction involved in the reaction by writing the chemical reaction, balancing it
and then calculate the charge.
1
(a) The oxidation reaction is: H2O → O2 + 2H+ + 2e− ; Q= 2 × F =
2 × 96500 =
193000 coulomb
1mole 2 2mole

1 1
(b) The oxidation reaction is: FeO + H2O → Fe2O3 + H+ + e− ; O= F= 96500 coulomb
2 2

Illustration 5: An aqueous solution of sodium chloride on electrolysis gives H2 (g),Cl2 (g) and NaOH according to
the reaction. 2Cl− (aq.) + 2H2O → 2OH− (aq.) + H2 (g) + Cl2 (g) .
A direct current of 25 ampere with a current efficiency 62% is passed through 20 L of NaCl solution (20% by mass).
Write down the reactions taking place at the anode and cathode. How long will it take to produce 1 kg of Cl2? What
will be the molarity of the solution with respect to hydroxide ion? Assume no loss due to evaporation. 
 (JEE ADVANCED)
Chem i str y | 17.7

Sol: Time can be calculate by using charge and current relationship. Effective current is determined by using
current efficiency. Here it is given that we have to find out the molarity of the solution with respect to hydroxide
Ion. Volume is given. We have to find out the no of moles of oxygen.
This can be achieved by calculating the no of mole of Cl2 present in 1 kg.
Reactions at anode and cathode are: 2Cl− → Cl2 + 2e− (at anode)
1000
2H2O + 2e− → H2 + 2OH− ( at cathode) 1kg of=
Cl2 = 14.08 mole
71.0

Charge to produce one mole of Cl2=2 x 96500


Charge to produce 14.08 mole of Cl2=2x96500x14.08
62
Effective current = × 25.0 =
15.5 ampere
100
Charge 2 × 96500 × 14.08
Time
= = = 175318.7 second
= 48.699 hour
Current 15.5

OH- ions produced = 2 × moles of Cl2 = 2x14.08 = 28.16

Mole 28.16
Molarity
= = = 1.408M
Volume 20

Illustration 6: An acidic solution of Cu2+ salt containing 0.4 g of Cu2+ is electrolyzed until all the copper is deposited.
The electrolysis is continued for seven more minutes with volume of solution kept at 100 mL and the current at 1.2
amp. Calculate the gases evolved at NTP during the entire electrolysis. (JEE ADVANCED)

0.4
Cu2+
Sol: 0.4 g of = = 0.0126g − equivalent
31.75
8
At the same time, the oxygen deposited at anode = × 0.0126g =
0.00315g − mole
32
After the complete deposition of copper, the electrolysis will discharge hydrogen at cathode and oxygen at anode.
The amount of charge passed = 1.2 × 7 × 60= 504 coulomb
1 8
So, Oxygen liberated= × 504= 0.00523g − equivalent = × 0.00523 =
0.001307g − mole
96500 32
1
0.00523g − equivalent =
Hydrogen liberated = × 0.00523 =0.00261g − mole
2
Total gases evolved =(0.00315 + 0.001307 + 0.00261)g
= − mole 0.007067g − mole

NTP 22400 × 0.007067mL = 158.3mL


Volume of gases evolved at=

4. ARRHENIUS THEORY OF ELECTROLYTIC DISSOCIATION


In order to explain the properties of electrolytic solutions, Arrhenius put forth a comprehensive theory. The main
postulates of the theory are:
(a) An electrolyte, when dissolved in water, breaks up into two types of charged particles, one carrying a positive
charge and the other a negative charge. These charged particles are called ions. Positively charged ions are
termed as cations and negatively charged as anions.

A +B− + aq. → A + (aq.) + B− (aq.)


1 7 . 8 | Electrochemistr y

(b) The process of splitting of the molecules into ions of an electrolyte is called ionization. The fraction of
the total number of molecules present in solution as ions is known as degree of ionizations or degree of
dissociation. It is denoted by ‘ α ’

Number of molecules dissociated int o ions


(c) α =
Total number of molecules

(d) Ions present in solution constantly re-unite to form neutral molecules and, thus, there is a state of dynamic
equilibrium between the ionized and non-ionized molecules, i.e. AB  A + + B−
[A + ][B− ]
(e) Applying the law of mass action to the above equilibrium = K . K is known as ionization constant. The
[AB]
electrolytes having high value of K are termed strong electrolytes and those having low value of K as weak
electrolytes.

(f) When an electric current is passed through the electrolytic solution, the positive ions (cations) move towards
cathode and the negative ions (anions) move towards anode and get discharged, i.e., electrolysis occurs. The
ions are discharged always in equivalent amounts, no matter what their relative speeds are.

(g) The electrolytic solution is always neutral in nature as the total charge on one set of ions is always equal to
the total charge on the other set of ions. However, it is not necessary that the number of two sets of ions must
be equal always.

AB  A + + B− (Both ions are equal)

NaCl  Na+ + Cl− (Both ions are equal)

AB2  A2+ + 2B− (Anions are double that of cations)



2+ −
BaCl2  Ba + 2Cl (Anions are double that of cations)

A2B  2A + + B2− (Cations are double that of anions)

Na2SO 4  2Na+ + SO24− (Cations are double that of anions)

(h) The properties of electrolytes in solution are the properties of ions present in solution. For example, acidic
solution always contains H+ ions while basic solution contains OH− ions and characteristic properties of
solutions are those of H+ ions and OH− ions respectively.

Limitations of Arrhenius Theory


(i) You cannot apply Ostwald’s dilutions law which is based on Arrhenius theory to strong electrolytes.
(ii) Strong electrolytes conduct electricity in a fused state, i.e., in the absence of water. This is in contradiction of
Arrhenius theory which states that the presence of solvent is imperative for ionization.
(iii) Arrhenius theory assumes independent existence of ions but fails to account for the factors which influence
the mobility of the ions.

4.1 Factors Affecting Degree of Ionization


(a) Nature of solute: When the ionizable parts of a molecule of a substance are held more by covalent bonding
than by electrovalent bonding, less ions are furnished in solution.
(b) Nature of solvent: The main function of the solvent is to weaken the electrostatic forces of attraction between
the two ions and separate them.
(c) Dilution: The extent of ionization of an electrolyte is inversely proportional to the concentration of its
solution. Thus, degree of ionization increases with the increase of dilution of the solution, i.e., decreasing the
concentration of the solution.
Chem i str y | 17.9

(d) Temperature: The degree of ionization increases with the increase in temperature. This is due to the fact
that at higher temperatures molecular speed is greater than before which overcomes the forces of attraction
between the ions.

5. ELECTRICAL CONDUCTANCE
The conductance is the property of the conductor (metallic as well as electrolytic) which facilitates the flow of
electricity through it. It is equal to the reciprocal of resistance, i.e.
1 1
Conductance
= =  ... (i)
Resistance R
It is expressed in the unit called reciprocal ohm ( ohm−1 or mho) or Siemens.

5.1 Specific Conductance or Conductivity


The resistance of any conductor varies directly with its length (l) and inversely with its cross-sectional area (a),
l l
i.e. R ∝ or R = ρ  …..... (ii)
a a
Where, ρ is called the specific resistance. If l = 1 cm and a = 1cm2 , then R = ρ  ... (iii)
The specific resistance is, thus, defined as the resistance of one centimeter cube of a conductor.
The reciprocal of specific resistance is termed the specific conductance or it is the conductance of one centimeter
cube of a conductor. It is denoted by the symbol κ, Thus,
1
κ= , κ= kappa − The specific conductance ... (iv)
ρ
Specific conductance is also called conductivity.
a. 1 l .1 l l 
From eq. (ii), we=
have ρ R or
= ; κ= × C  = cell constant 
l ρ a R a a 
or Specific conductance = conductance × cell constant

5.2 Equivalent Conductance


Equivalent conductance is defined as the conductance of all the ions produced by one gram-equivalent of an
electrolyte in a given solution. It is denoted by Λ .
In general Λ = κ × V  ... (v)
Where, V is the volume in mL containing 1 g-equivalent of the electrolyte.
In case the concentration of the solution is c g-equivalent per liter, then the volume containing
1 g-equivalent of the electrolyte will be 1000/c.
1000
So, equivalent conductance Λ = κ ×  ... (vi)
c
1000
Λ = κ× ; where, N = normality. The unit of equivalent conductance is ohm−1 cm2 eq−1 .
N

5.3 Molar Conductance


The molar conductance is defined as the conductance of all the ions produced by ionization of 1 g-mole of an
electrolyte when present in V ml of solution. It is denoted by µ.
Molar conductance µ = κ × V  ... (vii)
1 7 . 1 0 | Electrochemistr y

Where, V is the volume in mL containing 1 g-mole of the electrolyte. If c is the concentration of the solution in
1000
g-mole per liter, then µ = κ × Its unit is ohm−1 cm2 mol−1 .
c
Molar conductance Molecular mass
Equivalent conductance = ; where, n =
n Equivalent mass

Illustration 7: 1.0 N solution of a salt surrounding two platinum electrodes 2.1 cm apart and 4.2 sq. cm in area was
found to offer a resistance of 50 ohm. Calculate the equivalent conductivity of the solution. (JEE MAIN)

Sol: As Equivalent conductivity = κ × V


In order to find equivalent conductivity we have to calculate specific conductance.
l 1
Specific conductance ( κ ) is given as κ = .
a R
l 1
Given, l = 2.1 cm, a = 4.2 sq. cm, R = 50 ohm. Specific conductance, κ = .
a R
2.1 1
Or =
κ × = 0.01 ohm−1 cm−1 ; Equivalent conductivity = κ × V
4.2 50
V = The volume containing 1 g-equivalent = 1000 mL
= 0.01 × 1000 = 10 ohm−1 cm2 eq−1
So, Equivalent conductivity

Illustration 8: The specific conductivity of 0.02M KCl solution at 25ºC is 2.768 × 10−3 ohm−1 cm−1 . The resistance
of this solution at 25ºC when measured with a particular cell was 250.2 ohm. The resistance of 0.01 M CuSO 4
solution at 25ºC measured with the same cell was 8331 ohm. Calculate the molar conductivity of the copper
sulphate solution. (JEE ADVANCED)
1000
Sol: Molar conductivity is given
= by Sp. cond. × so first we have to calculate specific conductivity of the
C
solution. Sp.conductivity is given as a product of cell constant and conductance. Now cell constant is not provided;
we can calculate it from the conductance and Sp.conductivity of KCl solution.
Sp. cond. of KCl 2.768 × 10−3
Cell constant = = = 2.768 × 10−3 × 250.2
Conductance of KCl 1 / 250.2
For 0.01 M CuSO4 solution
1
Sp. Conductivity = Cell constant × Conductance = 2.768 × 10−3 × 250.2 ×
8331
1000 2.768 × 10−3 × 250.2 1000
= Sp. cond.
Molar conductance = × = × 8.312 ohm−1 cm2 mol−1
C 8331 1 / 100

6. KOHLRAUSCH’S LAW
At infinite dilution, when dissociation is complete, each ion makes a definite contribution towards molar conductance
of the electrolyte, irrespective of the nature of the ion with which it is associated and the value of molar conductions
of its constituent ions, i.e., Λ = λ + + λ − λC and λa are called the ionic conductance of cation and anion at infinite
dilution respectively. The ionic conductance are proportional to their ionic mobilities. Thus, at infinite dilution,
λC = kuC and λa = kua, where, uC and ua are ionic mobilities of cation and anion respectively at infinite dilution. The
value of k is equal to 96500 C, i.e., one Faraday.
Thus, assuming that increase in equivalent conductance with dilution is due to increase in the degree of dissociation
of the electrolyte, it is evident that the electrolyte achieves the degree of dissociation as unity when it is completely
ionized at infinite dilution. Therefore, at any other dilution, the equivalent conductance is proportional to the
degree of dissociation. Thus,
Chem i str y | 17.11

Λ Equivalent conductance at a given concentration


Degree of dissociation =
α =
Λ∞ Equivalent conductance at inf inite dilution

Ionic Mobility, µ: It is the distance travelled by an ions per second under a potential gradient of 1 volt per meter.
 1. For an, µ = λ º /F
 2. Ionic mobility of an ion depends on its charge, size, viscosity of solvent, temperature, etc.
 3. For aqueous solution, greater the charge or smaller the size of gaseous ion, greater will be the size of aqueous
ion. When such a big ion moves in solution, it experiences greater resistance by the size of solvent particles.
This results in a decrease in its conductance as well as ionic mobility. Following are the increasing order of
ionic mobilities of some ions:

Li+ < Na+ < K + < Rb+ < Cs+ ; F− < Cl− < Br − < I − ; Al3+ < Mg2+ < Na+
 4. The size of gaseous H+ ion is smallest among all the ions and hence its ionic mobility should be minimum
but among all the ions, it is maximum. The ion with second highest ionic mobility is OH–. The very high ionic
mobilities of these ions are due to interchange of hydrogen bonds and covalent bonds, by which migration of
charge occurs without any large displacement in the ions (Grotthus mechanism).

Applications of Kohlrausch’s Law:


0 0
(a) Determining Λm of a weak electrolyte: In order to calculate Λm of a weak electrolyte say CH3COOH, we
0
determine experimentally Λm values of the following three strong electrolytes:
(i) A strong electrolyte containing same cation as in the test electrolyte, say HCl
(ii) A strong electrolyte containing same anion as in the test electrolyte, say CH3COONa
(iii) A strong electrolyte containing same anion of (a) and cation of (b) i.e. NaCl.
0 0 0 0 0
Λm of CH3COOH is then given as: Λm (CH3COOH) = Λm (HCl) + Λm (CH3COONa) − Λm (NaCl)
0
Proof: Λm (HCl) = λH0 + λ  ... (i)
Cl−
0
Λm (CH3COONa) = λ0 +λ  ... (ii)
CH3COO− Na+

0
Λm (NaCl) = λ0 + λ0 −  ... (iii)
Na+ Cl

Adding equation (I) and equation (II) and subtracting (III) from them:
0 0 0
Λ(HCl) + Λ(CH − Λ(NaCl) = λ0 + + λ0 = Λ0(CH
3COONa) (H ) (CH3COO− ) 3COOH)

No. of molecules ionised Λm


(b) Determination
= of degree of dissociation (α): α =
Total number of molecules dissolved Λ0
m

0 1000 κ
(c) Determination of solubility of sparingly soluble salt: Λm = ,
C
Where C is the molarity of solution and hence the solubility.
0 0
(d) Determination of ionic product of water: From Kohlrausch’s law, we determine Λm of H2O where Λm is the
molar conductance of water at infinite dilution when one mole of water is completely ionized to give one mole
0
of H+ and one mole of OH− ions i.e. Λm (H2O) = λ0 + + λ0
H OH−

κ × 1000
Again using the following Λm = , where C=molar concentration i.e. mole L−1 or mole dm−3
C
1 7 . 1 2 | Electrochemistr y

κ
⇒ Λm = , where C = concentration in mole m−3
C
0 0 κ κ
Assuming that Λm differs very little from Λm ; Λm = ⇒C=
C Λm0

Specific conductance ( κ ) of pure water is determined experimentally. Thereafter, molar concentration of


dissociated water is determined using the above equation. K w is then calculated as: K w = C2

7. THEORY OF WEAK ELECTROLYTES


(i) Electrolytes that are not completely ionized when dissolved in a polar medium like water are called weak
electrolytes. There exists equilibrium between ions and unionized molecules. AB  A + + B−
(ii) The Concept of chemical equilibrium and law of mass action can be applied to ionic equilibrium also.
AB  A⁺ + B⁻
t = 0 C 0 0
[A + ][B− ] Cα × Cα Cα 2
teq. C – Cα Cα; K
Cα = = ; K=  ... (i)
[AB] C(1 − α ) 1−α

For weak electrolytes, α << 1 ∴ (1 − α ) ≈ 1


K
Thus, equation (i) can be written as: K= Cα2 ⇒ α =  ... (ii)
C
From eq. (ii), it is clear that on dilution concentration decreases, as a result of which degree of ionization 'α'
increases. Both equivalent and molar conductance increase when at a high degree of ionization.
ΛCe Λm
C
(iii) Degree of ionization can be calculated as: =
α =  ... (iii)
Λe∞ Λm

ΛCe , Λm
C
= Equivalent and molar conductance at concentration ‘C’

Λe∞ , Λm

= Equivalent and molar conductance at infinite dilution. 2
 ΛC 
C ×  ∞e 
Λ  C( ΛCe )2
Substituting the values of ' α ' from eq. (iii) in eq. (i),=
we get K =  e  ... (iv)
ΛCe Λe∞ ( Λe∞ − ΛeC )
C 2
C( Λm ) 1 −
Similarly K =  Λe∞ ... (v)
∞ ∞ C 
Λm ( Λm − Λm )

Equations (iv) and (v) are called Ostwald equation.

Illustration 9: A decinormal solution of NaCl has specific conductivity equal to 0.0092. If ionic conductance of Na+
and Cl− ions at the same temperature are 43.0 and 65.0 ohm−1 respectively, calculate the degree of dissociation of
NaCl solution.  (JEE MAIN)

Sol: Degree of dissociation is calculated as equivalent conductance at a particular dilution divided by equivalent
conductance at infinite dilution.so first we have to calculate Λ ∞
Λ v . Λ ∞ is determined by summing up ionic conductance of each ion. Λ v is product of specific conductance and
dilution.
Equivalent conductance of N/10 NaCl solution
=Λ v Sp.conductivity × dilution = 0.0092 × 10,000 = 92 ohm−1 ;

Λ∞ = λ +λ = 43.0 + 65.0 = 108 ohm−1


Na+ Cl−
Chem i str y | 17.13

Λv 92
Degree of dissociation, =
α = = 0.85
Λ ∞ 108

Illustration 10: At 18ºC, the conductivities at infinite dilution of NH4 Cl,NaOH and NaCl are 129.8, 217.4 and 108.9
mho respectively. If the equivalent conductivity of N/100 solution of NH4 OH is 9.93 mho, calculate the degree of
dissociation of NH4 OH at this dilution. (JEE ADVANCED)

Sol: Degree of dissociation is calculated as equivalent conductance at a particular dilution divided by equivalent
conductance at infinite dilution. Λ v is given. Λ ∞ is determined by summing up ionic conductance of each ion
Λ ∞NH =λ +λ = 129.8  ... (i)
4 Cl NH+
4 Cl−
Λ ∞NaOH = λ +λ = 217.4  ... (ii)
Na+ OH−

Adding eqs. (i) and (ii) and subtracting eq. (iii),


Λ +λ +λ +λ −λ −λ =λ +λ = 129.8 + 217.4 − 108.9
NH+
4 Cl− Na+ OH− Na+ Cl− NH+
4 OH−

Λv 9.93
Λ ∞NH 238.3 mho . Degree of dissociation, =
= α = = 0.04167 or 4.17% dissociated.
4 OH Λ ∞ 238.3

8. ELECTROCHEMICAL CELLS

8.1 Electrolytic Cells


Electrolytic cells are devices in which electrolysis (chemical reaction involving oxidation and reduction) is carried
out by using electricity or in which conversion of electrical energy into chemical energy is done.

8.2 Galvanic Cells


This is a device where a redox reaction is used to convert chemical energy into electrical energy, i.e., electricity is
obtained with the help of oxidation and reduction reaction. The chemical reaction responsible for production of
electricity takes place in two separate compartments. Each compartment consists of a suitable electrolyte solution
and a metallic conductor. The metallic conductor acts as an electrode and the compartments containing the
electrode and the electrolyte solution are called half-cells. When the two compartments are connected by a salt
bridge and electrodes are joined by a wire through the galvanometer, the electricity begins to flow. This is the
simple form of voltaic cell.

8.3 Daniel Cell

Figure 17.1: Representation of a daniel cell


1 7 . 1 4 | Electrochemistr y

Oxidation half reaction, Zn(s) → Zn2+ (aq.) + 2e−

Reduction half reaction, Cu2+ (aq.) + 2e− → Cu(s)

Net reaction Zn(s) + Cu2+ (aq.) → Zn2+ (aq.) + Cu(s)

Salt Bridge: A Salt bridge is usually an inverted U-tube filled with a concentrated solution of inert electrolytes. An
inert electrolyte is one whose ions are neither involved in any electrochemical change nor do they react chemically
with the electrolytes in the two half-cells.
Significance of salt bridge: The following are the functions of the salt bridge:
(i) It connects the solutions of two half-cells and completes the cell circuit.
(ii) It prevents transference or diffusion of the solutions from one half-cell to the other.
(iii) It keeps the solutions in two half-cells electrically neutral.
(iv) It prevents liquid-liquid junction-potential, i.e., the potential difference which arises between two solutions
when in contact with each other.
A broken vertical line or two parallel vertical lines in a cell reaction indicates the salt bridge.
Zn | Zn2+ || Cu2+ | Cu

Electrode Potential: A metal placed in a solution of its ions obtains either a positive or negative charge with respect
to the solution. On account of this, a definite potential is developed between the metal and the solution. This potential
difference is called electrode potential. It depends on the nature of electrode, concentration of ions and temperature.

Oxidation Potential: It is the tendency of an electrode to get oxidized, i.e., to lose electrons.
M → Mn+ + ne−
Reduction potential: It is the tendency of an electrode to get reduced, i.e., to accept electrons.
Mn+ + ne− → M
Standard Electrode Potential: The potential difference developed between metal electrode and the solution of its
ions of unit molarity (1 M) at 25ºC (278 K) is called standard electrode potential.

The magnitude of potential depends on the following factors:


(i) Nature of the electrode,
(ii) Concentration of the ions in solution,
(iii) Temperature.

Standard Electrode Potential: While dipping an electrode in a solution in order to compare the electrode
potentials of different electrodes, it is essential to first specify the ion concentration in the solution as well as the
temperature of the half cell. The potential difference developed between metal electrode and the solution of its
ions of unit molarity (1 M) at 25ºC (298 K) is called standard electrode potential. Standard oxidation potential =
-Standard reduction potential
EMF of a cell: It is the difference in the potential across left and right electrodes due to which electrons flow from
anode to cathode.
Standard EMF: The EMF values of an electrode under standard conditions (1 atm, 298 K) and the unit concentrations

of its ions is called as standard EMF and is denoted by Ecell
º º º º º º
Ecell Ecathode
= − Eanode or Ecell Eright
= electrode − Eleft electrode
Chem i str y | 17.15

8.4 Reference Electrode (Standard Hydrogen Electrode, SHE or NHE)


The potential of an individual half-cell cannot be measured but the difference in the potential of two half-cells
can be measured experimentally. It is therefore, necessary to couple the electrodes with another electrode whose
potential is known. This electrode is termed as reference electrode like standard hydrogen electrode (SHE). Which
is standard electrode potential considered zero.

H2(g)
(at 1 atm)

H3 O+(aq.) Pt black
(1 M) electrode

Figure 17.2: Representation of reference electrode

The hydrogen electrode thus obtained forms one of two half-cells of a voltaic cell. A voltaic cell is created when this
half-cell is connected with any other half-cell. The hydrogen electrode can act as cathode or anode with respect to
other electrode.
SHE half reaction Electrode potential
+ −
H2 → 2H + 2e 0.0 V (Anode)
2H+ + 2e− → H2 0.0 V (Cathode)

8.5 Some other Reference Electrodes


(i) Calomel Electrode: Pt wire

To salt

bridge
Saturated
KCl solution

Hg2Cl2 and
Hg paste

Mercury

Figure 17.3: Representation of calomel electrode

1 
→ Hg + Cl
Reaction when electrode act as cathode: Hg2Cl2 + e− ←
2
(ii) Silver-silver chloride electrode: This is another widely used reference electrode. It is reversible and stable
and can be combined with cells containing chlorides without inserting liquid junction.
Silver chloride is deposited electrolytically on a silver or platinum wire and it is then immersed in a solution
containing chloride ions. Its standard electrode potential with respect to the standard hydrogen electrode is
0.2224 V at 298 K. The electrode is represented as: Ag | AgCl | Cl–
The electrode reaction is: AgCl + e− → Ag + Cl−
1 7 . 1 6 | Electrochemistr y

PLANCESS CONCEPTS

In MnO −4 + 8H+ + 5e → Mn2+ + 4H2O , oxidant should be taken as [MnO −4 ][H+ ]8 ,i.e., all ions
concentration present with oxidant should be reported accordingly in Nernst half-cell potential. Similarly
for reductant, all ions present with reductant should be considered.
Aman Gour (JEE 2012 AIR 230)

8.6 Nernst Equation

Nernst Equation: Suppose, for example, that we reduce the concentration of Zn2+ in the Zn/Cu cell from its unit-
activity value of around 0.5 M to a much smaller value:

Zn(s) Zn2+ (0.001M) || Cu2+ || Cu(s)

This will reduce the value of Q for the cell reaction Zn(s) + Cu2+ → Zn2+ + Cu(s)

The free energy change ∆G more negative than ∆G0, so than E would be more positive than Eº.
The relation between the actual cell potential E and the standard potential Eº is developed in the following way.
According to cell potential and Gibb’s free energy change: ∆G0 = –nEoF; ∆G = –nEF
These expressions can then be substituted into the relation ∆G = ∆G0 + RTIn Q
RT
Which gives –nEF = –nEoF + RTIn Q . Which can be rearranged to E= E − lnQ
nF
This is Nernst Equation, which relates the cell potential to the standard potential Eº. If Q is unity then at 25ºC
0.059
Nernst Equation will be E= Eº − logQ
n
And for a general electrochemical reaction of the type aA+bBcC+dD
RT RT [C]c [D]d
Nernst equation can be written as: Ecell = 
E(cell) − lnQ = 
E(cell) − ln
nF nF [A]a [B]b

PLANCESS CONCEPTS

• The overall reaction and ∆Gº for each cell is same.


º
• Ecell and 'n' values are different for each cell.
º
• Ecell × n is same for each cell.
º
• ∆Gº depends on cell reaction and Ecell depends upon making up of a cell.

B Rajiv Reddy (JEE 2010 AIR 11)


Chem i str y | 17.17

8.7 Electrochemical Series

Characteristics of electrochemical series


(a) Negative sign of SRP (standard reduction potential) indicates that an electrode when joined with SHE acts as
anode and oxidation occurs on this electrode. Similarly positive sign of SRP indicates that an electrode when
joined with SHE acts as cathode and reduction occurs on this electrode.
(b) In the series, those substances that are stronger reducing agents than hydrogen are placed above it.
(c) The substances which are stronger oxidizing agents than H+ ion are placed below hydrogen in the series.
(d) The activity decreases from top to bottom and the metals on top are called active metals.

Application of electrochemical series


(i) Reactivity of metals
•• Alkali metals and alkaline earth metals having high –ve values of SRP which are chemically active react
with cold water, evolve hydrogen and readily dissolve in acids.
•• Metals like Fe, Pb, Sn, Ni, Co etc. do not react with cold water but react with steam to evolve hydrogen.
•• Metals Li, Be, Cu, Ag and Au which lie below hydrogen are less reactive and do not evolve hydrogen from
water.
(ii) Electropositive character of metals: Electropositive character of metals decreases from top to bottom.
(iii) Displacement reactions: The metal having low SRP will displace the metal from its salt’s solution which has
higher value of SRP.
(iv) Reducing power of metals: Reducing nature decreases from top to bottom in the electrochemical series.
(v) Oxidizing nature of non-metals: Oxidizing nature increases from top to bottom in the electrochemical
series.
(vi) Thermal stability of metallic oxides: The thermal stability of the metal oxide decreases from top to bottom.
(vii) Products of electrolysis: The ion which is a stronger oxidizing agent is discharged first at cathode.
K + ,Ca2+ ,Na+ ,Mg+2 , Al+3 , Zn+2 ,Fe+2 ,H+ ,Cu+2 , Ag+ , Au+3 increasing order of deposition.
(viii) Corrosion of metals: Corrosion is defined as the deterioration of a substance because of its reaction with its
environment. The corrosion tendency decreases from top to bottom.
(ix) Extraction of metals: Ag and Au extracted by cyanide process.
1 7 . 1 8 | Electrochemistr y

Table 17.3: Reduction potential of different ions

-
Reaction (Oxidized form + ne ) → Reduced form Eº/V
2.87
F2 (g) + 2e− → 2F−
1.81
Co3+ + e− → Co2+
→ 2H2O 1.78
H2O2 + 2H+ + 2e−
→ Mn2+ + 4H2O 1.51
MnO −4 + 8H+ + 5e−
1.40
Au3+ + 3e− → Au(s)
1.36
Cl2 (g) + 2e− → 2Cl−
→ 2Cr3+ + 7H2O 1.33
Cr2O27− + 14H+ + 6e−
→ 2H2O 1.23
O2 (g) + 4H+ + 4e−
2+
→ Mn + 2H2O 1.23
MnO2 (s) + 4H+ + 2e−
1.09
Br2 + 2e− → 2Br −
Increasing strength of oxidizing agent

Increasing strength of reducing agent


→ NO(g) + 2H2O 0.97
NO3− + 4H+ + 3e−
→ Hg22+ 0.92
2Hg2+ + 2e−
0.80
Ag+ + e− → Ag(s)
0.77
Fe3+ + e− → Fe2+
→ H2O2 0.68
O2 (g) + 2H+ 2e−
0.54
I2 + 2e− → 2I −
0.52
Cu+ + e− → Cu(s)
0.34
Cu2+ + 2e− → Cu(s)
0.22
AgCl(s) + e− → Ag(s) + Cl−
0.10
AgBr(s) + e− → Ag(s) + Br −

→ H2 (g) 0.00
2H+ + 2e-
-0.13
Pb2+ + 2e− → Pb(s)
-0.14
Sn2+ + 2e− → Sn(s)
-0.25
Ni2+ + 2e− → Ni(s)
Chem i str y | 17.19

-
Reaction (Oxidized form + ne ) → Reduced form Eº/V

→ Fe(s) -0.44
Fe2+ + 2e−
→ Cr(s) -0.74
Cr3+ + 3e−
Increasing strength of oxidizing agent

Increasing strength of reducing agent


→ Zn(s) -0.76
Zn2+ + 2e−
2H2O + 2e− → H2 (g) + 2OH− (aq) -0.83

Al3+ + 3e− → Al(s) -1.66

Mg2+ + 2e− → Mg(s) -2.36

Na+ + e− → Na(s) -2.71

Ca2+ + 2e− → Ca(s) -2.87

K + + e− → K(s) -2.93

Li+ + e− → Li(s) -3.05

Two important parameters that can be determined from a cell potential are the equilibrium constant for the cell
reaction and the free energy change for the cell reaction.
º
1. Determining the equilibrium constant from Ecell
º
2. Determining the standard state free energy change from Ecell

3. Determining the non-standard free energy change


º
Determining the Equilibrium Constant from Ecell
To calculate the equilibrium constant for an electrochemical cell we need to know:
1. The standard state potential for a cell
2. The half-reactions involved
º RT
The Nernst equation is used in calculating the equilibrium constant. Ecell = lnQ
nF
At equilibrium Q = K, Substituting in K for Q and the values for R, T and F we get:

º 0.0257 0.0592
=Ecell = lnK logK
n n

Example: Find the value of the equilibrium constant at 25ºC for the cell reaction for the following electrochemical
cell: Cu | Cu2+ (1M) || Ag+ (1M) | Ag

Sol: (i) Write the equations for the cell half-reactions, calculate the standard cell potential and determine the
number of electrons transferred.
º
2Ag+ (aq) + 2e− → 2Ag(s) Ereduction = +0.799 V

º
Cu(s) → Cu2+ (aq) + 2e− Eoxidation = −0.518 V

º
2Ag+ (aq) + Al(s) → 2Ag(s) + Cu2+ (aq) Ecell = +0.281 V
1 7 . 2 0 | Electrochemistr y

n = 2 moles of electrons
(ii) Substitute into the above equations and solve for K.
0.0592 0.0592
º
Ecell = logK ; 0.281 = K 109.49
logK ; logK = 9.49 ; = = 3.1 × 109
n 2
Note: values for the equilibrium constant for electrochemical cell reactions are sometimes very large.
º
Determining the Standard State Free Energy Change from Ecell
To determine the standard state free energy change for a cell reaction
º
1. Determine the Ecell
2. Determine the number of moles of electrons transferred in the reaction.
º
3. Solve for ∆G using the equation ∆G =
−nFEcell

∆Gº =standard state free energy change ( joules); n = number of moles of electrons transferred
º
F = Faraday’s constant (96,485 C/mole e− ); Ecell = standard state cell potential (volts or joules/C)

Example: Find the value of the equilibrium constant at 25ºC for the cell reaction for the following electrochemical
cell: Cu | Cu2+ (1M) || Ag+ (1M)Ag
º
(The solution for the determination of the Ecell and the number of moles of electrons, n, are shown in the example
in the previous section.)
º º
1. Determine the Ecell . Ecell = +0.281 volts
2. Determine the number of moles of electrons transferred. n = 2 moles of e−
3. Substitute into the equation and solve.
∆G =−(2mole− )(96, 485C / mole− )0.281 J / C; ∆G =−54,200 J or − 54.2kJ

Determining the Non-Standard State Free Energy Change


To determine the non-standard state free energy change:
º
1. Calculate the standard cell potential, Ecell
2. Determine the number of moles of electrons transferred, n
3. Calculate the reaction quotient, Q
4. Calculate the non-standard cell potential, Ecell, using the Nernst equation
5. Calculate the non-standard free energy change using the equation: ∆G =−nFEcell

Example: Calculate the free energy change for the following electrochemical cell.

Zn(s) | Zn2+ (1.50M) || Cu2+ (0.25M) | Cu(s)


º
1. Calculate Ecell .
º
Zn(s) → Zn2+ (aq) + 2e− Eoxidiation = +0.762 volts

º
Cu2+ (aq) + 2e− → Cu(s) Ereduction = +0.339 volts

º
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) Ecell = +1.101 volts

2. Determine “n”. n = 2 moles of electrons


Chem i str y | 17.21

[Zn2+ ] 1.50
3. Calculate Q;
= Q = = 6.0
[Cu2+ ] 0.25
0.0257
4. Calculate Ecell ; Ecell = 1.101 volts − ln6 = 1.078 volt
2
5. Calculate ∆G.
∆G =−nFEcell =−(2mole e− )(96, 485C / mole e− )(1.078 volts) ; ∆G =−208,000 joules or − 208kJ

8.8 Corrosion
The weakening and deterioration of a substance because of its reaction with its environment is called as corrosion.
This is also defined as the process by which metals have the tendency to go back to their combined state, i.e.,
reverse of extraction of metals.
Water drop

O2 O2

OH- 2+ OH-
Fe
Rust Rust
Cathode Anode Cathode

Iron
e- e-

Figure 17.4 : Process of corrosion

Oxidation: Fe(s) → Fe2+ (aq.) + 2e−

Reduction: O2 + 4H+ (aq.) + 4e− → 2H2O(l )

Atmospheric: 4Fe2+ + O2 + 4H2O(l ) → 2Fe2O3 (s) + 8H+ (aq.)

Oxidation: Fe2O3 + xH2O → Fe2O3 . xH2O


Rust

8.9 Dry Cell


In this cell, once the chemicals have been consumed, further reaction is not possible. It cannot be regenerated by
reversing the current flow through the cell using an external direct current source of electrical energy.
As the cell operates, the zinc is oxidized to Zn2+ ; Zn → Zn2+ + 2e− (Anode reaction)
The electrons are utilized at carbon rod (cathode) as the ammonium ions are reduced.
2NH+4 + 2e− → 2NH3 + H2 (Cathode reaction)

The cell reaction is Zn + 2NH+4 → Zn2+ + 2NH3 + H2

Hydrogen is oxidized by MnO2 in the cell. 2MnO2 + H2 → 2MnO(OH)

Ammonia produced at cathode combines with zinc ions to form complex ion.

Zn2+ + 4NH3 →[Zn(NH3 )4 ]2+ ; Ecell is 1.6 volt.


1 7 . 2 2 | Electrochemistr y

PLANCESS CONCEPTS

• T
 hese are called dry cells but are not actually dry. These contain moist paste and operate only as long
as the paste in it remains wet.
• In alkaline cells, e.m.f. is independent of concentration of alkali because redox reaction does not
involve [OH⁻].
• Alkaline cells retards corrosion as corrosion is favored more in H+ ions.
• Alkaline cells show more efficient ion transport because of alkaline electrolyte and thus give rise to
more stable current and voltage.
Mredul Sharda JEE Advanced 2013 AIR

8.10 Fuel Cell


Fuel cells are another means to convert chemical energy to electrical energy. . The main disadvantage of a primary
cell is that it can deliver current for a short period only. This is because the quantity of oxidizing agent and
reducing agent is limited. But energy can be obtained indefinitely from a fuel cell as long as the outside supply of
fuel is maintained. One of the examples is the hydrogen-oxygen fuel cell. The cell consists of three compartments
separated by a porous electrode. Hydrogen gas is introduced into one compartment and oxygen gas is fed into
another compartment. These gases then diffuse slowly through the electrodes and react with electrodes that are
made of porous carbon and the electrolyte is a resin containing concentrated aqueous sodium hydroxide solution.
Hydrogen is oxidized at anode and oxygen is reduced at cathode. The overall cell reaction produces water. The
reactions which occur are:

Anode: [H2 (g) + 2OH− (aq.) → 2H2O(l ) + 2e− ] × 2

Cathode: O2 (g) + 2H2O(l ) + 4e− → 4OH− (aq.)

Overall: 2H2 (g) + O2 (g) → 2H2O(l )

These type of cells are used in space-crafts. Fuel cells are efficient and pollution free.
Thermodynamic efficiency of fuel cells is the ratio of the electrical free energy to the enthalpy of the reaction.
∆G
η=
∆H

8.11 Concentration Cell


(a) Electrode concentration cells: In these cells, the potential difference is developed between two like electrodes
at different concentrations dipped in the same solution of the electrolyte. For example, two hydrogen
electrodes at different gas pressures in the same solution of hydrogen ions constitute a cell of this type.

Pt,H2 (Pr essure p1 ) H2 (Pressure p2 )Pt


[H+ ]
Anode Cathode
If p1 > p2 , oxidation occurs at LHS electrode and reduction occurs at RHS electrode.

0.0591 (p )
Ecell = log 1 at 25º C
2 (p2 )

In the amalgam cells, two amalgams of the same metal at two different concentrations are immersed in the
same electrolytic solution. M(HgC1 ) | M n+ | Zn(HgC2 )
Chem i str y | 17.23

0.0591 C
The e.m.f of the cell is given by the expression Ecell = log 1 at 25º C
n C2
(b) Electrolyte concentration cells: In these cells, electrodes are identical but these are immersed in a solution
of the same electrolyte of different concentrations. The source of electrical energy in the cell is the tendency
of the electrolyte to diffuse from a solution of higher concentration to that of lower concentration. With the
expiry of time, the two concentrations tend to become equal. Thus, at the beginning, the e.m.f of the cell is at
its maximum and it gradually falls to zero. Such a cell is represented in the following manner: ( C2 is greater
than C1 ).

Zn | Zn2+ (C1 ) || Zn2+ (C2 ) | Zn


M | Mn+ (C1 ) || Mn+ (C2 ) | M or
Anode Cathode
0.0591 C
The e.m.f of the cell is given by the following expression: Ecell = log 2(RHS) at 25ºC
n C1(LHS)
The concentration cells are used to determine the solubility of sparingly soluble salts, valency of the cation of the
electrolyte and transition point of the two allotropic forms of a metal used as electrodes, etc.

Example: Find the standard cell potential for an electrochemical cell with the following cell reaction.
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)

Sol:
(i) Write the half-reactions for each process. Zn(s) → Zn2+ (aq) + 2e− ; Cu2+ (aq) + 2e− → Cu(s)
º
(ii) Look up the standard potentials for the reduction half-reaction. Ereduction of Cu2+ = +0.339 V
(iii) Look up the standard reduction potential for the reverse of the oxidation reaction and change the sign.
º
Ereduction of Zn2+ = −0.762 V,Eoxidation
º
of Zn = −( −0.762 V) = +0.762 V
(iv) Add the cell potentials together to get the overall standard cell potential.
º º
Oxidation: Zn(s) → Zn2+ (aq) + 2e− Eoxidation = −Ereduction = −( −0.762 V) = +0.762 V
º
Reduction: Cu2+ (aq) + 2e− → Cu(s) Ereduction = +0.339 V
º
Overall: Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) Ecell = +1.101 V

Example: Predict the cell potential for the following reaction when the pressure of the oxygen gas is 2.50 atm, the
hydrogen ion concentration is 0.10 M and the bromide ion concentration is 0.25 M.
O2 (g) + 4H+ (aq) + 4Br − (aq) → 2H2O(l ) + 2Br2 (l )
º
Sol: (i) Calculate the standard cell potential for the reaction, Ecell, using the tabled values:
º º
Oxidation: 4Br (aq) → 2Br2 (l ) + 4e Eoxidation = −Ereduction = −( +1.077 V) = −1.077 V
− −

+ − º
Reduction: O2 (g) + 4H (aq) + 4e → 2H2O(l ) Ereduction = +1.229 V

Overall: O2 (g) + 4H+ (aq) + 4Br − (aq) → 2H2O(l ) + 2Br2 (l ) Eº = +0.152 V


cell

(ii) Determine the new cell potential resulting from the changed conditions.
(iii) Calculate the value for the reaction quotient, Q. (Note: We calculate Q using molar concentrations for solutions
and pressures for gases. Water and bromine are both liquids, therefore they are not included in the calculation of Q.)
1 7 . 2 4 | Electrochemistr y

1 1
Q = ; Q Q 1.02 × 106
;=
+ 4 − 4
PO [H ] [Br ] (2.50atm)(0.10 M)4 (0.25M)4
2

(iv) Calculate the number of moles of electrons transferred in the balanced equation, n.
n = 4 moles of electrons
(v) Substitute values into the Nernst equation and solve for the non-standard cell potential, Ecell .

+0.152 V − (0.0257 / 4)ln(1.02 × 106 ),Ecell =


Ecell = 0.063V

Illustration 11: Reaction → 2Ag + Cd2+ . The standard electrode potentials for Ag+ → Ag and Cd2+ → Cd couples
are 0.80 volt and −0.40 volt respectively
(i) What is the standard potential E for this reaction?
(ii) For the electrochemical cell, in which this reaction takes place which electrode is negative electrode?
 (JEE MAIN)
Sol: First write down the two half-cell. Standard potential E for the cell is given by standard potential of reducing
electrode+ standard potential of oxidising electrode. The electrode having less electrode potential act as negative
electrode.

(i) The half reactions are: 2Ag+ + 2e− → 2Ag


Re duction
(Cathode)

Eº = 0.80 volt (Reduction potential); Cd → Cd2+ + 2e−


Ag+ /Ag Oxidation
( Anode )

Eº = −0.40 volt (Reduction potential) or Eº = +0.40 volt


Cd2 + /Cd Cd/Cd2 +

Eº = Eº + Eº = 0.40 + 0.80 = 1.20 volt


Cd/Cd2 + Ag+ /Ag

Illustration 12: The standard oxidation potential of zinc is 0.76 volt and of silver is − 0.80 volt. Calculate the e.m.f
of the cell:
Zn | Zn(NO3 )2 || AgNO3 | Ag At 25ºC. (JEE MAIN)
0.25M 0.1M

Sol: First calculate the standard potential for reaction which is calculated as
º º º
Ecell
= Eoxidation − Ereduction
º
After calculating Ecell e.m.f of the cell can be easily calculated using following equation

º 0.0591 [Products]
E=
cell Ecell − log
n [Reactants]
º
The cell reaction is Zn + 2Ag+ → 2Ag + Zn2+ ; Eoxidation of Zn = 0.76 volt

º º º º
Ereduction of Ag = 0.80 volt ; Ecell = Eoxidation of Zn + Ereduction of Ag = 0.76 + 0.80 = 1.56 volt

º 0.0591 [Products]
We know that, E=
cell Ecell − log
n [Reactants]

º 0.0591 0.25 0.0591


= Ecell − log 1.56 −
= × 1.3979
= (1.56 − 0.0413) volt = 1.5187 volt .
n 0.1 × 0.1 2
Chem i str y | 17.25

Illustration 13: Calculate the e.m.f of the cell. Mg(s) | Mg2+ (0.2M) || Ag+ (1 × 10 −3 ) | Ag

Eº +0.8 volt, Eº 2+
= −2.37 volt
=
Ag+ /Ag Mg /Mg

What will be the effect on e.m.f if concentration of Mg2+ ion is decreased to 0.1 M?  (JEE MAIN)

Sol: First calculate the standard potential for reaction which is calculated as
º º º
Ecell
= Eoxidation − Ereduction
º
After calculating Ecell e.m.f of the cell can be easily calculated using following equation

º 0.0591 [Products]
E=
cell Ecell − log
n [Reactants]
º º
Ecell
= ECathode − EºAnode
= 0.80 − ( −2.37)
= 3.17 volt
º 0.0591 Mg2+
Cell reaction, Mg + 2Ag+ → 2Ag + Mg2+ ; E=
cell Ecell − log
n [Ag+ ]2
0.0591 0.2
= 3.17 − log 3.0134 volt when Mg2+ = 0.1M
3.17 − 0.1566 =
=
2 [1 × 10−3 ]2

º 0.0591 0.1
E=
cell Ecell − log = (3.17 − 0.1477) volt = 3.0223 volt.
2 (1 × 10−3 )2

Illustrations 14: To find the standard potential of M3+ / M electrode, the following cell is constituted:
Pt | M | M3+ (0.0018mol−1L) || Ag+ (0.01mol−1L) Ag
The e.m.f of this cell is found to be 0.42 volt. Calculate the standard potential of the half reaction
M3+ + 3e− → M. Eº = 0.80 volt.  (JEE MAIN)
Ag+ /Ag

Sol: Here e.m.f is given we have to calculate standard potential of anode. So first we have to calculate standard
potential of the cell and subtract it from the provided standard potential of cathode.
Standard potential of cell can be determined using following expression, Nernst equation

º 0.0591 [M3+ ]
E=
cell Ecell − log
3 [Ag+ ]3
The cell reaction is M + 3Ag+ → 3Ag + M3+

º 0.0591 [M3+ ]
Applying Nernst equation, E=
cell Ecell − log
3 [Ag+ ]3

º 0.0591 (0.0018) º º
0.42 =
Ecell − log Ecell
= − 0.064 ; Ecell =(0.42 + 0.064) =0.484 volt
3 (0.01)3

º º
Ecell
= ECathode − EºAnode or =
EºAnode ECathode
º º
− ECell =(0.80 − 0.484) =0.32 volt .
1 7 . 2 6 | Electrochemistr y

PROBLEM-SOLVING TACTICS

(a) Related to electrolysis: Electrolysis comprises of passing an electric current through either a molten salt or
an ionic solution. Thus the ions are “forced” to undergo either oxidation (at the anode) or reduction (at the
cathode). Most electrolysis problems are really stoichiometry problems with the addition of some amount of
electric current. The quantities of substances produced or consumed by the electrolysis process is dependent
upon the following:
(i) Electric current measured in amperes or amps
(ii) Time measured in seconds
(iii) The number of electrons required to produce or consume 1 mole of the substance

(b) To calculate amps, time, coulombs, faradays and moles of electrons:


Three equations related these quantities:
(i) Amperes × time = Coulombs
(ii) 96,485 coulombs = 1 Faraday
(iii) 1 Faraday = 1 mole of electrons
The through process for interconverting amperes and moles of electrons is:
Amps and time Coulombs Faradays Moles of electrons
Use of these equations are illustrated in the following sections.

(c) To calculate the quantity of substance produced or consumed: To determine the quantity of substance
either produced or consumed during electrolysis, given the time a known current flowed:
(i) Write the balanced half-reactions involved.
(ii) Calculate the number of moles of electrons that were transferred.
(iii) Calculate the number of moles of substance that was produced/consumed at the electrode.
(iv) Convert the moles of substance to desired units of measure.

(d) Determination of standard cell potentials: A cell’s standard state potential is the potential of the cell under
standard state conditions, and it is approximated with concentrations of 1 mole per liter (1 M) and pressures
of 1 atmosphere at 25ºC.
(i) To calculate the standard cell potential for a reaction.
(ii) Write the oxidation and reduction half-reactions for the cell.
º
(iii) Look up the reduction potential, Ereduction, for the reduction half-reaction in a table of reduction potentials.
(iv) Look up the reduction potential for the reverse of the oxidation half-reaction and reverse the sign to
º º
obtain the oxidation potential. For the oxidation half-reaction, Eoxidation = −Ereduction .
(v) Add the potentials of the half-cells to get the overall standard cell potential.
º º º
Ecell −Ereduction
= + Eoxidation

(e) For determining non-standard state cell potentials: To determine the cell potential when the conditions
are other than standard state (concentrations not 1 molar and/or pressures not 1 atmosphere):
(i) Determine the standard state cell potential.
(ii) Determine the new cell potential resulting from the changed conditions.
(iii) Determine Q, the reaction quotient.
Chem i str y | 17.27

(iv) Determine n, the number of electrons transferred in the reaction “n”.


(v) Determine Ecell, the cell potential at the non-standard state conditions using the Nernst equation.
º
E=
cell Ecell − (RT / nF)lnQ
º
Ecell = cell potential at non-standard state conditions; Ecell = standard state cell potential
R = constant (8.31 J/mole K); T = absolute temperature (Kelvin scale)
F = Faraday’s constant (96,485 C/mole e− )
n = Number of moles of electrons transferred in the balanced equation for the reaction occurring in the cell;
[C]c [D]d
Q = Reaction quotient for the reaction. aA + bB → cC + dD, Q =
[A]a [B]b
If the temperature of the cell remains at 25ºC, the equation simplifies to:
º º
E=
cell Ecell − (0.0257 / n)lnQ or in terms of log10 ; E=
cell Ecell − (0.0592 / n)logQ

POINTS TO REMEMBER

S.No. Description
1 Electrolyte Any substance which dissolves in water to form a solution that will conduct an electric
current (ionic substances).Electrolytes may be classified as strong (NaCl, HCl, NaOH) or
weak (NH4OH, CH3COOH, HF). Solutions that do not conduct electricity at all are called
non-electrolytes.
2 Strong and Weak Strong electrolyte - Solutions in which the substance dissolved (solute) is present
Electrolytes entirely as ions.
Weak electrolyte - A solute that yields a relatively low concentration of ions in solution.
3 Dissociation The separation of ions that occurs when an ionic substance dissolves: CaCl2(s) + H2O →
Ca+2(aq) + 2Cl-(aq).
4 Electrochemical Cells A system of electrodes and electrolytes in which a spontaneous or
non-spontaneous redox reaction occurs.
5 Components of a. Electrode: An electrical conductor (metal strip) used to establish contact with a non-
Electrochemical cells metallic part of the circuit (usually an electrolyte).
b. Anode: The electrode at which oxidation occurs.
c. Cathode: The electrode at which reduction occurs.
d. Electrolyte: A liquid, paste, or gel that serves to conduct charge by moving ions in
the cell.
e. Half-cell: A single electrode immersed in a solution of its ions.
f. Salt bridge: A device (porous disk or bridge i.e. U-tube containing inert electrolytic
solution, KCl, NH4NO3, etc.) placed between the cells which maintains electrical
neutrality by allowing ions to migrate between the cells.
g. External circuit: The part of the cell where charge is conducted as a current of moving
electrons.
h. Standard Electrode Reduction Potential E : The measurement, in volts, of the
tendency for a half reaction to occur as a reduction half reaction.
1 7 . 2 8 | Electrochemistr y

S.No. Description
6 Voltaic/Galvanic Cells Redox reactions are spontaneous and chemical energy is transformed into electrical
energy. The cell potential E is positive and the anode is the negative electrode. i.e.
batteries
Zn(s) Zn+2(1M) Cu+2(1M) Cu(s)
anode  cathode
7 Electrolytic Cells Cell in which an external electric current is required to drive a non-spontaneous redox
reaction. The cell potential (Eo) is negative and the anode is the positive electrode. i.e.
electrolysis, electroplating, etc.
Cu(s) Cu+2(1M) Cu+2(1M) Cu(s)
anode  cathode
8 Quick Comparison of Type of redox reaction cell Galvanic/Voltaic Electrolytic
Electrolytic Cells potential (Eºcell) Electron
Spontaneous Non-spontaneous
flow
(Eºcell is positive) (Eºcell is negative)
Site of oxidation
Creates one Requires one
Site of reduction
Anode Anode
Positive electrode
Cathode Cathode
Negative electrode
Cathode Anode
Flow of electrons
Anode Cathode
Anode to cathode Anode to cathode
(negative to positive) (positive to negative)
Batteries Electrolysis, electroplating

9 Faraday’s First law of The amount of electrolyte discharged at an electrode is directly proportional to the
Electrolysis quantity of electricity passed:
W ∝ Q where, = I. t
I = Current strength in ampere
T = time in seconds
⇒ W = ZQ = Zit
Z is a constant called electrochemical equivalence (ECE)
10 Electrochemical It is the amount of an electrolyte discharged on passing one coulomb of electricity.
Equivalent
11 Faraday’s Constant It is the charge possessed by 1.0 mole of electrons and it is equal to 96500 coulombs
(approx.). In terms of faraday’s constant the number of gram equivalent of electrolyte
discharged at an electrode is equal to the number of faraday’s passed.

 Q 
⇒ W=E   where, E = Equivalent weight
 96500 

12 Faraday’s Second Law Second Law: If same quantity of electricity is passed through different cells connected
in series, same number of gram equivalent of electrolytes are discharged at each of the
electrodes:
W1 E1
⇒ =
W2 E2

Where, W1 and W2 are the weights of electrolytes discharged at two different electrodes
in two different cells connected in series and E1 and E2 are their respective equivalent
weights.
Chem i str y | 17.29

S.No. Description
13 Nernst Equation
 2.303 RT [Reduced form]
Ehalf–cell = E half–cell – log
nF [Oxidised form]

At 298 K, the Nernst equation can be written as,

Ehalf–cell = E half–cell – 0.0591log [Reduced form]


n [Oxidised form]

Solved Examples

JEE Main/Boards Pt(H2 ) H+


Ag+ Ag Eo
cell = 0.7991 V
1bar =
a 1=
a 1
Example 1: Zn and iron can replace Cu in a solution but
Pt and Au cannot. Why?
Sol: Since platinum electrode has zero reduction
Sol: Both Zn and iron have more EOP than Cu, whereas potential the standard electrode potential will be equal
Pt and Au have less EOP to the standard electrode potential of the cell.
Ecell = EOP 
+ ERP
Example 2: Which of the following metals cannot H/H+ Ag+ /Ag
be obtained by the electrolysis of their aqueous salt  
solution and why? Or 0.7991=0 + ERP ∴ ERP = 0.7991 V
Ag+ /Ag Ag+ /Ag
Al, Na, Cu, Ag.
Example 5: Standard reduction potential of the Ag+/Ag
Sol: Al and Na cannot be obtained because they have
electrode at 298 K is 0.799 V. Given that for AgI, Ksp = 8.7
higher EOP than H and thus, reduction of Cu2+ and Ag+
× 10–17, evaluate the potential of the Ag+/Ag electrode in
will give Cu and Ag.
a saturated solution of AgI. Also calculate the standard
reduction potential of I– / AgI/Ag electrode.
Example 3: Calculate the no. of electron lost or gained
during electrolysis of 2 g Cl– from NaCl (aq) to give Cl2 Sol: Here solubility product is given from this calculate
at anode. the concentration of silver ions. Now substituting this
Sol: First calculate the equivalent of Cl- used during the value in Nernst equation determine E +
Ag /Ag
reaction and on multiplying it with avogadro number
will give us the no of electron lost during the reaction As we have found out E , EI/AgI/Ag can find out by
Ag+ /Ag
∵ 2Cl– → Cl2 + 2e⁻
using the value of solubility product.
Eq. of Cl– used = 2/35.5
∵ 1 eq. of an element involves 1 faraday charge or N E = E +(0.059/1) log [Ag+]  … (i)
Ag+ /Ag Ag+ /Ag
electrons
∴ (2/35.5) eq. of an element involves Also, K sp = [Ag+ ][I – ]
AgI
N× 2 6.023 × 1023 × 2 ∵ [Ag]+ = [I–] (for a saturated solution)
= electrons =
35.5 35.5
= 3.4 × 1022 electrons ∴ [Ag+] = (K sp=) (8.7 × 10 –17 )
AgI

Example 4: Evaluate the E + and E 2+ from the = 9.32 × 10–19 … (ii)


Ag /Ag Zn /Zn
given values:
∴ By Eq. (i),
1 7 . 3 0 | Electrochemistr y

E calculate the concentration of hydrogen ion. From the


Ag+ /Ag
= 0.799 + (0.059/1) log (9.32 × 10–9)
concentration one can easily find out the pH as using
the following expression
= 0.799 – 0.474 = 0.32 V
Also, EI/AgI/Ag = E + (0.059/1) log K sp pH= –logH+
Ag+ /Ag AgI
Ni → Ni2+ + 2e⁻; EOP = 0.236V
= 0.799 + (0.059/1) log [8.7 × 10 ] –17


2H+ + 2e⁻ → H2; ERP =0
= 0.799 – 0.948 = – 0.149 V
∴ ECell = EOP
 
+ ERP = 0.236 + 0.0 = 0.236 V
Ni H
Example 6: The reduction potential diagram for Cu in
acid solution is: 0.059 [H+ ]2
∴ Ecell = Ecell + log10
2 [Ni2+ ]
2+ +0.15 V + +0.50 V
Cu Cu Cu 0.059
0 = 0.236 + log10 [H+]2
o 2
E = X volt
or –logH+ = 4

∴ pH = 4
Calculate X. Does Cu+ disproportionate in solution?

Example 8: A current of 3 ampere was passed for 2


Sol: Given;
hour through a solution of CuSO4.3g of Cu2+ ions were
Cu2+ + e⁻ → Cu+ ; E1 = 0.15V discharged at cathode. Calculate current efficiency. (At
wt. of Cu = 63.5)
−∆G1 = 1 × E1 × F  ... (i)
Sol: Find out current in ampere and from the calculated
Cu+ + e⁻ → Cu ; E2 = 0.5 V
current passed, determine the current efficiency.
−∆G2 = 1 × E2 × F  … (ii) Current efficiency =
Cu + 2e⁻ → Cu ;
2+
E3 =? Current passed actually
× 100
−∆G3 = 2 × E3 × F  Total current passed experimentally
… (iii)
∵ wCu = E. i. t / 96500
Adding Eqs. (i) and (ii)

Cu2+ + 2e⁻ → Cu ; – ( ∆G1 + ∆G2 )  ... (iv) 63.5 × i × 2 × 60 × 60


∴3= or i = 1.266 ampere
2 × 96500
i.e., −∆G3 = −( ∆G1 + ∆G2 )
Current efficiency
2× E3 × F = [1 × 0.15 × F + 1 × 0.5 × F] Current passed actually
= × 100
∴ E3 = 0.325V Total current passed experimentally

= (1.266/3)×100 = 42.2%
Example 7: The standard oxidation potential of Ni/Ni 2+

electrode is 0.236 V. If this is combined with a hydrogen Example 9: An ammeter and copper voltmeter are
electrode in acid solution, at what pH of the solution connected in series in an electric circuit through which a
will the measured e.m.f. be zero at 25ºC? constant direct current flows. The ammeter shows 0.525
(Assume [Ni2+] = 1 M) ampere. If 0.6354 g of Cu is deposited in one hour, what
is percentage error of ammeter? (At. Wt. of Cu = 63.54)
Sol: Here we are provided with standard oxidation
potential of nickel electrode and we all know that Sol: In order to find out the error first from the given
reduction potential of hydrogen electrode is always Weight, time and other term calculate the actual
zero so first the standard electrode potential of the cell current flow. The difference between the two will give
is equal the oxidation potential of nickel electrode. Here us the error shown by the ammeter. As we are asked
it we are also with e.m.f of the cell (zero) so substitute to calculate percentage error divide the error by actual
the values of different term in Nernst equation and current flow
Chem i str y | 17.31

Current flown = 0.525 ampere as shown by ammeter ∴ wNaOH = {710[71/2]} × 40 = 800 g


Actual current flown
And wH = {710/[71/2]} × 1 = 20g
w 2
(I) = × 96500
E×t ∴ VH = wRT / mp
2
0.6354 × 96500 = [20 × 0.0821 × 300] / [2 × 1] = 246.3 liter
(∵ t = 60 × 60 sec)
(63.54 / 2) × 60 × 60
∴ i = 0.536 ampere Example 2: 50 mL 0.1 M CuSO4 solution is electrolyzed
Thus, error in (I) = 0.536 – 0.525 = 0.011 using Pt electrodes with a current of 0.965 ampere for
a period of 1 minute. Assuming that volume of solution
0.011 × 100
∴ % error in ammeter = = 2.05% does not change during electrolysis, calculate [Cu2+],
0.536 [H+] and [SO24− ] after electrolysis. What will be the
concentration of each species, if current is passed using
Example 10: 3 ampere current was passed through Cu electrodes?
an aqueous solution of unknown salt of Pd for 1 hour
2.977 g of Pdn+ was deposited at cathode. Find n. (At. Sol: Meq. Of CuSO4 in solution = Meq. Of Cu2+
Wt. of Pd = 106.4)
= 50 × 0.1 × 2 = 10 (∵ Meq. Of N× V in mL)
Sol: For the reduction: Pd n+
+ ne → Pd
- The redox changes are:

Eq. of Pd or (w/E) = (I × t)/96500 Cu2+ + 2e → Cu (at cathode)

2.977 3 × 1 × 60 × 60 2H2O → 4H + O2 + 4e
+
(at anode)
or =
106.4 / n 96500 ∵ w/E = i.t/96500
And Eq. of Cu2+ lost = Equivalent of H+ formed
∴ n = 4 (an integer).
i. t. 0.965 × 1 × 60
= = = 6 × 10–4
96500 96500
JEE Advanced/Boards Or Meq. Of Cu2+ lost = 0.6

Example 1: Calculate the quantity of electricity that will ∴ Meq. of Cu2+ or Meq. of CuSO4 left in solution
be required to liberate 710g of Cl2 gas by electrolyzing a = 10 – 0.6 = 9.4
conc. solution of NaCl. What weight of NaOH and what
N Meq. of Cu2+
volume of H2 at 27ºC and 1 atm pressure is obtained ∴[Cu2+]= Cu2 +
=
during this process? 2 2 × Volume of solution (in mL)
9.4
= = 0.094 M
Sol: Quantity of electricity can be calculated using 2 × 50
Simple relationship [H+]= (N / 1) = (0.6/50) = 0.012 M
H+
E×i× t [SO24− ] = 0.1M
W= (∵ Q = i × t)
96500
(∵ SO2–
4 is not involved in redox changes)
Similarly calculate wNaOH and wH from the value of
2
wH volume can be calculated using ideal gas equation. Also, if Cu electrodes are used, Cu2+ ions are discharged
2
at cathode and Cu2+ are formed at anode and thus
∵ 2Cl– → Cl2 + 2e; 2H+ + 2e → H2 no changes in molarity of CuSO4 solution. Anode
Cu → Cu2+ + 2e-
∴ Eq. wt. of Cl2 = M. Wt./2
Cathode Cu2+ + 2e → Cu
E×i× t E×Q
Now w = = (∵ Q = i × t)
96500 96500 Example 3: Two students use same stock solution
w 710 ZnSO4 and a solution of CuSO4. The e.m.f., of one cell is
∴ Q= × 96500 = × 96500
E 71 / 2 0.03 V higher than the other. The conc. of CuSO4 in the
cell with higher e.m.f. value is 0.5 M. Find out the conc.
= 1.93 × 106 coulomb
of CuSO4 in the other cell.
Also Eq. of NaOH formed  2.303RT 
= Eq. of H+ discharged= Eq. of Cl2 formed  = 0.06 
 F 
1 7 . 3 2 | Electrochemistr y

Sol: First write down the half-cell reaction and nernst 1 1


equation for both the half cell. By comparing both the ∴ pH1 = pK a − log C
2 1 2
equation, value of C2 can be calculated.
1 1
pH2
Similarly,= pK a − log C
Cell I: Zn | ZnSO4 || CuSO4 | Cu 2 2 2
0.060 [Cu2+ ] (∵ C are same) By Eqs. (i) and (ii), Ecell
(C2 = 0.5 M); Ecell = Ecell + log
2 [Zn2+ ] 1 1 
0.060 [C ] = EOP 
+ ERP + 0.059  pK a − pK a 
= Eocell + log 2  ... (i) H/H+ H/H+ 2 2 2 1

2 [C1 ]
= 0 + 0.059 × 5[5 – 3]/2 = + 0.059 volt
Cell II: Zn | ZnSO 4 || CuSO 4 | Cu
C1 C'2
Example 5: Calculate the minimum weight of NaOH
required to added in RHS to consume all the H+ present
' 0.06 [C'2 ]
E=
cell Ecell + log  ... (ii) in RHS of cell of e.m.f. +0.701 V at 25ºC before its use.
2 [C1 ] Also report the e.m.f. of cell after addition of NaOH.
0.06 [C ]
By Eqs. (i) and (ii) Ecell − E'cell = log 2 Zn Zn HCl Pt(H2 ) E
2+
2 [C' ] 2 + = +0.760V
2
0.1M 1 litre 1 atm Zn|Zn
0.06 0.5
0.03 = log or C'2 = 0.05M
2 C' 2
Sol: For given cell ∵ EOP > EOP
Zn/Zn2 + H/H+
Example 4: Two weak acid solutions HA1 and HA2 each
∴ Redox changes will be: Zn → Zn2+ + 2e
with the same concentration and having pKa values 3
and 5 are placed in contact with hydrogen electrode
2H+ + 2e →
= H2, Ecell EOP + ERP
(1 atm at 25ºC)) and are interconnected through a salt Zn/Zn2 + H+ /H

bridge. Find e.m.f. of cell.


0.059
= EOP − log10 [Zn2+ ]
Sol: First write down the nernst equation for two half- Zn/Zn2 + 2
cell as both solutions are acid we have to find out the
concentration of hydrogen ion we can express it in  0.059 [H+ ]2
+ ERP + log10
the form of pH. As an acid undergoes dissociation, by H+ /H 2 (PH )
substituting pH in terms of degree of dissociation and 2

concentration in nernst equation, e.m.f of the cell can 0.059 [H+ ]2


be easily determined. E=
cell Ecell + log
2 [Zn2+ ](PH )
2
Consider the cell
Pt H2(1 atm) | HA2 || HA1 | (H2 ) (1atm) Pt
0.059 [H+ ]2
0.701 = 0.760 + log10
2 [Zn2+ ](PH )
2
0.059
At L.H.S.=
E + EOP − log[H+ ]2
H/H H/H+ 1 0.059 [H+ ]2
0.701 = 0.760 + log10
∵ –log H+ = pH 2 [0.1] × 1
[H+] = 0.0316 mole liter–1
E + EOP
∴ = + 0.059(pH)2 ….. (i)
H/H H/H+  Since, H+ must be used by NaOH
0.059
At R.H.S.=
E + 
ERP + log[H+ ]1 ∴ Meq. of NaOH = Meq. of [H+]
H /H H+ /H 1
(w/40) × 1000 = 0.0316 × 1000 (∵ V = 1 liter)

E +
= ERP − 0.059(pH)1  ... (ii)
H /H H+ /H ∴ w = 1.265 g
For acid HA1 HA1 

 + −
 H + Al After addition of NaOH to cathode solution [H+]
becomes 10–7 since both acid and base are neutralized
[H+] = C α = Ka . C completely. Thus, new e.m.f. of cell,
Chem i str y | 17.33

 0.059 [H+ ]2 Example 7: Ecell values for


E=
cell E=
cell log10
2 (0.1) Fe → Fe2+ + 2e- and Fe → Fe3+ + 3e- are 0.440 and 0.036
0.059 (10−7 )2 V respectively:
= 0.760 + log10 Ecell = 0.3765 V
2 0.1 (a) Design and point out the number of cells showing
the overall reaction Fe + 2Fe3+→ 3Fe2+
Example 6: For the galvanic cell: (b) Also calculate Ecell and ∆G values for each cell. Also
comment on the result.
AgCl(s) KCl KBr AgBr(s)
Ag Ag
0.2 M 0.001 M Sol: Standard free energy can be calculated using the
equation
Calculate the e.m.f generated and assign correct
polarity to each electrode for a spontaneous process ∆G =−n EF
after taking an account of cell reaction at 25ºC.
Fe → Fe2+ + 2e- ; – ∆G1 = +0.440 × 2 × F
−10 −13
[Give, K sp = 2.8 × 10 , K sp = 3.3 × 10 ]
AgCl AgBr Fe3+ + 3e- → Fe ; – ∆G2 = – 0.036 × 3 × F
Sol: Write down the half-cell equation for both the cell.
∴ Fe3+ + e- → Fe2+ ; – ∆G3 = – ( ∆G2 + ∆G1 )
Here we are provided with solubility product of the two
solution. From the value of solubility product first find −n EF = [2 × 0.440 – 3 × 0.036] × F (n = 1)
out the concentration of silver ion in each solution. Now
substitute this value in Nernst equation and calculate Eº = + 0.772 V
the e.m.f.
Cell no. I: Fe | Fe+2 || Fe3+ | Fe
Ecell EOP
= + ERP ; L.H.S. R.H.S. 3Fe → 3Fe2+ + 6e⁻
Ag Ag

2Fe3+ + 6e⁻ → 2Fe


0.059
= EOP – log [Ag+]L.H.S.
Ag 1 Redox Fe + 2Fe3+ → 3Fe2+

0.059 Ecell = EOP 


+ERP =0.440–0.036=0.404V

+ ERP + log[Ag+ ]R.H.S. Fe|Fe2 + Fe3+ |Fe
Ag 1
0.059 [Ag+ ]R.H.S. Also, ∆G = –6 ×0.404 × F = – 2.424 F
Ecell = log  …. (i)
1 [Ag+ ] Cell no. II: Fe | Fe2+ || Fe3+, Fe2+ | Pt
L.H.S.

For L.H.S. Ksp of AgCl = 2.8 × 10–10 Fe → Fe2+ + 2e-

or [Ag+][Cl–] = 2.8 × 10–10 2Fe3+ + 2e- → 2Fe2+


2.8 × 10−10 2.8 × 10−10 Redox Fe + 2Fe3+ → 3Fe2+
or [Ag+] = = =1.4×10–9 M
[Cl ] − 0.2

= Ecell 
EOP 
+ ERP
For R.H.S. Ksp of AgBr = 3.3 × 10–13 Fe/Fe2+ Fe3+ /Fe2 +

or [Ag+][Br–] = 3.3 × 10–13


Example 8: Oxidizing power of Cr2O27− is more in acidic
or [Ag+] = (3.3 × 10–13) / 0.001 = 3.3 × 10–10 M medium than in alkaline medium.
∴ By Eq. (i), 
Sol: ERP o
in acidic medium is more than ERP in alkaline
0.059 3.3 × 10−10 medium.
Ecell = log = –0.037V
1 1.4 × 10−9 Acid: Cr2O27− + 14H+ + 6e⁻ → 2Cr3+ + 7H2O ;
o
Thus, to get cell reaction (i.e. Ecell, Ecell = +ve) polarity
ERP = +1.33V
of cell
Alkali: Cr2O27− + H2O → 2CrO24− + 2H+

CrO24− + 4H2O + 3e− → Cr(OH)3 + 5OH− ; ERP = −0.13V
1 7 . 3 4 | Electrochemistr y

Example 9: Color of KI solution containing starch turns º


After calculating Ecell e.m.f of the cell can be easily
blue when Cl2 water is added. Explain. calculated using following equation
Sol: Chlorine placed below iodine in electrochemical 0.0591 [Products]
º
series having lesser EOP than iodine and thus, shows E=
cell Ecell − log
n [Reactants]
reduction whereas I– undergoes oxidation. The I2 so
formed gets absorbed in starch to give blue color. ECell ECathode
= 
− EAnode = 0.80–(–2.37)= 3.17 volt
2I– → I2 + 2e- Cell reaction, Mg + 2Ag+ → 2Ag + Mg2+
Cl2 + 2e- → 2Cl– 0.0591 Mg2+

E=
cell Ecell − log
Cl2 + 2I– → I2 + 2Cl– n [Ag+ ]2
0.0591 0.2
= 3.17 – log
Example 10: Calculate the e.m.f of the cell. 2 [1 × 10−3 ]2
Mg(s) | Mg2+(0.2 M) || Ag+ (1 × 10–3) | Ag = 3.17 – 0.1566 = 3.0134 volt
Eo = + 0.8 volt, Eo = – 2.37 volt When Mg2+ = 0.1 M
Ag+ |Ag Mg2 + /Mg
0.0591 0.1
What will be the effect on e.m.f if concentration of Mg2+ E=
cell Ecell − log
ion is decreased to 0.1 M? 2 (1 × 10−3 )2
= (3.17 – 0.1477) volt= 3.0223 volt
Sol: First calculate the standard potential for reaction
º º º
which is calculated =as Ecell Eoxidation − Ereduction

JEE Main/Boards

Exercise 1 Q.4 In the button cells widely used in watches and other
devices the following reaction takes place:
Q.1 Depict the galvanic cell in which the reaction Zn(s) Zn(s) +Ag2O(s) + H2O(l) → Zn2+(aq) + 2Ag(s) + 2OH–(aq)
+ 2Ag+ (aq) → Zn2+ (aq) + 2Ag(s) takes place. Further
show: Determine ∆rG’ and E’ for the reaction.

(i) Which of the electrode is negatively charged?


Q.5 The conductivity of 0.20 M solution of KCl at 298 K
(ii) Individual reaction at each electrode. is 0.0248 S cm–1. Calculate it molar conductivity.

Q.2 Electrolytic conductivity of 0.20 mole L–1 solution of Q.6 How much electricity in terms of faraday is required
KCl at 298 K is 2.48 × 10–2 ohm–1cm–1. Calculate its molar to produce
conductivity.
(i) 20.0 g of Ca from molten CaCl2?

Q.3 Write the Nernst equation and e.m.f of the following (ii) 40.0 g of Al from molten Al2O3?
cells at 298K:
Q.7 How much electricity is required in coulomb for the
(i) Mg(s)|Mg2+ (0.001M)||Cu2+(0.0001 M)|Cu(s)
oxidation of:
(ii) Fe(s)|Fe2+(0.001M)||H+(1M)|H2(g)(1bar)|Pt(s) (i) 1 mole of H2O to O2?
(iii) Sn(s)|Sn (0.050 M)||H (0.020 M)|H2(g)(1 bar)|Pt(s)
2+ +
(ii) 1 mole of FeO to Fe2O3?
(iv) Pt(s)|Br2(l)|Br–(0.010 M) || H+(0.030 M)|H2(g)
(1 bar)|Pt(s)
Chem i str y | 17.35

Q.8 The resistance of a conductivity cell containing Q.16 The standard electrode potentials of Ag+|Ag,
0.001 M KCl solution at 298 K is 1500 Ω. What is the cell Cl2|Cl– and O3|O2 electrodes are +0.80V, +1.36V and
constant if conductivity of 0.001 M KCl solution at 298 +2.07 V, respectively. Using these information, answer
K is 0.146 × 10–3 S cm–1? the following:
(i) Which of the following is strongest oxidizing agent:
Q.9 Conductivity of 0.00241 M acetic acid is Ag+, Cl2, and O3?
7.896 × 10–5 S cm–1. Calculate its molar conductivity.
o
If Λ ∞ for acetic acid is 390.5 S cm2 mole–1, what is its (ii) Which of the following is the strongest oxidizing
dissociation constant? agent: Ag, Ag+, O3, and O2?

(iii) Which of the following is the strongest reducing


Q.10 A solution of Ni(NO3)2 is electrolyzed between agent: Ag, Cl–, and O2
platinum electrodes using a current of 5 amperes for
20 minutes. What mass of Ni deposited at the cathode? (iv) Which of the following is the strongest reducing
agent: Ag, Ag+, O3, and O2
Q.11 The conductivity of sodium chloride at 298 K has
been determined at different concentrations and the Q.17 The following reactions represent the reduction of
results are given below: IO– ion into I–ion in acidic and basic medium.

Concentration M IO3− + 6H+ + 6e− → I – + 3H2O ; Eº = + 0.907 V


0.001 0.010 0.020 0.050 0.100 IO3− + 3H2O + 6e− → I – + 6OH− ; Eº = + 0.260 V
102 × k/S m–1 [Acid Medium]

1.237 11.85 23.15 55.53 106.74
Calculate Λ ∞ for all concentrations and draw a plot Q.18 Can Fe3+ oxidize Br– to Br under standard
o
between Λ ∞ and S. Find the values of Λ ∞ conditions?
Given: E = + 0.77 V, E = + 1.09 V
Fe3+ |Fe2 + Br2 | Br −
Q.12 Three electrolytic cells A, B, C containing solution
of ZnSO4, AgNO3 and CuSO4, respectively are connected
in series. A steady current of 1.5 amperes was passed Q.19 Calculate the electrode potential of the following
through them until 1.45 g of silver deposited at the electrodes at 25ºC:
cathode of cell B. How long did the current flow? What (i) Cu2+ (0.001 M) | Cu ; E = + 0.34 V
mass of copper and zinc were deposited? Cu3+ | Cu

(ii) Zn | Zn2+ (0.02 M) ; E = –0.76 V


Zn2 + | Zn
Q.13 Using the standard electrode potentials of
electrochemical series, predict if the reaction between (iii) AgCl (stand. sol) | Ag ; E + = +0.80 V, Ksp of
Ag | Ag
the following is feasible: AgCl = 2 × 10–10.

(i) Fe3+(aq) and I– (aq) (ii) Ag+(aq) and Cu(s) (iv) Pt | Cl2 (0.5 atm) | Cl– (0.02 M); E

= 1.36 V
Cl 2| Cl–
(iii) Fe (aq) an Br (aq)
3+ –
(iv) Ag(s) and Fe (aq)
3+

(v) HCl (pH = 4.4) | H2(2 atm) | Pt


(iv) Br2(aq) and Fe2+(aq).

Q.20 Calculate the reduction potential at 25ºC for Fe3+/


Q.14 The standard electrode potentials of Cu2+|Cu+ an Fe2+ electrode if the concentration of Fe2+ ion is five
Cu+|Cu electrodes are +0.18 V and +0.50 V, respectively. times that of Fe3+ ion.
Calculate the standard potential of Cu2+| Cu electrode.
E = 0.77 volt.
Fe3+ | Fe2 +

Q.15 Arrange Zn, Pb and Al in the increasing order of


their reducing power under standard conditions. Q.21 Calculate electrode potential for the half-cell
Pt|H2 (1 atm) | 0.357M – CH3COOH. Ka for CH3COOH =
Given: E = –0.76 V, = –0.13 V, E = –1.66 V 1.74 × 10–5.
Zn2 + |Zn Al2 + |Al]

Q.22 The standard reduction potential for Cu2+| Cu is +


1 7 . 3 6 | Electrochemistr y

0.34 V. Calculate the reduction potential at pH = 13 for Q.2 One mole of electron passes through each of the
the above couple. Ksp of Cu(OH)2 is 1.0 × 10–10. solution of AgNO3, CuSO4 and AlCl3 when Ag, Cu and
Al are deposited at cathode. The molar ratio of Ag, Cu
Q.23 Calculate and Al deposited are:
(A) 1: 1: 1 (B) 6: 3: 2 (C) 6: 3: 1 (D) 1: 3: 6
(i) E ; E = 0.80 V, Ksp of AgCl = 2 × 10–10
Cl + | AgCl | Ag Ag+ | Ag

(ii) E ; E = + 0.80 V, Q.3 Salts of A (atomic weight = 7), B (atomic weight =


Cl– (0.004M)AgCl | Ag Ag+ | Ag
27) and C (atomic weight = 48) were electrolyzed under
Ksp of AgCl = 2 × 10–10 identical conditions using the same quantity of electricity.
It was found that when 2.1 g of A was deposited, the
weights of B and C deposited were 2.7 and 7.2 g. The
Q.24 Calculate the e.m.f of the cell in which the
valencies of A, B and C respectively are:
following reaction takes place:
Ni(s) + 2Ag+(0.002 M) → Ni2+ (0.160 M) + 2Ag(s) (A) 3, 1 and 2 (B) 1, 3 and 2

Given that E cell = 1.05 V (C) 3, 1 and 3 (D) 2, 3 and 2

Q.4 The density of Cu is 8.94 g cm–3. The quantity of


Q.25 The molar conductivity of 0.025 mole methanoic
electricity needed to plate an area 10 cm × 10 cm to
acid is 46.1 S cm2 mole–1. Calculate its degree of
a thickness of 10–2 cm using CuSO4 solution would be
dissociation and dissociation constant.
Given Λ0 (H+) = 349.6 S cm2 mol/L and (A) 13586 C (B) 27172 C
λ°(HCOO⁻) = 54.6 S cm mol/L. 2
(C) 40758 (D) 20348 C

Q.26 Suggest a list of metals that are extracted Q.5 During electrolysis of an aqueous solution of
electrolytically. sodium sulphate, 2.4L of oxygen at STP was liberated
at anode. The volume of hydrogen at STP, liberated at
Q.27 Represent the cell in which following reaction cathode would be
takes place: (A) 1.2 L (B) 2.4 L (C) 2.6 L (D) 4.8 L
Mg(s) + 2Ag+ (0.0001 M) → Mg2+(0.130 M) + 2Ag(s)
calculate its Ecell if Eºcell = 3.17V. Q.6 When an aqueous solution of lithium chloride is
electrolyzed using graphite electrodes
Q.28 Calculate the reduction potential of the following (A) Cl2 is liberated at the anode
electrodes: (B) Li is deposited at the cathode
(a) Pt2 H2 (4 atm) | H2SO4 (0.01 M) (C) As the current flows, pH of the solution around the
cathode remains constant
(b) Pt2 H2 (1 atm) | HCl (0.2 M)
(D) As the current flows, pH of the solution around the
(c) Calculate the potential of hydrogen electrode in cathode decreases.
contact with a solution whose
(i) pH = 5 (ii) pOH = 4 Q.7 A standard hydrogen electrons has zero electrode
potential because
Q.29 Calculate the equivalent conductivity of 1M H2SO4 (A) Hydrogen is easier to oxidize
solution, if its conductivity is 26 × 10–2 ohm–1 cm–1.
(B) This electrode potential is assumed to be zero
(C) Hydrogen atom has only one electron
Exercise 2 (D) Hydrogen is the lightest element.
Single Correct Choice Type
Q.8 If the pressure of H2 gas is increased from 1 atm to
Q.1 One gm. metal M+2 was discharged by the passage of 100 atm keeping H+ concentration constant at 1 M, the
1.81 × 1022 electrons. What is the atomic weight of metal? change in reduction potential of hydrogen half-cell at
25ºC will be
(A) 33.35 (B) 133.4 (C) 66.7 (D) 55
(A) 0.059 V (B) 0.59 V (C) 0.0295 V (D) 0.118 V
Chem i str y | 17.37

Q.9 The equilibrium constant for the reaction Sr(s) + Q.16 The dissociation constant of n-butyric acid is
Mg+2 (aq) → Sr+2 (aq) + Mg(s) is 2.69 × 1012 at 25ºC 1.6 × 10–5 and the molar conductivity at infinite dilution
is 380 × 10–4 S m2 mol–1. The specific conductance of
The E for a cell made up of the Sr/Sr+2 and Mg+2/Mg
the 0.01 M acid solution is
half-cells
(A) 1.52 × 10 S m–1 (B) 1.52 × 10–2 S m–1
(A) 0.3667 V (B) 0.7346 V
(C) 1.52 × 10–3 S m–1 (D) None of these
(C) 0.1836 V (D) 0.1349 V

Q.17 Consider the reaction of extraction of gold from


Q.10 A silver wire dipped in 0.1 M HCl solution
its ore
saturated with AgCl develop a potential of –0.25 V. If
Au+2CN–(aq.)+ 1 O2(g)+ 1 H2O→Au (CN)2 + OH–

E = –0.799 V, the Ksp of AgCl in pure water will be:
Ag/ Ag+ 4 2

(A) 2.95 × 10–11 (B) 5.1 × 10–11 Use the following data to calculate ∆Gº for the reaction,
Kf{Au(CN)2} = X
(C) 3.95 × 10–11 (D) 1.95 × 10–11
O2 + 2H2O + 4e– → 4OH– ; E° = + 0.41 volt
Q.11 During electrolysis of an aqueous solution Au3+ + 3e– → Au ; E° = + 1.5 volt
of CuSO4 using copper electrodes, if 2.5 g of Cu is Au + 2e → Au ; E°= + 1.4 volt
3+ – +

deposited at cathode, then at anode


(A) –RT ln X + 1.29 F (B) –RTln X –2.11 F
(A) 890 ml of Cl2 at STP is liberated
(B) 445 ml of O2 at STP is liberated (C) –RTln 1 + 2.11 F (D) –RTln X –1.29 F
X
(C) 2.5 g of copper is deposited
Q.18 Consider the following Galvanic cell
(D) A decrease of 2.5 g of mass takes place
voltmeter
Q.12 The cost at 5 paise / KWH of operating an electric H2(g) Cl2(g)
motor for 8 hours which takes 15 amp at 110 V is KNO3

(A) Rs 66 (B) 66 paise HCl HCl


Pt(s)
(C) 37 paise (D) Rs. 6.60

Anode Cathode
Q.13 The resistance of 0.5 M solution of an electrolyte
in a cell was found to be 50Ω. If the electrodes in the By what value the voltage change when concentration
cell are 2.2 cm apart and have an area of 4.4 cm2 then of ions in anodic and cathodic compartments both
the molar conductivity (in S m2 mole–1) of the solution is increases by factor of 10 at 298 K
(A) 0.2 (B) 0.02 (C) 0.002 (D) None of these
(A) 0.0591 (B) –0.0591 (C) –0.1182 (D) 0

Q.14 Equivalent conductance of 0.1 M HA (weak acid)


Q.19 For the cell
solution is 10 S cm2 equivalent–1 and that at infinite
dilution is 200 S cm2 equivalent–1 Hence pH of HA Pt||H2 (0.4 atm) | H+ (pH=1) || H+ (pH =2) | H2 (0.1 atm) | Pt
solution is
The measured potential at 25ºC is
(A) 1.3 (B) 1.7 (C) 2.3 (D) 3.7
(A) –0.1 V (B) –0.5 (C) –0.041 (D) None of these

Q.15 If x is specific resistance of the electrolyte solution


Q.20 For the fuel cell reaction:
and y is the molarity of the solution, then Λm is given by

y 2H2 (g) + O2 (g) → 2H2O (l); ∆ fH298 (H2O,(l)= –285.5 KJ/mole
1000x
(A) (B) 1000 
y x What is ∆S298 for the given fuel cell reaction?
1000 xy Given O2 (g) + 4H+ (aq) + 4e– → 2H2O (l) E = 1.23 V
(C) (D)
xy 1000
(A) –0.322 J/K (B) –0.635kJ/K
(C) 3.51 kJ/K (D) –0.322 kJ/K
1 7 . 3 8 | Electrochemistr y

Q.21 The standard reduction potentials of Cu2+/Cu Q.6 The highest electrical conductivity of the following
and Cu2+/Cu+ are 0.337 and 0.153 V respectively. The aqueous solution is of (2005)
standard electrode potential of Cu+/Cu half-cell is:
(A) 0.1 M acetic acid
(A) 0.184 V (B) 0.827 V (B) 0.1 M chloroacetic acid
(C) 0.521 V (D) 0.490 V (C) 0.1 M fluoroacetic acid
(D) 0.1 M difluoroacetic acid
Previous Years' Questions
Q.7 The equivalent conductance’s of two strong
electrolytes at infinite dilution in H2O (where ions move
Q.1 When the sample of copper with zinc impurity is to
freely through a solution) at 25ºC are given below: A t
be purified by electrolysis, the appropriate electrodes
25ºC are given below: (2007)
are (2002)
Λ CH = 91.0 S cm2 / equivalent
Cathode Anode 3COONa

(a) Pure zinc Pure copper ΛHCl = 426.2 S cm2/equivalent
What additional information/quantity one needs to
(b) Impure sample Pure copper
calculate Λ° of an aqueous solution of acetic acid
(c) Impure zinc Impure sample
(A) Λ° of NaCl
(d) Pure copper Impure sample
(B) Λ° of CH3COOK
o +
(C) The limiting equivalent conductance of H+ ( Λ H )
Q.2 In the electrolytic cell, flow of electrons is from
 (2003) (D) Λ  of chloroacetic acid (Cl/CH2COOH)

(A) Cathode to anode in solution


 
Q.8 The molar conductivities λNaOAc and λHCl at infinity
(B) Cathode to anode through external supply
dilution in water at 25ºC are 91.0 and 426.2 S cm2/mole
(C) Cathode to anode through internal supply 
respectively. To calculate λHOAc , the additional value
(D) Anode to cathode through internal supply required is (2006)
  
(A) λH (B) λKCl (C) λNaOH (D) λNaCl
Q.3 During the electrolysis of a solution of AgNO3, 9650 2O
coulombs of charge pass through the electroplating
both, the mass of silver deposited in the cathode will Q.9 Resistance of a conductivity cell filled with a solution
be  (2003) of an electrolyte of concentration 0.1 M is 100 Ω. The
conductivity of this solution is 1.29 S m–1. Resistance of
(A) 1.08 g (B) 10.8 g (C) 21.6 g (D) 108 g the same cell when filled with 0.2 M of the same solution
is 520 Ω. The molar conductivity of 0.02 M solution of
Q.4 During the process of electrolytic refining of copper, the electrolyte will be (2006)
some metals present as impurity settle as ‘anode mud.’
(A) 12.4 × 10–4 S m2 mole–1
These are  (2005)
(B) 1240 × 10–4 S m2 mole–1
(A) Sn and Ag (B) Pb and Zn
(C) 1.24 × 10–4 S m2 mol–1
(C) Ag and Au (D) Fe and Ni
(D) 1.24 × 10–4 Sm2 mole–1

Q.5 Conductivity (unit Siemen’s) is directly proportional


Q.10 Saturated solution of KNO3 is used to make ‘salt-
to area of the vessel and the concentration of the
bridge’ because (2002)
solution in it and is inversely proportional to the
length of the vessel then the unit of the constant of (A) Velocity of K+ is greater than that of NO3–
proportionality is (2002) (B) Velocity of NO3– is greater than that of K+
(A) S m mole –1
(B) S m mole
2 –1 (C) Velocities of both K+ and NO3– are nearly the same
(C) S–2 m2 mole (D) S2 m2 mole–2 (D) KNO3 is highly soluble in water
Chem i str y | 17.39

Q.11 The reduction potential of hydrogen half-cell will


3
be negative if (2011) CH3OH( ) + O2 (g) → CO2 (g) + 2H2O( ) at 298K
2
(A) P(H ) = 1 atm and [H+] = 2.0 M standard Gibb’s energies of formation for CH3OH(l),
2
(B) P(H ) = 1 atm and [H+] = 1.0 M H2O(ll) and CO2 (g) are -166.2, -237.2 and 394.4 kJ mol1
2
respectively. If standard enthalpy of combustion of
(C) P(H ) = 2 atm and [H+] = 1.0 M methanol is -726kJ mol-1, efficiency of the fuel cell will
2
(D) P(H ) = 2 atm and [H+] = 2.0 M be (2009)
2
(A) 80 % (B) 87% (C) 90% (D) 97%

Q.12 The cell, Zn|Zn (1M) ||Cu (1M) |Cu ( Ecell = 1.10
2+ 2+

V) was allowed to be completely discharged at 298 K. Q.18 Given:



EFe = 
−0.036V, EFe =
−0.439V .
3+ 2+
The relative concentration of Zn2+ to /Fe /Fe
The value of standard electron potential for the change,
 Zn2+ 
3+
Cu  is (2007) + e − →Fe 2+ (aq) will be: 
2+
 2+ Fe(aq) (2009)
 [Cu ] 
(A) -0.072 V (B) 0.385 V (C) 0.770 V (D) -0.270
(A) Antilog (24.08) (B) 37.3
(C) 1037.3 (D) 9.65 × 104 Q.19 The reduction potential of hydrogen half-cell will
be negative if:  (2011)
Q.13 The standard reduction potential for Fe2+/ Fe and (A) p(H2 ) = 1 atm and [H+ ] =1.0 M
Sn2+/Sn electrodes are –0.44 and –0.14 volt respectively,
For the given cell reaction Fe2+ + Sn → Fe + Sn2+, the (B) p (H2) =2 atm and [H+ ] =1.0 M
standard EMF is (1990) (C) p (H2) = 2 atm and [H+ ] = 2.0 M
(A) +0.30 V (B) –0.58 V (C) +0.58 V (D) –0.30 V (D) p (H2) =1 atm and [H+ ] = 2.0 M

Q.14 Given E −0.036V, E 2+


= −0.439V
=
Fe3+ /Fe Fe /Fe Q.20 The standard reduction potentials for Zn2+/ Zn,
The value of standard electrode potential for the Ni2+/ Ni, and Fe2+/ Fe are –0.76, –0.23 and –0.44 V
change, Fe3(aq) + e− → Fe2+ (aq) will be →
+
respectively. The reaction X + Y2+ X2+ + Y will be
(A) –0.072 V (B) 0.385 V spontaneous when: (2012)
(C) 0.770 V (D) –0.270 V (A) X = Ni, Y = Fe (B) X = Ni, Y = Zn
(C) X = Fe, Y = Zn (D) X = Zn, Y = Ni
Q.15 For the redox reaction:
Zn(s) + Cu2+ (0.1M) → Zn2+ (1M) + Cu(2) taking place in Q.21 Given: E°Cr3+ /Cr3+ =
−0.74V; E° −
MnO /Mn2 +
1.51 V
=
4

a cell, Ecell is 1.10 volt. Ecell for the cell will be
E° 2 − 3+
= 1.33
= V; E° − 1.36 V
Cr2 O7 /Cr Cl/Cl
 RT 
 2.303 = 0.0591   (2003) Based on the data given above, strongest oxidising
 F 
agent will be: (2013)
(A) 2.14 volt (B) 1.80 volt

(C) 1.07 volt (D) 0.82 volt (A) Cl (B) Cr3+ (C) Mn2+ (D) MnO 4

  Q.22 The equivalent conductance of NaCl at


Q.16 Given E
Cr 3 + /Cr
=
−0.72V, EFe 2+
/Fe
=
−0.42V .
concentration C and at infinite dilution are λC and λ∞,
The potential for the cell Cr|Cr3+ (0.1M)||Fe2+(0.01M)|Fe
is (2008) respectively. The correct relationship between λC and λ∞,
is given as (Where the constant B is positive)  (2014)
(A) 0.26 V (B) 0.399 v (C) -0.339 V (D) -0.26 V
(A) λC = λ∞ + (B)C (B) λC = λ∞ - (B)C
Q.17. In a fuel cell methanol is used as fuel and oxygen
(C) λC = λ∞ - (B) C (D) λC = λ∞ + (B) C
gas is used as an oxidizer. The reaction is
1 7 . 4 0 | Electrochemistr y

Q.23 Given below are the half-cell reactions Q.24 Two Faraday of electricity is passed through a
 (2014) solution of CuSO4. The mass of copper deposited at the
cathode is: (at. mass of Cu = 63.5 amu) 
Mn2+ + 2e– → Mn; E° = — 1.18 V  (2015)
(Mn + e → Mn ); E° = + 1.51 V
3+ – 2+
(A) 0 g (B) 63.5 g (C) 2 g (D) 127 g
The E° for 3 Mn → Mn + 2Mn will be
2+ 3+

(A) –2.69 V; the reaction will not occur


(B) –2.69 V; the reaction will occur
(C) –0.33 V; the reaction will not occur
(D) –0.33 V; the reaction will occur

JEE Advanced/Boards

Exercise 1 Q.6 The Edison storage cell is represented as Fe(s) |


FeO(s) | KOH (aq) | Ni2O3(s) |Ni(s) the half-cell reaction are
Q.1 The standard reduction potential values, E° (Bi3+|Bi) Ni2O3(s) + H2O (i) + 2e– l 2NiO(s) + 2OH–,
and E° (Cu2+|Cu) are 0.226 V and 0.344 V respectively.
A mixture of salts of bismuth and copper at unit E° = +0.40 V
concentration each is electrolyzed at 25ºC. To what
FeO(s) + H2O (l) + 2e– l Fe(s) + 2OH–,
value can [Cu2+] be brought down before bismuth starts
to deposit, in electrolysis. E° = –0.87 V

Q.2 The cell Pt, H2 (1 atm) | H+ (pH = x) || Normal calomel (i) What is the cell reaction?
electrode has an EMF of 0.67 V at 25°C. Calculate the pH (ii) What is the cell e.m.f.? How does it depend on the
of the solution. The oxidation potential of the calomel concentration of KOH?
electrode on hydrogen scale is –0.28 V.
(iii) What is the maximum amount of electrical energy
Q.3 Voltage of the cell Pt, H2 (1 atm) |HOCN (1.3 × 10–3 that can be obtained from one mole of Ni2O3?
M) ||Ag+ (0.8 M)| Ag(s) is 0.982 V. Calculate the Ka for
HOCN. Neglect [H+] because of oxidation of H2 (g). Q.7 The standard reduction potential for Cu2+/Cu is
0.34 V. Calculate the reduction potential at pH = 14 for
Ag+ + e → Ag(s) = 0.8 V.
the above couple. Ksp of Cu (OH) 2 is 1 × 10–19.
Q.4 Calculate the potential of an indicator electrode
Q.8 Determine the degree of hydrolysis and hydrolysis
versus the standard hydrogen electrode, which
constant of aniline hydrochloride in M/32 solution of
originally contained 0.1 M MnO4– and 0.8 M H+ and
salt at 298 K from the following cell data at 298 K.
which was treated with 90% of the Fe2+ necessary to
reduce all the MnO4– to Mn+2. Pt|H2 (1 atm) | H+ (1M) ||M/32 C6H5NH3Cl|H2 (1 atm) | Pt;
Ecell = –0.188 V
MnO4– + 8H+ + 5e → Mn2+ + 4H2O,
E° = 1.51 V Q.9 The e.m.f of the cell, Pt|H2(1 atm), | H+ (0.1 M, 30 ml)
|| Ag+(0.8 M)|Ag is 0.9 V. Calculate the e.m.f when 40 ml
Q.5 Calculate the e.m.f of the cell of 0.05 M NaOH is added.

Pt, H2 (1.0 atm) | CH3COOH (0.1 M) || NH3 (aq, 0.01M) | Q.10 The e.m.f of the cell Ag | AgI | KI (0.05 M) || AgNO3
H2 (1.0 atm), Pt (0.05 M) | Ag is 0.788 V. Calculate the solubility product
Ka (CH3COOH) = 1.8 × 10–5, of AgI.
Kb (NH3) = 1.8 × 10–5.
Chem i str y | 17.41

Q.11 Consider the cell Q.20 Estimate the cell potential of a daniel cell having
1 M Zn++ & originally having 1 M Cu++ after sufficient
Ag | AgBr(s) Br– || AgCl(s), Ag | Cl– at 25ºC. The solubility
NH3 has been added to the cathode compartment
product constants of AgBr & AgCl are respectively 5 ×
to make NH3 concentration 2M. Kf for [Cu (NH3)4]2+
10–13 & 1 × 10–10. For what ratio of the concentration of
= 1. × 1012, E° for the reaction,
Br– and Cl– ions would the e.m.f of the cell be zero?
Zn + Cu2+ → Zn2+ + Cu is 1.1 V.
Q.12 The pKsp of Agl is 16.07. If the E° value for Ag+|Ag
is 0.7991 V. Find the E° for the half-cell reaction AgI (s)
Q.21 The normal oxidation potential of Zn referred to
+ e– → Ag + I–
SHE is 0.76 and that of Cu is –0.34 V at 25ºC. When
excess of Zn is added to CuSO4, Zn displaces Cu2+ till
Q.13 For the galvanic cell: Ag AgCl(s) | KCl (0.2 M) || KBr
equilibrium is reached. What is the ratio of Zn2+ to Cu2+
(0.001 M)| AgBr(s) | Ag, Calculate the EMF generated
ions at equilibrium?
and assign correct polarity to each electrode for a
spontaneous process after taking into account the cell
Q.22 Kd for complete dissociation of [Ag(NH3)2]+ into
reaction at 25ºC.
Ag+ and 2NH3 is 6 × 10–8. Calculate E for the following
[Ksp (AgCl)] –2.8 × 10–10; Ksp (AgBr) – 3.3 × 10–13] half reaction; Ag(NH3)2+ + e– → Ag + 2NH3
Ag+ + e– → Ag, Eº = 0.799 V
Q.14 Given, E° = –0.268 V for the Cl–|PbCl2|Pb couple
and –0.126 V for the Pb2+|Pb couple, determine Ksp for Q.23 The overall formation constant for the reaction of
PbCl2 a 25ºC? 6 mole of CN– with cobalt (II) is 1 × 1019. The standard
reduction potential for the reaction
Q.15 Calculate the voltage, E, of the cell at 25ºC [Co(CN]6]3– e– → Co(CN)64– is –0.83 V. Calculate the
Mn(s) | Mn (OH2) (s) |Mn2+ (xM), OH– (1.00 × 10–4M) || formation constant of [Co(CN)6]3– Given Co3++ e– →
Cu2+ (0.675 M) | Cu(s) given that Ksp = 1.9 × 10–13 for Mn Co2+ ; E° =1.82 V
(OH) 2(s) E (Mn2+/Mn) = –1.18 V
Q.24 Calculate E° for the following reactions at 298 K,
Q.16 Calculate the voltage, E, of the cell Ag(NH3)2+ + e– → Ag + 2NH3
Ag(s) | AgIO3(s) | Ag+(x M), HIO3 (0.300 M) || Zn2+
Ag(CN)2– e– → Ag + 2CN–
(0.175 M) | Zn(s) if Ksp = 3.02 × 10–8 for AgIO3(s) and Ka
= 0.162 for HIO3. Given: E – 0.7991 V,
Ag+ |Ag

Q.17 The voltage of the cell Kins [Ag(NH3)2+] = 6.02 × 10–8 and
Pb(s) || PbSO4(s) | NaHSO4 (0.600 M) || Pb2+ (2.50 × Kins[Ag(CN)2–] = 1.995 ×10–19
10–5M) | Pb(s) is E = +0.061 V. Calculate K2 = [H+] [SO42–
]/ [HSO4–], the dissociation constant for HSO4–. Given Q.25 Calculate the equilibrium constant for the reaction:
Pb(s) + SO42–(aq) → PbSO4(s) + 2e– (E° = 0.356) E° (Pb2+/
3Sn(s) + 2Cr2O72– + 28H+ → 3Sn4+ + 4Cr3+ + 14H2O
Pb) = –0.126 V
E° for Sn/Sn2+ = 0.136 V E° for Sn2+/Sn4+ = – 0.154 V
Q.18 The voltage of the cell E° for Cr2O72–/Cr3+ = 1.33 V
Zn(s) | Zn(CN)42–(0.450M), CN–(2.65 × 10–3M) || Zn2+
(3.84 × 10–4M) | Zn(s) is E = + 0.099 V. Calculate the Q.26 Calculate the equilibrium concentration of all ions
constant Kf for in an ideal solution prepared by mixing 25.00 mL of
0.100 M Ti+ with 25.00 mL of 0.200M Co3+.
Zn2+ + 4CN– → Zn(CN)42–, the only Zn2+ + CN⁻
E° (Ti+/Ti3+) =–1.25 V; E° (Co3+/Co2+) = 1.84 V
complexation reaction of importance.
Q.27 Same quantity of electricity is being used to
Q.19 Given the standard reduction potentials Ti+ + e– → liberate iodine (at anode) and a metal x (cathode).
Ti, E° = –0.34 V and Ti3+ + 2e– →Ti+, E° = 1.25 V. Examine The mass of x deposited is 0.617 g and the iodine is
the spontaneity of the reaction, 3Ti+ → 2Ti + Ti3+. Also completely reduced by 46.3 cc of 0.124 M sodium
find E° for this disproportionation. thiosulphate. Find the equivalent mass of x.
1 7 . 4 2 | Electrochemistr y

Q.28 In a fuel cell, H2 & O2 react to produce electricity. battery. Note that the water is produced by the reaction
In the process, H2 gas is oxidized at the anode & O2 at as H2SO4 is used up. Overall reaction is
the cathode. If 67.2 liter of H2 at STP react in 15 minutes,
Pb(s) + PbO2(s) + 2H2SO4 (l) → 2PbSO4(s) + 2H2O (l)
what is the average current produced? If the entire
current is used for electrode deposition of Cu from Cu Q.36 100ml CuSO4 (aq) was electrolyzed using inert
(II) solution, how many grams of Cu will be deposited? electrodes by passing 0.965 A till the pH of the
Anode: H2 + 2OH– → 2H2O + 2 e– resulting solution was 1. The solution after electrolysis
Cathode: O2 + 2H2O + 4e– → 4OH– was neutralized, treated with excess KI and titrated
with 0.04 M Na2S2O3. Volume of Na2S2O3 required was
Q.29 One of the methods of preparation of per 35 ml. Assuming no volume change during electrolysis,
disulphuric acid, H2S2O8, involve electrolytic oxidation calculate:
of H2S O4 at anode (2H2S O4 → H2S2O8 + 2H+ + 2e–) (a) Duration of electrolysis if current efficiency is 80%
with oxygen and hydrogen as by-products. In such (b) Initial concentration (M) of CuSO4.
an electrolysis, 9.722 L of H2 and 2.35 L of O2 were
generated at STP. What is the weight of H2S2O8 formed? Q.37 An external current source giving a current of 0.5
A was joined with Daniel cell and removed after 10 hrs.
Q.30 During the discharge of a lead storage battery Before passing the current the LHE and RHE contained
the density of sulphuric acid fell from 1.294 to 1.139 g. 1L each of 1M Zn2+ and Cu2+ respectively. Find the EMF
mL–1 H2SO4 of density 1.294 g mL–1 is 39% and that of supplied by the Daniel cell after removal of the external
density 1.139 g mL–1 is 20% by weight. The battery holds current source. E of Zn2+/Zn and Cu2+/Cu at 25ºC is
3.5 L of acid and the volume practically remains constant
– 0.76 and + 0.34 V respectively.
during the discharge. Calculate the number of ampere
hours for which the battery must have been used. The
Q.38 Determine at 298 for cell
discharging reactions are:
Pt | Q, QH2, H+ || 1M KCl | Hg2Cl2(s) | Hg (l) | Pt
Pb + SO42– → PbSO4 + 2e– (anode)
(a) Its e.m.f when pH = 5.0
PbO2 + 4H+ + SO42– + 2e– →PbSO4+ 2H2O (cathode)
(b) The pH when Ecell = 0
Q.31 A current of 3 amp was passed for 2 hour through (c) The positive electrode when pH = 7.5
a solution of CuSO4, 3g of Cu2+ ions were deposited as
Given E° RP (RHS) = 0.28, E° RP (LHS) = 0.699
Cu at cathode. Calculate percentage current efficiency
of the process.
Q.39 At 25ºC, ∆Hf (H2O, l) = –56700 cal/mole and
Q.32 An acidic solution of Cu salt containing 0.4 g of
2+ energy of ionization of H2O (l) = 19050 Cal/mol. What
Cu2+ is electrolyzed until all the copper is deposited. The will be the reversible EMF at 25ºC of the cell?
electrolysis is continued for seven more minutes with Pt | H2 (g) (1 atm) | H+ || OH– | O2 (g) (1 atm) | Pt, if at
the volume of solution kept at 100 ml and the current 26ºC the e.m.f increase by 0.001158 V.
at 1.2 amp. Calculate the volume of gases evolved at
NTP during the entire electrolysis. Q.40 Calculate the cell potential of a cell having
reaction: Ag2S + 2e– →2Ag + S2– in a solution buffered
Q.33 In the refining of silver by electrolytic method at pH = 3 and which is also saturated with 0.1 M H2S.
what will be the weight of 100 gm. Ag anode if
For H2S: K1 = 10–8 and K2 = 1.1 × 10–13, Ksp (Ag2S) = 2 ×
5 ampere current is passed for 2 hours? Purity of silver
is 95% by weight. 10–49, E = −0.8 .
Ag+ /Ag

Q.34 Dal Lake has water 8.2 × 1012 liter approximately. Q.41The equivalent conductance of 0.10N solution
A power reactor produces electricity at the rate of of MgCl2 is 97.1 mho cm2 equi–1 at 25ºC. A cell with
1.5 × 106 coulomb per second at an appropriate voltage. electrode that are 1.5 cm2 in surface area and 0.5 cm
How many years would it take to electrolyze the lake? apart is filled with 0.1 N MgCl2 solution. How much
current will flow when potential difference between the
Q.35 A lead storage cell is discharged which causes the
electrodes is 5 volt?
H2SO4 electrolyte to change from a concentration of
34.6% by weight (density 1.261 g ml–1 at 25ºC) to 27% Q.42 A dilute aqueous solution of KCl was placed
by weight. The original volume of electrolyte is one between two electrodes 10 cm apart, across which
liter. Calculate the total charge released at anode of the a potential of 6 volt was applied. How far would the
Chem i str y | 17.43

K+ ion move in 2 hours at 25ºC? Ionic conductance of K+ Q.2 The charge required for the oxidation of one mole
ion at infinite dilution at 25ºC is 73.52 ohm–1 cm2 mole–1? Mn3O4 into MnO42– in presence of alkaline medium is
(A) 5 × 96500C (B) 96500 C
Q.43 When a solution of specific conductance
1.342 ohm–1 meter–1 was placed in a conductivity cell (C) 10 × 96500 C (D) 2 × 96500 C
with parallel electrodes, the resistance was found to be
170.5 ohm. Area of electrodes is 1.86×10–4m2. Calculate Q.3 A solution of sodium sulphate in water is
separation of electrodes. electrolyzed using inert electrodes. The products at the
cathode and anode are respectively.
Q.44 The specific conductance at 25ºC of a saturated
solution of SrSO4 is 1.482 × 10–4 ohm–1 cm–1 while that (A) H2 , O2 (B) O2 , H2 (C) O2, Na (D) None
of water used is 1.5 × 10–6 mho cm–1. Determine at
25ºC the solubility in gm. per liter of SrSO4 in water. Q.4 A hydrogen electrode X was placed in a buffer
Molar ionic conductance of Sr2+ and SO42– ions at solution of sodium acetate and acetic acid in the ratio
infinite dilution are 59.46 and 79.8 ohm–1 cm2 mole–1 a: b and another hydrogen electrode Y was placed in
respectively. [Sr = 87.6, S =32, O = 16] a buffer solution of sodium acetate and acetic acid in
the ratio b: a. If reduction potential values for two cells
Q.45 Calculate the solubility and solubility product are found to be E1 and E2 respectively w.r.t. standard
of Co2 [Fe(CN)6] in water at 25ºC from the following hydrogen electrode, the pKa value of the acid can be
data: Conductivity of a saturated solution of given as
Co2[Fe(CN)6] is 2.06 × 10–6Ω–1cm–1 and that of water
used 4.1 × 10–7Ω–1cm–1.The ionic molar conductivities E1 + E2 E2 − E1 E1 + E2 E1 − E2
(A) (B) (C) − (D)
of Co2+ and Fe(CN)64– are 86.0 Ω–1cm2 mole–1 and 0.118 0.118 0.118 0.118
444.0 Ω–1cm–1 mole–1.
Q.5 The conductivity of a saturated solution of Ag3PO4
Q.46 A sample of water from a large swimming pool has
is 9 × 10–6 S m–1 and its equivalent conductivity is
a resistance of 9200 Ω at 25ºC when placed in a certain
1.50 × 10–4 S m–2 equivalent–1. The Ksp of Ag3PO4 is:
conductance cell. When filled with 0.02 M KCl solution,
the cell has a resistance of 85 Ω at 25ºC. 500 gm. of (A) 4.32 × 10–18 (B) 1.8 × 10–9
NaCl were dissolved in the pool, which was thoroughly (C) 8.64 × 10–13 (D) None of these
stirred. A sample of this solution gave a resistance of
7600 Ω. Calculate the volume of water in the pool.
Q.6 Equal volumes of 0.015 M CH3COOH & 0.015 M
Given: Molar conductance of NaCl at that concentration
NaOH are mixed together. What would be molar
is 126.5 Ω–1cm–1mol–1 and molar conductivity of KCl at
conductivity of mixture if conductivity of CH3COONa is
0.02 M is 138 Ω–1 cm2 mole–1.
6.3 × 10–4 S cm–1?
(A) 8.4 S cm2 mole–1 (B) 84 S cm2 mole–1
Exercise 2 (C) 4.2 S cm2 mole–1 (D) 42 S cm2 mole–1
Single Correct Choice Type
Multiple Correct Choice Type
Q.1 An aqueous solution containing one mole per liter
each of Cu(NO3)2 AgNO3, Hg2(NO3)2, Mg(NO3)2 is being Q.7 Pick out the correct statements among the
electrolyzed by using inert electrodes. The value of following from inspection of standard reduction
standard potentials are potentials (Assume standard state conditions).

E − 0.80V, E − 0.79V, Cl2 (aq.) + 2e → 2Cl–(aq.) E = +1.36 volt


Ag+ |Ag Hg22+ |Hg Cl2 /Cl–

E − 0.34V and E −2.3V


= Br2 (aq.) + 2e → 2Br–(aq.) E = + 1.09 volt
Cu2+|Cu Mg2+|Mg Br2 /Br –

With increasing voltage, the sequence of deposition of I2(s) + 2e → 2I–(aq.) E = + 0.54 volt
I 2 /l–
metals on the cathode will be
(A) Ag, Hg, Cu, Mg (B) Mg, Cu, Hg, Ag S2O28− (aq.) + 2e → 2SO24− (aq.)
(C) Ag, Hg, Cu (D) Cu, Hg, Ag E = + 2.00 volt
S2O32− /SO24−
1 7 . 4 4 | Electrochemistr y

2− Assertion Reasoning Type


(A) Cl2 can oxidize SO 4 from solution
(A) 
Statement-I is true, statement-2 is true and
(B) Cl2 can oxidize Br– and I– from aqueous solution statement-II is correct explanation for statement-I
(C) S2O8
2−
can oxidize Cl–, Br– and I– from aqueous (B) 
Statement-I is true, statement-II is true and
statement-II is NOT the correct explanation for
solution
statement-I.
2−
(D) S2O8 is added slowly, Br– can be reduce in presence (C) Statement-I is true, statement-II is false
of Cl– (D) Statement-I is false, statement-II is true

Q.8 Which of the following arrangement will produce Q.12 Statement-I: The voltage of mercury cell remains
oxygen at anode during electrolysis? constant for long period of time.
(A) Dilute H2SO4 solution with Cu electrodes. Statement-II: It because net cell reaction does not
(B) Dilute H2SO4 solution with inert electrodes. involve active species.

(C) Fused NaOH with inert electrodes.


Q.13 Statement-I: We can add the electrode potential
(D) Dilute NaCl solution with inert electrodes. in order to get electrode potential of net reaction.
Statement-II: Electrode potential is an intensive
Q.9 If 270.0 of water is electrolyzed during an property.
experiment performed by Miss Abhilasha with 75%
current efficiency then Q.14 Statement-I: The SRP of three metallic ions A+,
(A) 168 L of O2 (g) will be evolved at anode at 1 atm & B2+ C3+ are –0.3, –0.5, 0.8 volt respectively, so oxidizing
273 K power of ions is C3+ > A+ > B2+.
(B) Total 504 L gases will be produced at 1 atm & 273 K Statement-II: Higher the SRP, higher the oxidizing
power
(C) 336 L of H2(g) will be evolved at anode at 1 atm &
273 K
Comprehension type
(D) 45 F electricity will be consumed
Paragraph 1: A sample of water from a large swimming
pool has a resistance of 10000 Ω at 25ºC when placed
Q.10 During discharging of lead storage battery, which
in a certain conductance cell. When filled with 0.02 M
of the following is/are true?
KCl solution, the cell has a resistance of 100 Ω at 25ºC.
(A) H2SO4 is produced 585 gm. of NaCl were dissolved in the pool, which was
(B) H2O is consumed thoroughly stirred. A sample of this solution gave a
resistance of 8000 Ω.
(C) PbSO4 is formed at both electrodes
[Given: Molar conductance of NaCl at that concentration
(D) Density of electrolytic solution decreases is 125 Ω–1cm2 mole–1 and molar conductivity of KCl at
0.02 M is 200 Ω–1 cm2 mole–1.]
Q.11 The EMF of the following cell is 0.22 volt.
Q.15 Cell constant (in cm–1) of conductance cell is:
Ag(s) | AgCl(s) |KCl (1M) |H+ (1M) |H2 (g) (1atm); Pt(s)
(A) 4 (B) 0.4 (C) 4 × 10–2 (D) 4 × 10–5
Which of the following will decreases the EMF of cell
(A) Increasing pressure of H2 (g) from 1 atm to 2 atm
Q.16 Conductivity (Scm–1) of H2O is:
(B) Increasing Cl concentration in Anodic compartment

(A) 4 × 10–2 (B) 4 × 10–3
(C) Increasing H concentration in cathodic compartment
+
(C) 4 × 10–5 (D) None of these
(D) 
Decreasing KCl concentration in Anodic
compartment. Q.17 Volume (in Liters) of water in the pool is:
(A) 1.25 × 105 (B) 1250
(C) 12500 (D) None of these
Chem i str y | 17.45

Paragraph 2: Copper reduces NO3– into NO and NO2 Q.3 The half-cell reaction for rusting of iron are:
depending upon conc. Of HNO3 in solution. Assuming 1
2H+ + 2e– + O → H2O (l); E° = + 1.23 V
[Cu2+] = 0.1 M2 and PNO = PNO = 10–3 atm and using 2 2
2
given data answer the following questions:
Fe2+ + 2e– → Fe(s), E = –0.44 V
E  = + 0.34 volt
Cu2 + /Cu ∆Gº (in kJ) for the reaction is  (2005)

E = + 0.96 volt (A) –76 (B) –322 (C) –122 (D) –176
NO3− /NO

E − = +0.79 volt
NO3 /NO2 Q.4 Electrolysis of dilute aqueous NaCl solution was

RT carried out by passing 10 mA current. The time required
At 298 K (2.303) = 0.06 volt to liberate 0.01 mole of H2 gas at the cathode is 
F
(1 F = 96500 C mole–1) (2008)
Q.18 ECell for reduction of NO3– → NO by Cu(s), when (A) 9.65 × 104 s (B) 19.3 × 104 s
[HNO3] = 1 M is [At T = 298]
(C) 28.95 × 104 (D) 38.6 × 104 s
(A) ~0.61 (B) ~0.71 (C) ~ 0.51 (D) ~0.81

Q.5 AgNO3 (aqueous) was added to an aqueous KCl


Q.19 At what HNO3 concentration thermodynamic solution gradually and the conductivity of the solution
tendency for reduction of NO3– into NO and NO2 by was measured. The plot of conductance (Λ) versus the
copper is same? volume of AgNO3 is (2011)
(A) 101.23 M (B) 100.56 M (C) 100.66 M (D) 100.12 M

Match the Columns V V

Q.20

Column I Column II Volume Volume


(P) (Q)
(Electrolysis product using
inert electrode)
V V
(A) Dilute solution of HCl (p) O2 evolved at anode
(B) Dilute solution of NaCl (q) H2 evolved at cathode
(C) Concentrated Solution (r) Cl2 evolved at anode Volume Volume
of NaCl (R) (S)

(D) AgNO3 solution (s) Ag deposition at cathode (A) (P) (B) (Q) (C) (R) (D) (S)

Q.6 Consider the following cell reaction,


Previous Years' Questions 2Fe(s) + O2 (g) + 4H+ (aq) →
2Fe2+ (aq) + 2H2O (l), E = 1.67 V
Q.1 In the electrolytic cell, flow of electrons is from
 (2003) At [Fe2+] = 10–3 M, P (O2) = 0.1 atm and pH = 3, the cell
(A) Cathode to anode is solution potential at 25ºC is  (2011)
(B) Cathode to anode through external supply (A) 1.47 V (B) 1.77 V (C) 1.87 V (D) 1.57 V
(C) Cathode to anode through internal supply
(D) Anode to cathode through internal supply Q.7 For the reduction of NO3– ion in an aqueous
solution E° is + 0.96 V. Values of E° for some metal ion
are given below
Q.2 Zn|Zn2+ (a = 0.1 M) || Fe2+ (a = 0.01 M) | Fe.
V2+ (aq) + 2e– → V E° = –1.19 V
The e.m.f of the above cell is 0.2905 V. Equilibrium
constant for the cell reaction is  (2004) Fe3+ (aq) + 3e– → Fe E° = –0.04 V
(A) 100.32/0.059 (B) 100.32/0.0295 Au3+ (aq) +3e– → Au E° = + 1.40 V
(C) 100.26/0.0295 (D) 100.32/0.295
1 7 . 4 6 | Electrochemistr y

Hg2+ (aq) +2e– → Hg E° = + 0.86 V A 4.0 M aqueous solution of NaCl is prepared and 500
mL of this solution is electrolyzed. This lead to the
The pair (s) of metals that is (are) oxidized by NO3– in
evolution of chlorine gas at one of the electrodes
aqueous solution is (are)  (2009)
(Atomic mass: Na = 23, Hg = 200, 1 F = 96500C). (2007)
(A) V and Hg (B) Hg and Fe
(C) Fe and Au (D) Fe and V Q.11 The total number of moles of chlorine gas evolved is
(A) 0.5 (B) 1.0 (C) 2.0 (D) 3.0
Paragraph 1: Tollen’s reagent is used for the detection
of aldehydes. When a solution of AgNO3 is added to
glucose with NH4OH then gluconic acid is formed. Q.12 If the cathode is a Hg electrode, the maximum
weight (in gram) of amalgam formed this solution is
Ag+ + e– → Ag; E red = 0.80 V
(A) 200 (B) 255 (C) 400 (D) 446
RT F
[Use 2.303 × = 0.0592 and = 38.92 at 298 K]
 F RT (2006) Q.13 The total charge (coulombs) required for complete
electrolysis is

Q.8 2Ag+ + C6H12O6 + H2O → 2Ag(s) C6H12O7 + 2H+ (A) 24125 (B) 48250 (C) 96500 (D) 193000

Find in K of this reaction.


Paragraph 3: Redox reaction play a pivotal role in
(A) 66.13 (B) 58.38 (C) 28.30 (D) 46.29 chemistry and biology. The values of standard redox
potential ( E ) of two half-cell
Q.9 When ammonia is added to the solution, pH is Reactions decide which way the reaction is expected to
raised to 11. Which half-cell reaction is affected by pH proceed. A simple example is a Daniel cell in which zinc
and by how much? goes into solution and copper gets deposited. Given

(A) Eoxi will increase by a factor of 0.65 from Eoxi below are a set of half-cell reaction (acidic medium)

along with their Eº (V with respect to normal hydrogen
(B) Eoxi will decrease by a factor of 0.65 from Eoxi electrode) values. Using this data obtain the correct
(C) Ered will increase by a factor of 0.65 from Ered
 explanations to

(D) Ered will decrease by a factor of 0.65 from Ered


 I2 + 2e– → 2I– E = 0.54
Cl2 + 2e– → 2Cl– E = 1.36
Q.10 Ammonia is always added in this reaction. Which Mn3+ + e– → Mn2+ E = 1.50
of the following must be incorrect?
Fe3+ + e– → Fe2+ E = 0.77
(A) NH3 combines with Ag to form a complex
+
O2 + 4H+ + 4e– → 2H2O E = 1.23 (2007)
(B) Ag (NH3)2 is a stronger oxidizing reagent than Ag
+ +

(C) In absence of NH3 silver salt of gluconic acid is Q.14 Among the following, identify the correct
formed statement
(D) NH3 has no effect on the standard reduction
(A) Chloride ion is oxidized by O2
potential of glucose/gluconic acid electrode
(B) Fe2+ is oxidized by iodine
Paragraph 2: Chemical reactions involve interaction (C) Iodide ion is oxidized by chlorine
of atoms and molecules. A large number of atoms/
(D) Mn2+ is oxidized by chlorine
molecules (approximately 6.023 × 1023) are present
in a few grams of any chemical compound varying
with their atomic/molecular masses. To handle such Q.15 While Fe3+ is stable, Mn3+ is not stable in acid
large numbers conveniently, the mole concept was solution because
introduced. This concept has implications in diverse (A) O2 oxidizes Mn2+ to Mn3+.
areas such as analytical chemistry, biochemistry,
electrochemistry and radiochemistry. The following (B) O2 oxidizes both Mn2+ to Mn3+ and Fe2+ to Fe3+
example illustrates a typical case, involving chemical/ (C) Fe3+ oxidizes H2O to O2
electrochemical reaction, which requires a clear (D) Mn3+ oxidizes H2O to O2
understanding of the mole concept.
Chem i str y | 17.47

Q.16 Sodium fusion extract, obtained from aniline, on Under standard conditions, the number of moles of M+
treatment with iron (II) sulphate and H2SO4 in presence oxidized when one mole of X is converted to Y is
of air gives a Prussian blue precipitate. The blue color is [F = 96500 C mol/L]  (2015)
due to the formation of
(A) Fe4 [Fe (CN) 6]3 (B) Fe3 [Fe (CN) 6]2 Q.20 The molar conductivity of a solution of a weak
(C) Fe4 [Fe (CN) 6]2 (D) Fe3 [Fe (CN) 6]3 acid HX (0.01 M) is 10 times smaller than the molar
conductivity of a solution of a weak acid HY (0.10 M).
If λ ≈ λ 0Y − , the difference in their pKa values, a pKa
0
Paragraph 4: The concentration of potassium ions X−
inside a biological cell is at least twenty times higher (HX) - pKa (HY), is consider degree of ionization of both
than the outside. The resulting potential difference acids to be << 1)  (2015)
across the cell is important in several processes such as
transmission of nerve impulses and maintaining the ion
Q.21 For the following electrochemical cell at 298 K,
balance. A simple model for such a concentration cell
involving a metal M is: Pt(s) | H2(g, 1 bar) | H+ (aq, 1M)|| M4+(aq), M2+ (aq) | Pt(s)
M(s) | M+ (aq; 0.05 molar) || M+ (aq; 1 molar) | M (s)
M2+ (aq) 
For the above electrolytic cell the magnitude of the cell Ecell = 0.092 V when 4+
= 10 x .
potential | Ecell | = 70 mV.  (2010) M (aq) 
Given: E° 4 + 2 + 0.151 RT
Q.17 For the above cell = = V; 2.303 0.059 V
M /M F
(A) Ecell < 0 ; ∆G > 0 (B) Ecell > 0 ; ∆G < 0 The value of x is  (2016)
(C) Ecell < 0 ; ∆Gº > 0 (D) Ecell > 0 ; ∆Gº < 0 (A) -2 (B) -1 (C) 1 (D) 2

Q.18 If the 0.05 molar solution of M+ is replaced by a Q.22 In a galvanic cell, the salt bridge  (2014)
0.0025 molar M+ solution, then the magnitude of the
cell potential would be (A) Does not participate chemically in the cell reaction.

(A) 35 mV (B) 70 mV (C) 140 mV (D) 700 mV (B) Stops the diffusion of ions from one electrode to
another.
Q.19 All the energy released from the reaction 0 –1 (C) Is necessary for the occurrence of the cell reaction.
X → Y. ∆ G° = -193 kJ mol/L
r (D) Ensures mixing of the two electrolytic solutions.
is used for oxidizing M as M → M
+ + 3+
+ 2e ,
-

E° = -0.25V.
1 7 . 4 8 | Electrochemistr y

PlancEssential Questions
JEE Main/Boards JEE Advanced /Boards

Exercise 1 Exercise 1
Q.3 Q.4 Q.8 Q.1 Q.6 Q.12

Q.9 Q.12 Q.16 Q.19 Q.22 Q.30

Q.23 Q.30 Q.35 Q.42 Q.45

Exercise 2 Exercise 2
Q.3 Q.5 Q.9 Q.4 Q.7 Q.16

Q.12 Q.15 Q.18 Q.18

Q.20

Previous Years' Questions


Previous Years' Questions
Q.5 Q.7 Q.17
Q.3 Q.8

Answer Key

JEE Main/Boards Q.21 0.1536 V


Q.22 –0.1615 V
Exercise 1
Q.23 (i) 0.2278 V ; (ii) 0.3692
Q.2 124 ohm cm mole
–1 2 –1
Q.24 0.91 V
Q.4 ∆rG° = -213.04 kJ, E°cell ==++1.104
1.104 V V Q.25 3.67 × 10–4
Q.5 λm = 124 Ω-1cm2mol-1 Q.26 Na, Ca, Mg and Al.
Q.8 0.219cm
-1
Q.27 2.96 V
Q.9 ∧m = 32. 765 cm2 mol–1 , ka = 2. 2 × 10–4 Q.28 (a) –0.118 V; (b) –0.0413 V; (c) (i) –0.0295 V
Q.10 3. 66 gm (ii) –0.59 V

Q.14 E° = 0. 34 V Q.29 1.3 × 102 ohm–1 cm2 equi–1

Q.19 (i) 0.2515 V; (ii) 0.8101 V (iii) 0.226 V (iv) 1.451 V;


(v) –0.268 V
Q.20 0.7288 V
Chem i str y | 17.49

Exercise 2
Single Correct Choice Type
Q.1 C Q.2 B Q.3 B Q.4 B Q.5 D Q.6 D
Q.7 B Q.8 A Q.9 A Q.10 B Q.11 B Q.12 B
Q.13 C Q.14 C Q.15 C Q.16 B Q.17 A Q.18 C
Q.19 C Q.20 D Q.21 C

Previous Years Questions


Q.1 D Q.2 D Q.3 B Q.4 C Q.5 B Q.6 D
Q.7 A Q.8 D Q.9 A Q.10 C Q.11 C Q.12 C
Q.13 D Q.14 C Q.15 C Q.16 A Q.17 D Q.18 C
Q.19 B Q.20 D Q.21 D Q.22 C Q.23 A Q.24 A

JEE Advanced/Boards
Exercise 1
Q.1 [Cu2+] = 10–4 M Q.2 pH = 6.61
Q.3 Ka = 6.74 × 10 4
Q.4 1.39 V
Q.5 – 0.46 V Q.6 (ii) 1.27V (ii) 245.1 kJ
Q.7 Eº = – 0.22 V Q.8 h =2.12 × 10–2, Kh = 1.43 × 10–5 M
Q.9 0.95 V Q.10 Ksp = 1.1 × 10–16
Q.11 [Br–]: [Cl–] = 1: 200 Q.12 Eº = –0.1511 V
Q.13 –0.037 V Q.14 1.536 × 10–5 M3
Q.15 1.66 V Q.16 –1.188V
Q.17 10 –2
Q.18 5.24 × 1016
Q.19 Eº = 1.59 V, non–spontaneous Q.20 Eº = 0.71 V
Q.21 [Zn ]/[Cu ] = 1.941 × 10
2+ 2+ 37
Q.22 0.373 V
Q.23 Kf = 8.227 × 1063 Q.24 0.372 V, –0.307 V
Q.25 K = 10268 Q.26 Ta+ = 5x10–9 ; Co3+ = 10–8
Q.27 Eq. wt. = 107.3 Q.28 643.33 amp, 190.5 g
Q.29 43.456 g Q.30 265 Amp. Hr.
Q.31 42.2 %
Q.32 V (O2) = 99.68 mL, V (H2) = 58.46 mL, Total vol. = 158.1 mL
Q.33 57.5894 gm. Q.34 1.9 million year
Q.35 2.4 × 105 coulomb Q.36 1250 s, 0.064 M
Q.37 1.143 V Q.38 (a) –0.124 V, (b) 7.1 (c) calomel electrode
Q.39 0.4414 V Q.40 –0.167 V
Q.41 0.1456 ampere Q.42 3.29 cm
1 7 . 5 0 | Electrochemistr y

Q.43 4.25 × 10–2 meter Q.44 0.1934 gm. /liter


Q.45 Ksp = 7.682 × 10–17 Q.46 2 × 105dm3

Exercise 2

Single Correct Choice Type

Q.1 C Q.2 C Q.3 A Q.4 C Q.5 A Q.6 B

Multiple Correct Choice Type

Q.7 B, C Q.8 B, C, D Q.9 A, B Q.10 C, D Q.11 D, C

Assertion Reasoning Type

Q.12 A Q.13 D Q.14 A

Comprehension Type

Paragraph - 1 Q.15 B Q.16 C Q.17 A

Paragraph - 2 Q.18 B Q.19 C

Match the Columns


Q.20 A → p, q; B → p, q; C → q, r; D → p, s

Previous Years' Questions


Q.1 C Q.2 B Q.3 B Q.4 B Q.5 D Q.6 D
Q.7 A, B, D Q.8 B Q.9 C Q.10 D Q.11 B Q.12 D
Q.13 D Q.14 C Q.15 D Q.16 A Q.17 B Q.18 C
Q.21 D Q.22 A
Chem i str y | 17.51

Solutions

JEE Main/Boards (iii) Sn + 2H+ → Sn2+ + H2


0. 02 0. 05
Exercise 1 n=2
−0.0591 [Sn2+ ]
Sol 1: Zn(s) | 2+
Zn(aq) || +
Ag(aq) | Ag(s) E = E° – log .PH
2 [H+ ]2 2
(i) Zinc electrode is negatively charged
0.05
E = E° – 0. 03 log
(ii) At anode: 0.04
2+ E = E° – 0. 0029
Zn(s) → Zn(aq) + 2e–
E = 0. 14 – 0. 0029
At cathode
⇒ E = 0. 1371 V
Ag+(aq) + e– → Ag(s)
(iv) Br2 + H2 → 2Br– + 2H+

k × 1000 2.48 × 10−2 × 1000 0.0591


Sol 2: ∧m = = E = E° – log [H+] 2[Br-] 2
M 0.2 2

∧m = 124 Ω-1 cm2 mol–1 = E° – 0. 02955 log (0. 01)2(0. 03)2


E = E° + 0. 208
Sol 3: (i) Reaction: E = 1. 09 + 0. 208
Mg ( s ) + Cu2+ ( aq. ) → Cu ( s ) + Mg2+ ( aq. ) E = 1. 298 V
       0. 0001 M                    0. 001 M
Sol 4: The formula of standard cell potential is
−1
2.303 RT  [Cu2+ ] 
E = E – log   E°cell Eright
= ° °
− Eleft
nF  [Mg2+ ] 
 
Use this link to get all values
0.0591 0.001
E = E – log
2 0.0001
°
E=
cell 0.344 − ( −0.76 )

E = E – 0. 02955 E°cell 0.344 + 0.076 V


=

E = E – 0. 03 E°cell = +1.104 V
= 2. 70 – 0. 03 In balanced reaction there are 2 electron are transferring
= 2. 67 V so that n = 2

(ii) Fe + 2H+ → Fe2+ + H2 Faraday constant, F=96500 C mol-1


  1     0.001 E°cell = +1.104 V
n=2
Use formula
0.0591 [Fe2+ ]PH
E= E – 
log 2
− n FE°cell
∆r G =
2 + 2
[H ]
0.001 × 1 Plug the value we get
E = E° – 0. 03 log
1 Then, =−2 × 96500 C mol−1 × 1.104 V
E = E° + 0. 09 = 0. 44 + 0. 09 = −212304 CV mol−1
⇒ E = 0. 53 V
= −212304 mol−1
1 7 . 5 2 | Electrochemistr y

Sol 11: We use the formula


= −212.304 kJ mol−1 = -213.04 kJ
k × 1000
∧m =
1000 C
Sol 5: ∧m =k×
C
0.0248 × 1000 C/M 0.001 0.010 0. 02 0. 05 0. 100
∧m = = 124 Ω–1cm2mol–1
0.2 102×k/sm–1 12.37 11.85 23. 15 55. 53 106.74

Sol 6: (i) Ca2+ + 2e⁻ → Ca ∧ ºm


12.37 11.85 11.575 11.106 10.674
20 S cm2/mol
Charge needed = 2 × nF = 2 × F = 1 F = 96500 C
40
(ii) Al + 3e⁻ → Al
3+
C 0. 03 0. 1 0. 14 0. 22 0. 31
Charge needed = (3nAl) × 96500C
∧m vs C
40
=3× × 96500 C = 4. 28 × 105 C
27

Sol 7: (i) H2O → O2 12.37

1 11.85
We have, H2O → O + 2H+ + 2e⁻
2 2 11.575
11.105
Charge required = 2 F = 1. 93 × 105 C 10.674

1 1
(ii) Fe2O + H2O → Fe2O3 + H++e– 0.001 0.1 0.02 0.05 0.1
2 2
Charge needed for 1 mole FeO = 1 F = 96500 C We have
∧m = ∧ º m – A C
Sol 8: k = 0. 146 × 10 s cm
–3 –1
At C = 0. 01,
R = 1500 Ω
∧m = 11. 85 = ∧ºm . A×0. 1 …(i)
G* = Rk = 0. 219 cm–1
At C = 0. 02
k 1000 × 7.896 × 10−5
Sol 9: ∧m = 1000 × = ∧m = 11. 575 = ∧ºm . A×0. 14 …(ii)
C 0.00241
∧m = 32. 765 cm2 mol–1 Subtracting
∧m 32.76
q= = 0. 01 A = 0. 275
∧ ºm 390.5
A = 6. 875
α = 0. 084
Cα 2 ∧ºm = 12. 5375 cm2 mol–1
ka = ;k = 2. 2 × 10–4
1−α a (putting A in (i))

Sol 10: Ni2+ + 2e⁻ → Ni


Sol 12: Ag+ + e⁻ → Ag
Charge supplied = 5 × 20 × 60 C = 6000 C
1.45
nAg = = 0. 0134
6000 108
Moles of Ni deposited =
96500 Charge, Q = nAg. F = 0. 0134 × 96500 C
6000
Mass of Ni deposited = × 59 = 3. 66 gm Q = 1295. 6 C
96500
Q 1295.6
t= =
I 1.5
t = 863. 735 s
Zn2+ + 2e⁻ → Zn
Chem i str y | 17.53

nAg ∆E1 = –nFEº = –0. 18 F


Q
Moles of Zn, nZn = =
2F 2 Cu+ + e → Cu,
w Ag 1
Wt. of Zn = nZn × 65 = × × 65 E° = 0. 50 V, n = 1
mAg 2
Wt. of Zn = 0. 43 gm ∆G2 = –nF E° = –0. 5 F

For Cu, Adding


Cu2+ + 2e⁻ → Cu Cu2+ + 2e → Cu,
Q
nCu = = nZn ∆G = ∆G1 + ∆G2, n = 2
2F
Wt. of copper = nCu × 63. 5 = 0. 426 gm –2F E°= –0. 18 F – 0. 5 F

E° = 0. 34 V
1
Sol 13: (i) Fe3(aq)
+ −
+ I(aq) 2+
→ Fe(aq) + I (g)
2 2
Sol 15: Element with maximum oxidation potential will
E = Eº− + Eº = –0. 54 + 0. 77 = +0. 23 > 0
I /I2 Fe3+ /Fe2 + have highest reduction potential.
This is feasible. Now, Eº = 0. 76 V,
Zn/Zn2 +
+
(ii) +
Ag(aq) + Cu(s) → Ag(s) + Cu(aq) Eº = 0. 13 V
Pb/Pb2 +
º º

E =E +E = 0. 8 – 0. 52 = 0. 2870 Eº 2 + = 1. 66 V
Ag+ /Ag Cu/Cu+
Al/Al

This is feasible. \Reducing order: Pb < Zn < Al


1 1
(iii) Fe3(aq)
+ −
+ Br(aq) → Br2(g) + Fe2+(g)
2 2 Sol 16: (i) Since O3 has the highest SRP, it is the strongest
º º oxidising agent.
Eº = E –E = 0. 77 – (1. 09) = –0. 32 < 0
Fe3+ /Fe2 + Br2 /Br −
(ii) As Ag cannot get reduced, O3 is still the strongest
So, this is not feasible oxidised agent.
(iii) Ag is the strongest reducing agent as it has the least
If Fe3+ → Fe, then, E = –0. 036
Fe3+ /Fe negative oxidation potential.
and E° = –1. 126, still not feasible. (iv) Ag is still the strongest reducing agent.
(iv) Ag(s)+Fe3+(aq) → Fe2+(aq) + Ag+(aq)
Sol 17: IO3– will act as better oxidising agent in acidic
E = Eº + Eº = –0. 8 + 0. 77 = –0. 03 < 0 medium due to its larger SRP in acidic medium then
Ag+ /Ag+ Fe3+ /Fe2 +
basic medium.
So, this is not feasible
1
if Fe3+ → Fe, Eº = –0. 03, Sol 18: Fe3+ + Br– → Br + Fe2+
Fe3+ /Fe 2 2

E° = –0. 836, still not feasible. E° = Eº + Eº


Fe3+ /Fe2 + Br − /Br2

1 = 0. 77 – 1. 09 = – 0. 32 < 0
(v) Br2(aq)+Fe2+(aq)→ Br–(aq)+Fe3+(aq)
2
∴ Fe3+ cannot oxidise Br– to Br2.
E° = Eº + Eº = 1. 09 – 0. 77 = 0. 32 > 0
Br2 /Br + Fe2 + /Fe3+
Sol 19: (i) Cu2+ + 2e⁻ → Cu
This reaction is feasible.
0.0591 1 1
E =E° – log = 0. 34 – 0. 0295 log
2 2
[Cu ]+ 0.001
Sol 14: Cu2+ + e → Cu+
E = 0. 2515 V
E° = +0. 18 V, n = 1
1 7 . 5 4 | Electrochemistr y

(ii) Zn → Zn2+ + 2e⁻ Sol 20: Fe3+ + e⁻ → Fe2+


0. 02 Eº = 0. 77 V
Fe3+ /Fe2 +

Eº = – Eº = 0. 76 [Fe2+ ]
Zn/Zn2 + Zn/Zn2 +
E = E – 0. 0591 log
[Fe3+ ]
0.0591 E = 0. 77 – 0. 0591 log 5
E = E – log[Zn2+ ] = 0. 76 – 0. 0295 log (0. 02)
2
( [Fe2+] = 5 × [Fe3+] )
E = 0. 8101 V
E = 0. 7287 V
(iii) AgCl + e⁻ → Ag + Cl–
Ag+ + e⁻ → Ag, E1 = 0. 8, n = 1 Sol 21: CH3COOH  CH3COO– + H+
∆G1 = – nF E1 Cα 2
ka = = Ca2
∆G1 = –0. 8 F 1−α

AgCl Ag+ + Cl–, ka


α=
K s = 2 × 10–10 C
1

∆G2 = –RT ln Ksp [H+] = Cα = Ck a

Adding [H+] = 0.357 × 1.74 × 10−5


AgCl + e → Ag + Cl–
[H+] = 2. 492 × 10–3
∆G = ∆G1 + ∆G2, n = 1 1
H → H+ + e
–F E° = –0. 8 F – 2. 303RT log (2×10 ) –10 2 2
E° = 0
2.303RT
E° = 0. 8 + log (2 × 10–10)
F E = –0. 0591 log[H+] = –0. 0295 log (2. 492 × 10–3)
E° = 0. 8 – 0. 57 E = 0. 1536 V
E° = 0. 226 V
Sol 22: pH = –log[H+]
1
(iv) Cl2 + e⁻ → Cl–
2 13 = –log[H+] ⇒ [H+] = 10–13

Eº = 1. 36 V kw 10 −14 1
Cl2 /Cl− [OH–] = = =
+
[H ] 10 −13 10
[Cl− ]
E = E° – 0. 0591 log Cu(OH)2 Cu + 2OH–
2+
(PCl )1/2
2
0.02 Ksp = [Cu2+] [OH–] 2
= 1. 36 – 0. 0591 log = 1. 36 – 0. 0591(–1. 548)
(0.5)1/2 K sp 1 × 10−19
[Cu2+] = =
E = 1. 451 V [OH− ]2 10−2
[Cu2+] = 10–17 M
1
(v) H + e⁻ → H2
+
2 Cu2+ + 2e → Cu
E° = 0
E° = 0. 34 V, n = 2
pH = – log[H+]
0.0591 1
E = E°– log
[H+] = 10–4. 4 2 [Cu2+ ]
PH21/2 1
E = 0. 0591 log = –0. 0591(log 2 –log[H+] ) = 0. 34 – 0. 0591 log = 0. 34 – 0. 5015
[H+ ] 10−17
= –0. 0591(0. 15 + 4. 4) E = –0. 1615 V
E = –0. 268 V
Chem i str y | 17.55

Sol 27: Mg(s)|Mg2+(aq)||Ag+(aq)|Ag(s)


Sol 23: (i) Ag+ + e → Ag ; E1 = 0. 80 V, n = 1
Mg(s) + 2Ag+ → Mg2+ + 2Ag
∆G1 = –nF E1 = –0. 8F
n = 2, E° = 3. 17 V
AgCl → Ag+ + Cl–
0.0591 [Mg2+ ]
∆G2 = –RT ln ksp = –2. 303 RT log(2×10–10) E = E° – log
2 [Ag+ ]2
Adding,
(0.13)
AgCl + e⁻ → Ag + Cl– = 3. 17 – 0. 0295 log = 3. 17 – 0. 209
(10−4 )2
∆G = –nF E° = ∆G1 + ∆G2, n = 1
E = 2. 96 V
–F E° = –0. 8 F – 2. 303 RT log(2×10–10)
2.303RT Sol 28: (a) H2SO4 → 2H+ + SO42–
E° = 0. 8 + log (2 × 10–10)
F
[H+] = 2[H2SO4] = 0. 02 M
E° = 0. 22 V
1
(ii) E = E° – 0. 0591 log[Cl–] = 0. 22 – 0. 0591 log (4 × 10–3) H → H+ + e⁻
2 2
E = 0. 36 V E° = 0, n = 1
[H+ ] 0.02
Sol 24: Ni(s) + 2Ag+(0. 002 M) E = E° – 0. 0591 log = –0. 0591 log
1/2
PH 4
2
→ Ni2+(0. 160 M) + 2 Ag(s) E = –0. 0591 log(0. 01)
n=2 E = +0. 1182 , Er = –0. 1182
0.0591 [Ni2+ ]
∴E = E1 – log (b) HCl → H+ + Cl–
2 [Ag+ ]2
[H+] = [HCl] = 0. 2
0.16
= 1. 05 – 0. 0295 log = 1. 05 – 0. 135 1
(2 × 10−3 )2 H → H+ + e⁻
2 2
E = 0. 91 V E° = 0, n = 1
0.0591 [H+ ] 0.2
Sol 25 HCOOH  H+ + HCOO– E = E – log = 0 – 0.0591 log
1 P 1/2 1
0 0 0 H2
∧m (HCOOH)= ∧m (HCOO–) + ∧m (H+)
E = 0. 0413 V, Er = –0. 0413 V
= 349. 6 + 54. 6
(c) E = 0, n = 1
0
∧m = 404. 2 S cm mol2 –1
−0.0591
E° = log[H+ ] = 0. 0591 p[H]
∧m 46.1 1
α= =
0
∧m 404.2 (i) pH = 5
α = 0. 114 E = 0. 0591 × 5 = 0. 2955 V
2 2
Cα 0.025(0.114) Er = –0. 2955 V
ka = =
1−α 1 − 0.114
(ii) pOH = 4
ka = 3. 67 × 10–4
pH = 14 – pOH = 10

Sol 26: (i) Potassium E = 0. 0591 × 10 = 0. 591 V

(ii) Sodium Er = –E = –0. 0591 V

(iii) Calcium
Sol 29: n for H2SO4 = 2
(iv) Magnesium
Normality = Molarity × n = 2M
(v) Aluminium
k × 1000 26 × 1000 × 10−2
∧e = = = 130 Scm2 equiv–1
N 2
1 7 . 5 6 | Electrochemistr y

Exercise 2 Sol 7: (B) This is a convention.

Single Correct Choice Type 1


Sol 8: (A) H+ + e– → H
2 2
Sol 1: (C) M+2 + 2e → M E° = 0
For one mole, charge required = 2F −0.0591 (PH )1/2
E= log 2 = –0. 0591 log 10 = –0. 0591 V
If atomic weight is M. 1 [H+ ]
∆E = 0. 0591 V
Then, for M gm, 2F charge
2F Sol 9: (A) We have,
For 1 gm, charge = = 1. 81 × 1022 × 1. 6 × 10–19
M
0.0591
⇒ M = 66. 7 gm E° = log kC
2
0.0591
Sol 2: (B) Moles of Ag = 1 E° = log(2. 69 × 1012) = 0. 3667 V
2
1
Moles of Cu =
2 Sol 10: (B) Ag+ + e⁻ → Ag
1 1
Moles of Al = E = E°– 0. 0591 log
3 [Ag+ ]
1 1 0. 25 = 0. 799 + 0. 059 log [Ag+]
1: : = 6: 3: 2
2 3
[Ag+] = 5. 13 × 10–10
2.1
Sol 3: (B) Moles of A = ksp = [Ag+] [Cl–] = 5. 1 × 10–11
7
2.1 2.7 7.2
Molar ratio = : : = 0. 3: 0. 1: 0. 15 Sol 11: (B) At cathode
7 27 78
Cu2+ + 2e⁻ → Cu
= 3: 1: 1. 5
At anode
= 6: 2: 3
1 1 2H2O → O2 + 4H+ + 4e⁻
= 1: :
3 2 1
Moles nO = nC
\ Valency = 1, 3 and 2
2 2 2
1 2.5
VO = 22400 nO = 22400 × × = 441 mL
Sol 4: (B) Volume of plate = 10×10×10 cm = 1 cm
–2 3 3 2 2 2 63.5
≈ 445 mL O2 is liberated
Mass = 8. 94 g
8.94
Moles = Sol 12: (B) P = VI
63.5
8.94 P = 1. 65 kW
Quantity of electricity = × 2F = 27172 C
63.5
q = 1. 65 × 8 kWh = 13. 2 kWh
1 Cost = 13. 2 × 5 paise = 66 paise
Sol 5: (D) H2O → H2 + O
2 2
2H2O → 2H2 + O2
1  1000
Only water will be oxidised and reduced. Sol 13: (C) ∧m = . .
R a C
VH = 2 × VO = 4. 8 L 1 2.2 1
2 2
= . × = 0. 002 Sm2 mol–1
50 4.4 × 10 −2 0.5
Sol 6: (D) At cathode, water will be reduced,
2H2O + 2e⁻ → H2 + 2OH– (aq) ∧m 10
Sol 14: (C) α = = = 0. 05
0
∧m 200
pH of the solution around cathode will decrease.
Chem i str y | 17.57

[H+] = Cα = 0. 005 Sol 19: (C) At cathode,


pH = –log[H+] = log[200] = 2. 3 1
H+ + e⁻ → H
2 2
1000 1000 1 At anode
Sol 15: (C) ∧m = k × = (k = , C = y)
C xy x 1
H → H+ + e⁻
2 2
ka 1.6 × 10−5 1 1
Sol 16: (B) α = = = 0. 04 H2 + H+ → H2 + H+
C 0.01 2 2
∧m 0. 410–20. → 10–1
α= 10−1.(0.1)1/2
0
∧m E = –0. 0591 log
10−2.(0.4)1/2
⇒ ∧m = 380 × 10–4 × 0. 04 = 1. 52 × 10–3
E = –0. 041 V
1000 × k
∧m =
C × 1000 Sol 20: (D) O2(g) + 4H+(aq) + 4e– → 2H2O()
k = 1. 52 × 10–2 S m–1 E° = 1. 23 V
∆G° = –nFE = –474. 78 kJ
Sol 17: (A) Au+ + 2CN– = Au(CN)2–
∆Hf (O2) = 0
∆G1 = –RT ln X ∆Hr = 2∆Hf(H2O, ) = –2 × 285. 5 kJ = –571 kJ
Au + 2e → Au
3+ – +
∆G = ∆H – T∆S
∆G2 = –nFEº = –2. 8F ∆H − ∆G
∆S = = –0. 322 kJ/k
Au → Au + 3e⁻
3+ T
∆G3 = –nF(–Eº) = 4. 5F
Sol 21: (C) Cu2+ + 2e⁻ → Cu; Eº = 0. 337
1 1
O2 + H2O + e– → OH– –nFE    = –0. 674 F
∆G1 =
4 2
∆G4 = –1F(Eº) = –0. 41F Cu2+ + e Cu+ ; E° = 0. 153
4 Cu+ → Cu2+ + e⁻; E° = –0. 153
Summing, ∆G = ∑ ∆G1 = –RT ln X + 1. 29 F
∆G2 = = + 0. 153 F
–nFE    
i=1
Adding,
Sol 18: (C) At anode Cu+ + e⁻ → Cu
1 ∆G = ∆G1  +∆G2  
H → H+ + e⁻
2 2
–F E° = –0. 674 F + 0. 153 F
At cathode
E° = 0. 521 V
1
Cl + e⁻ → Cl–
2 2
1 1 Previous Years’ Questions
H2 + Cl2 → H+ + Cl–
2 2
Sol 1: (D) Impure metal made anode while pure metal
[H+ ][Cl– ] made cathode.
E = Eº – 0. 0591 log
1/2 1/2
PH .PCl
2 2
Sol 2: (D) In electrolytic cell, cathode acts as source of
[H+ ]2 [Cl– ]2 electrons.
E1–E2 = 0. 0591 log = 0. 0591 × 2 = 0. 1182
[H+ ]1 [Cl– ]1
+ e–
Sol 3: (B) Ag+ 
→ Ag, 96500 C will liberate
∴E2 – E1 = –0. 1182
silver = 108 gm.
9650C will liberate silver = 10.8
1 7 . 5 8 | Electrochemistr y

Sol 4: (C) Gold (Au) and Silver(Ag) are present in the Sol 11: (C) 2H(aq)
+
+ 2e− → H2(g)
anode mud.
0.0591 P(H )
E=
red

Ered − log 2
Sm n (H+ )2
K[A]A C×l
Sol 5 (B) C = ,K= =
1 [A]A mol m-3m2 0.0591 2
Ered= 0 − log
= S m mol . 2 –1 2 (1)2
0.0591
Sol 6: (D) 0.1 M difluoroacetic acid has highest electrical Ered = log2
2
conductivity among the given solutions.
∴ Ered is found to be negative for (c) option
Sol 7: (A) From Kohlraush’s law
0.0591
Λ oCH = Λ oCH o
+ ΛHCl o
− ΛNaCl Sol 12: (C) E=
cell

Ecell − logQ
3COOH 3COONa n
Hence, (A) is the correct answer. [Zn2+ ]
Where, Q =
[Cu2+ ]
Sol 8: (D) According to Kohlrausch’s law, the molar For complete discharge, Ecell = 0
conductivity of an electrolyte at infinite dilution is the
sum of conductivities of its ions. Therefore to obtain 0.0591 [Zn2+ ]
o o o So, Ecell = log
∧HOAc from the conductivity of ∧NaOAc & ∧HCl ,the 2 [Cu2+ ]
o
conductivity value of NaCl i.e. ∧NaCl is also needed.  [Zn ] 
2 +
⇒ 
2+
 = 1037.3.
o o o o  [Cu ] 
ΛNaOAc + ΛHCl − ΛNaCl = ΛHOAc

i.e. Λ o + Λo + Λ o+ + Λo – − (Λo + Λo – ) Sol 13: (D) For the cell reaction, Fe acts as cathode and
Na+ OAc – H Cl Na+ Cl

= Λ o
+ Λ o+ = ΛHOAc
o Sn as anode. Hence,
OAc− H
Ecell =Ecathode − Eanode =−0.44 − ( −0.14) =−0.30V
Sol 9: (A) Cell constant The negative EMF suggests that the reaction goes
Conductivity(l) Conductivity(II) spontaneously in reverse direction.
= =
Conduc tance(l) Conduc tance(II)
129 Sol 14: (C) Fe3+ + 3e– → Fe;
Conductivity (II) = Sm−1
520
∆G1 = –3 × F × E
Fe3+ /Fe
0.2 M = 200 mol m–3.
Molar conductivity of 0.2 M solution Fe+2 + 2e– → Fe; ∆G2 = –2 × F × E
Fe2 + /Fe
129 / 520
= = 12.4 × 10–4 S m2 mol–1. Fe3+ + e– → Fe2+ ; ∆G = ∆G1 –∆G2
200
∆G = 3 × 0.036G – 2 × 0.439 × F
Note: From given data it is not possible to calculate
molar conductivity of 0.02 M solution exactly. However, it = – 1 × E ×F
(Fe3+ /Fe+2 )
is sure that its molar conductivity will be slightly greater
than 12.4 × 10–4 Sm2 mol–1. Assuming linear inverse
E = 2 × 0.439 − 3 × 0.036
variation of molar conductivity with concentration we (Fe3+ /Fe+2 )
can say that = 0.878 – 0.108 = 0.770 V
∴ Molar conductivity of 0.02M solution
0.059 [Zn++ ]
= 1.24 × 10–3 × 10 Sol 15: (C) E = E – log
n [Cu++ ]
= 124 × 10–4 S m2mol–1. 0.059 1
= 1.10 – log
2 0.1
Sol 10: (C) Velocities of both K+ and NO3– are nearly the
= 1.10 – 0.0295 log 10 = 1.07 volt.
same in KNO3 so it is used to make salt-bridge.
Chem i str y | 17.59

Sol 16: (A)


Sol 19: (B) 2H+ + 2e− → H2 ( g)
As E −0.72V and E 2+
= −0.42V
=
Cr3+ /Cr Fe /Fe  
 PH2  2
E= o
E − 0.059 log  (here E is − ve when PH > H+  )
2Cr + 3Fe2+ → 3Fe + 2Cr3+ 2  2  
 H+  
  
 0.0591 (Cr3+ )2
E=
cell Ecell − log −0.0591  2  −0.0591
6 (Fe2+ )3 = log10   = × 0.3010 = negative value
2 1 2
0.0591 (0.1)2 0.0591 (0.1)2
( −0.42 + 0.72) −
= log 0.30 −
= log
6 (0.01) 3 6 (0.01)3
Sol 20: (D)
0.0591 10−2 0.0591
0.30 −
= log 0.30 −
= log10 4 Zn + Fe+2 → Zn+2 + Fe
6 10 −6 6
Ecell=0.2606 V Fe + Ni+2 → Fe2+ + Ni

Zn + Ni2+ → Zn+2 + Ni


Sol 17: (D)
3 All these are spontaneous
CH3OH( ) + O2 (g) → CO2 (g) + 2H2O( ) ∆H = −726kJ mol−1
2
H2O( ) ∆H = −726kJ mol−1 Sol 21: (D)
Higher the SRP, better is oxidising agent.
−166.2 kJ mol−1
Also ∆Gf CH3OH( ) =
Hence, MnO −4 is strongest oxidising agent.
−1
∆Gf H3O( ) −237.2 kJ mol
=

−394.4 kJ mol−1
∆Gf CO2 ( ) = Sol 22: (C)

 ∆G = Σ∆Gf products − Σ∆Gf reac tants According to Debye Huckle onsager equation,

=-394.4-2(237.2) + 166.2 λC = λ ∞ + (A) C

=-702.6 kJ mol-1 Here A = B


∆G ∴ λC = λ ∞ + (B) C
now Efficiency of fuel cell = × 100
∆H
702.6 Sol 23: (A)
= × 100= 97%
726
(1) Mn2+ + 2e⁻ → Mn; E° = –1.18V;
Sol 18: (C) ∆G1 =−2F( −1.18) =2.36F
Fe3+ + 3e− → Fe; E = −0.036 V (2) Mn3+ + e⁻ → Mn2+; E° = +1.51 V;
∴ ∆G1 = −nFE = −3F( −0.036) = +0.108F ∆G1 =−F( −1.51) =−1.51F
Also Fe2+ + 2e− → Fe(aq); E = −0.439 V (1) - 2 × (2)
∴ ∆G1 = −nFE = −2F( −0.439) = 0.878F 3Mn2+ → Mn + 2Mn3+;
To find Eo for Fe3(aq)
+
+ e− → Fe2+ (aq) ∆G3 =∆G1 − 2∆G2
∆G1 =−nFE =−1FE = [2.36 – 2(–1.51)] F

 G= G1 − G2
= (2.36 + 3.02) F
∴ G =0.108F-0.878F = 5.38 F
∴ − FE = +0.108F − 0.878F
But ∆G3 =
12FE
∴ E= 0.878 − 0.108= 0.77v
− 2FE
⇒ 5.38F =
1 7 . 6 0 | Electrochemistr y

⇒ E =
−2.69 V E +E = 0. 982
H2 /H+ Ag+ /Ag
As E° value is negative reaction is non-spontaneous.
E = 0. 188
H2 /H+

Sol 24: (A) Cu2+ + 2e → Cu 1
2F 1mole H → H+ + e⁻
= 63.5g 2 2
0. 188 = 0 – 0. 059 log[H+]

JEE Advanced/Boards [H+] = 6. 6 × 10–4


Cα = 6. 6 × 10–4
Exercise 1 6.6 × 10−4
⇒α= = 0. 5
Sol 1: Cu + 2e → Cu
2+ 1.3 × 10−3

E = 0. 344 Cα 2
ka =
1−α
0.0591 1
E = E – log = 0. 226
2 [Cu2+ ] ka = 6. 74 × 10–4

As after E < 0. 226, Bi will also start to deposit


0.0591 [Mn2+ ]
0.0591 1 Sol 4: E = E – log
0. 344 – log = 0. 226 5 [H+ ]8 [MnO − ] 4
2 [Cu2+ ]
MnO4 + 8H + 5e → Mn + 4H2O
– + - 2+
0. 0295 log [Cu2+] = –0. 118
log [Cu2+] = –4 t = 0 0. 1 0. 8
[Cu2+] = 10–4 M t=t 0. 01 0. 08 0. 09
0.09
E = 1. 51 – 0. 01182 log = 1. 39 V
Sol 2: Reduction potential of calomel electrode = 0. 28 V (0.08)8 (0.01)
0. 67 = 0. 28 – Eº +
H /H2

º
Sol 5: CH3COOH CH3COO– + H+
E = –0. 39
H+ /H2
ka 1.8 × 10−5
1 α= = = 0. 0134
H+ + e → H2 C 0.1
2
[H ] = Cα = 1. 34 × 10–3
+
1
E = E – 0. 059 log

1
[H+ ] H → H+ + e⁻
2 2
1
–0. 39 = – 0. 059 log [H+ ]
[H+ ] E = Eº – 0. 0591 log
H2 /H+ H2 /H+ PH 1/2
−0.039
= log[H+] 2
0.059 E = 0 – 0. 0591 log 1. 34 × 10–3
H2 /H+
pH = –log[H+]
E = 0. 170 V
pH = 6. 61 H2 /H+

At cathode,
Sol 3: Ag+ + e⁻ → Ag
0.0591 1 NH3 + H2O NH4+ + OH–
º
E =E – log
Ag+ /Ag Ag+ /Ag 1 [Ag+ ] kb 1.8 × 10−5
1 α= =
= 0. 8 – 0. 0591 log C 0.01
0.8
α = 0. 042
E = 0. 794
Ag+ /Ag
Chem i str y | 17.61

[OH–] = Cα = 4. 24 × 10–4, 1
E = E°– 0. 0591 log
+
10 −14 [H ]cathode
[H+] = = 2. 35 × 10–11

[OH ] 1
–0. 188 = 0 – 0. 0591 log
1 [H+ ]
H+ + e– → H
2 2 log [H+] = 6. 59 × 10–4
1
E = Eº – 0. 0591 log
H+ /H2 H2 /H+ [H+ ] C6H5NH3Cl C6H5NH2 + H+ + Cl–
1
= 0. 0591 log = –0. 628 V Ch = [H+]
−11
2.35 × 10
6.59 × 10−4
h= = 2. 12 × 10–2
Ecell = E +E = 0. 170 – 0. 628 = 0. 458 V (1 / 32)
H2 /H+ H+ /H2

Cα 2
Sol 6: Fe(s) + 2OH → FeO(s) + H2O()+2e
– Θ kh =
1.α
E° = 0. 87 V kh = 1. 43 × 10–5
Ni2O3(s)+H2O + 2e⁻ → 2NiO(s)+2OH–
E° = +0. 4 V Sol 9: m. equivalents of OH– added = MV

(i) Cell reaction = 40 × 0. 05 = 2 meq.

Fe(s) + Ni2O3(s) → FeO(s) + 2NiO(s) m. equivalents of H+ = MV = 30 × 0. 1 = 3meq.

(ii) E° = 0. 87 + 0. 4 = 1. 27 V ∴ m. equivalents of H+ remaining = 1 meq.


1
It does not depend on [KOH] [H+] = = 0. 014
40 + 30
(iii) Maximum amount of electrical energy
1
H + Ag+ → H+ + Ag
= |–n F E° | 2 2
= |–2 × 96. 5 × 1. 27 kJ| PH = 1 atm,
2
= 245. 1 kJ [H+ ]
∴ E = E° – 0. 0591 log
[Ag+ ]
Sol 7: Cu(OH)2 Cu2+ + 2OH– [H+ ]1 [Ag+ ]2
∴ E2 – E1 = 0. 0591 log .
We have pH = –log[H+] = 14 [H+ ]2 [Ag+ ]1
[H+] = 10–14 0.1
−14
E2 – 0. 9 = 0. 0591 log .1
10 0.014
[OH–] = =1
[H+ ] E2 – 0. 9 = 0. 05
[Cu ] [OH ] = Ksp
2+ – 2
E2 = 0. 95 V
[Cu2+] = 1 × 10–19
Sol 10: E° = 0
Cu2+ + 2e⁻ → Cu
Ag+ + Ag → Ag+ + Ag
0.0591 1 1
E = E° – log = 0. 34 – 0. 0295 log [Ag+] c = 0. 05 M
2 2
[Cu ]+
10−19
−0.0591 [Ag+ ]a
E= log
= 0. 34 – 0. 56 = – 0. 22 V 1 [Ag+ ] c

[Ag+ ]a
1 1 0. 788 = –0. 0591 log
Sol 8: H2 + H+ → H2 + H+ 0.05
2 2
[Ag+ ]a
All conditions are standard except [H+] anode log = –13. 3
0.05
1 7 . 6 2 | Electrochemistr y

[Ag+] = 2. 32 × 10–15 ksp = [Ag+] a[Cl–]

AgI Ag+ + I– 2. 8 × 10–10 = [Ag+] a × 0. 2

ksp = [Ag+] [I–] [Ag+] a = 1. 4 × 10–9

[I–] = [KI] = 0. 05 Ag → Ag+ + e⁻

∴ ksp = 1. 16 × 10–16 At cathode

AgBr Ag+ + Br–


Sol 11: AgBr Ag + Br
+ –

ksp = [Ag+] c [Br–]


ksp = [Ag+] a. [Br] –
3.3 × 10−13
(k sp )AgBr [Ag+] c = = 3. 3 × 10–10
[Ag+] a = 10−3
[Br − ]
Ag + Ag+ + Ag + Ag+
(k sp )AgCl
Similarly, [Ag+] c = Cathode anode
[Cl− ]
Ag+ + Ag → Ag+ + Ag E = 0
[Ag+ ]a 1.4 × 10−9
cathode anode E = –0. 591 log = 0. 0591 log
[Ag+ ]c 3.3 × 10−10
E° = 0
[Ag+ ]a E = –0. 037 V
E = –0. 0591 log =0
[Ag+ ]c For a spontaneous process, electrodes should be
[Ag ] a = [Ag ] c
+ + reversed.

(k sp )AgBr (k sp )AgCl Sol 14: Pb2+ + 2e⁻ → Pb E = –0. 126 V


=
[Br − ] [Cl− ]
Pb → Pb2+ + 2e⁻ E = 0. 126 V
[Br − ] 5 × 10−13 
PbCl2 + 2e⁻ → Pb + 2Cl– E = –0. 268
=
− −10
[Cl ] 1 × 10
PbCl2 → Pb2+ + 2Cl– E = –0. 142 V
[Br − ] 1
= 5 × 10–3 =

[Cl ] 200 ∆G = –Fn E = –RT ln k
nF 
Sol 12: AgI Ag+ + I ln k = E
RT
∆G = –nFE1 nF
log k = E
RT × 2.303
Ag+ + e⁻ → Ag
log k = –4. 8n = 2
∆G = –nFE1
k = 1. 536 × 10–5
AgI + e⁻ → Ag+ + I–
Sol 15: Mn(OH)2 Mn2+ + 2OH–
∆n = –nF E = –nF E1 – RT ln k
Ksp = [Mn2+] [OH–] 2
RT
E =E +
 
lnk
nF 1.9 × 10−13
[Mn2+] =
2.303RT (10−4 )2
E = E1 – pk sp
nF [Mn2+] = 1. 9 × 10–5
Eº = –0. 15
Cell reaction:

Sol 13: At anode Mn + Cu2 → Mn2+ + Cu



AgCl Ag+ + Cl– E = –1. 18 V
Mn2 + /Mn
Chem i str y | 17.63

Eº = 0. 34 V [Pb2+ ]a
Cu2 + /Cu log = –2. 06
2.5 × 10−5
Eºcell = Eº – Eº
Cu2 + /Cu Mn2 + /Mn
[Pb2+] a = 2. 13 × 10–7
Eº = 0. 34 – (–1. 18)
At anode,
Eº = 1. 52 V
0.0591 [Mn2+ ] Pb + SO42– → PbSO4 + 2e⁻ E° = 0. 356
E = Eº – log
2 [Cu2+ ] Pb2+ + 2e⁻ → Pb, E° = –0. 126 V
1.9 × 10−5 Pb2+ + SO42– → PbSO4 E° = 0. 230
= 1. 52 – 0. 0295 log = 1. 52 – (–0. 14)
6.75 × 10−2
PbSO4 → Pb2+ + SO42– E° = –0. 230
E = 1. 66 V
∆G = –nF E° = –RT ln k
Sol 16: HIO3 H + IO3
+
nF
ln k = E°
ka RT
[IO3–] = Cα = C = Ck a
C nF
log k = E
[IO3 ] = 0. 22 M
– 2.303RT
k = 1.60 × 10–8
AgIO3 Ag+ + IO3–
ksp = 1.6 × 10–8 = [Pb2+] [SO4–2]
ksp = [Ag+] [IO3–]
1.6 × 10−8
3.08 × 10−8 [SO42–] =
[Ag+] = 2.13 × 10−7
0.22
[SO42–] = 7. 50 × 10–2
[Ag ] = 1. 37 × 10
+ –7

HSO4– H+ + SO42–
2Ag + Zn → 2Ag + Zn
2+ +

0. 525 0. 075 0. 075


Eº = –0. 80 V
Ag/Ag+
[H+ ][SO24− ]
ka =
Eº = –0. 76 V [HSO −4 ]
Zn2 + /Zn
ka = 9. 46 × 10–3
º º
E cell = EAg/Ag+ + EZn2+ /Zn = –1. 56 V ka ≈ 10–2

0.0591 [Ag+ ]2
E = E – log Sol 18: Cell reaction
2 [Zn2+ ]
Zn + Zn2+ → Zn + Zn2+
(1.37 × 10−7 )2
E = –1. 56 – 0. 0295 log Cathode anode
0.175
E = –1. 56 + 0. 372 E° = 0

E = –1. 188 V −0.0591 [Zn2+ ]a


E= log
2 [Zn2+ ] c

Sol 17: Pb + Pb2+ → Pb + Pb2+ −0.0591 [Zn2+ ]a


0. 099 = log
E = 0 2 3.84 × 10−4
0.0591 [Pb2+ ]a  [Zn2+ ] 
E=0– log +0. 061 log  a  = –3. 356
2 [Pb2+ ]  3.84 × 10−4 
c
 
2+
0.0591 [Pb ]a [Zn2+] a = 1. 69 × 10–7
= log
2 2.5 × 10−3
At anode
1 7 . 6 4 | Electrochemistr y

Zn2+ + 4CN– → Zn(CN)42– Now for Zn + Cu2 → Cu + Zn2+


[Zn(CN)24− ] 0.0591 [Zn2+ ]
kf = E = E – log
[Zn2+ ][CN– ]4 2 [Cu2+ ]
0.450 0.0591 1
= E = 1. 1 – log
1.69 × 10 −7
× (2.65 × 10 )) −3 4 2 1−x
1
kf = 5. 24 × 1016 = 1. 1 – 0. 0295 log
6.25 × 10−14
E = 0. 71 V
Sol 19: Ti+ + e– → Ti E° = –0. 34 V
∆G = –nF E° Sol 21: Zn + Cu2+ → Zn2+ + Cu

Ti3+ + 2e– → Ti+ E° = 1. 25 V we have, E° = 0. 76 – (–0. 34) = 1. 1 V


∆G = –nF E° = –RT ln k
Ti+ → Ti3+ + 2e– E° = –1. 25 V
nF
∆G1 = –nF E° = –2F(–1. 25) log k = E
2.303 × RT
2Ti+ + 2e–→ 2Ti [Zn2+ ]
k=
∆G2 = –2nF E° = –2F(–0. 34) [Cu2+ ]

3Ti+ → 2Ti + Ti3+ [Zn2+ ] 2


log = × 1. 1 = 37. 28
2+
[Cu ] 0.0591
∆G = ∆G1 + ∆G2

⇒ –2FEº = –2FEº1 – 2FEº2 [Zn2+ ]


= 1. 941 × 1037
[Cu2+ ]
Eº = E 1 + E 2

Eº = –0. 34 – 1. 25 Sol 22: Ag(NH3)2 Ag+ + 2NH3


Eº = –1. 59 V k0 = 6 × 10–8

Since, E° < 0, it is non spontaneous reaction. ∆G1 = –RT ln k0

Ag+ + e– → Ag E = 0. 799 V
Sol 20: Cu + 4NH3 → [Cu(NH3)4]
2+ 2+

∆G2 = –nF E = –F × 0. 799


t=0 1 A
t=t 1 – x A – 4x x (n = 1)

We have, A – 4x = 2 Adding,

[Cu(NH3 )4 ]2+ Ag(NH3)2 + e– → Ag + 2NH3


Kf =
[Cu2+ ][NH3 ]4 ∆G = –nF E° = ∆G1+∆G2
x
1 × 10 = 12
–n E° = –RT ln k0 – 0. 799 F
(1.x).24
1−x RT 2.303 RT
= 6. 25 × 10–14 Eº = ln k0 + 0. 799 = log(6 × 10–8) + 0. 799
x F F
1 E° = 0. 373 V
– 1 = 6. 25 × 10–14
x
1 Sol 23: We have,
x=
−14
1 + 6.25 × 10 (i) Co2+ + 6CN– → [Co(CN)6] 4–
6.25 × 10−14 kf = 1 × 1014
1–x= ≈ 6. 25×10–14
−14
1 + 6.25 × 10
Chem i str y | 17.65

∆G1 = –RT ln kf = – 43. 757 RT ∆G'1 = –nF E° = –2F × 0. 136 = –0. 272 F

(ii) [Co(CN)6] 3– + e– → [Co(CN)6] 4– For, 3Sn → 3Sn2+ + 6e⁻

E° = –0. 83 V, n=1 ∆G1 = 3∆G'1 = –0. 816 F

∆G2 = –nF E° = 0. 83 F Sn2+ → Sn4+ + 2e⁻, E° =–0. 154V, n = 2

(iii) Co3+ + e– → Co2+,Eº = 1. 82 V, n=1 ∆G2 = –nF E° = –2 × F × (–0. 154) = 0. 308 F

∆G3 = –nF E° = –1. 82 F For, 3Sn2+ → 3Sn4+ + 6e⁻,

(iii) + (i). (ii) gives, ∆G2 = 3∆G'2 = 0. 924 F

Co3+ + 6CN– → [Co(CN)6] 3– Cr2O72– + 14H+ + 6e⁻ → 2Cr3+ + 7H2O

∆G = ∆G3 + ∆G1 – ∆G2 Eº = 1. 33 V, n = 6

∆G = –RT ln kf = –1. 82F – 43. 757RT – 0. 83 F ∆G'3 = –nFE° = –6F(1. 33) = –7. 98 F

F F For, 2Cr2O72-+28H+ + 12e⁻ → HCr3+ 14H2O


⇒ln kf = × 1. 82 + 43. 757 + 0. 83
RT RT ∆G3 = 2∆G'3
1.82 + 0.83
log kf = + 19 ∆G3 = –15. 96 F
0.059
Now, (i) + (ii) + (iii) gives
kf = 8. 27 × 1063
3Sn(s) + 2Cr2O78– +28H+ → 3Sn4+ + 4Cr+3 + 14H2O
Sol 24: we have, ∆G = –RT ln k = ∆G1 + ∆G2 + ∆G3
(i)Ag + e → Ag E = 0. 7991 V, n=1
+ – 
–RT ln k=–0. 816 F + 0. 924 F –15. 96F
∆G 
1
= –nF E = –0. 7991 F

F
ln k = × 15. 852
RT
(ii) [Ag(NH3)2+] → Ag+ + 2NH3,
15.852
kins = 6. 02 × 10–8 log k =
0.0591
∆G2 = –RT ln kins log k = 268

Adding (i) and (ii), k = 10268

[Ag(NH3)2+] + e– → Ag + 2NH3, n = 1
Sol 26: Ti+ → Ti3+ + 2e⁻; Eº = –1. 25 V
∆G = ∆G1 + ∆G2
Co3+ + e⁻ → Co2+
–F E° = –0. 7991 F – RT ln kins
2Co3+ + 2e⁻ → 2Co2+ Eº = 1. 84 V
2.303RT
E° = 0. 7991 + log kins Adding,
F
= 0. 7991 + 0. 0591 log (6. 02×10–8) Ti+ + 2Co3+ → Ti3+ + 2Co2+

E° = 0. 372 V E° = 0. 59 V

Similarly for [Ag (CN)2–] ∆G = –nF E° = –RT ln k, n = 2

E° = 0. 7991 + 0. 0591 log (1. 995×10–19) 2F 0.59


log k = E = = 20
2.303 RT 0.0295
E° = –0. 307 V
k = 1020

Sol 25: We have, Now, if Ti+ = 0. 1 × 2. 5 = 25

Sn → Sn2+ + 2e, E°= 0. 136 V, n = 2


1 7 . 6 6 | Electrochemistr y

Initial milimoles of Co3+ = 25 × 0. 2 = 5 Charge produced by 3 mole H2=6F

Ti+ + 2Co3+ → Ti3+ + 2Co2+ 6F 6 × 96500


Current, I = =
t 15 × 60
t=0 2. 5 5 0 0
I = 643. 33 A
t = t 2. 5 – x 5–2x x 2x Cu2+ + 2e → Cu
3+ 2+ 2
[Ti ][Co ] number of moles of Cu produced = 3
k= = 1020
[Co3+ ]2 [Ti+ ] wt. = 3 × 63. 5 g
Vfinal = 50 ml wt. = 190. 5 g

x.4x2 .(50)2 .(50)


= 1020 Sol 29: At cathode, only reduction of water takes place
(50).(50)2 (2.5 – x)(5 – 2x)2
2H2O + 2e⁻ → H2(g) + 2OH–(aq)
x3
= 1020
(2.5 − x)(2.5 − x)2 9.722
Moles of H2 produced = =0. 434
22.4
x3
= 1020 Charge needed, Q = 2 × 0. 434 = 0. 868
(2.5 − x)3
At anode, for oxidation of water
x ≈ 2. 5 as k >>>1
2H2O → O2(g) + 4H+ + 4e–
Putting x = 2. 5 2.35
Moles of O2 produced, nO = = 0. 105
(2.5) 3 2 22.4
(2. 5 – x)3 = = 1. 5625 × 10–3
1020 Charge needed, q = 4 × nO = 0. 420
2
2. 5 – x = 2. 5 × 10 –7
Charge utilised for production of H2S2O8
2.5.x
[Ti+] = = 5 × 10–9 = Q. q = 0. 998
50
2(2.5 − x) charge utilised
[Co3+] = = 10–8 Moles of H2S2O8 = = 0. 224
50 2
Weight of H2S2O8 = 0. 224 × 194 = 43. 456 gm
Sol 27: For thiosulphate (S2O3 ), n = 2 2–

Number of equivalent = n. V. M. Sol 30: Initially, mass of H2SO4 solution


= 46. 3 × 0. 124 × 2 × 10–9 = 11. 4824 m. eq. = 1. 294 × 3. 5 × 1000 gm = 4. 529 kg
Equivalents of x = eq. of I– 39
Wt. of H2SO4 = ×4. 529 = 1. 76631 kg
1 100
eq.
=1× of I2 = × eq. of S2O32–
2 2 Moles of H2SO4 = 18. 02

11.4824 × 10−3 [H2SO4] = 5. 15 M


Eq. of x =
2
Finally, Mass H2SO4 solution = 1. 139 × 3. 5 kg
0.617 11.4824 × 10−3
=
M 2 = 3. 9865 kg
M = 107. 3 gm 20
Mass of H2SO4 = × 3. 9865 kg = 0. 7973 kg
100
Sol 28: At anode, Moles of H2SO4 = 8. 136
H2 +2OH → 2H2O + 2e
– –
[H2SO4] = 2. 324 M
67.2
Moles of H2 reacted = =3 ∴ ∆n = 9. 884
22.4 SO24−

Charge produced by 1 mole H2=2F 2F charge consumes 2 moles of [SO42–]


Chem i str y | 17.67

According to net reaction 0.373


\ Moles of Ag oxidised = = 0. 392
Charge required = 9. 884 F 0.95
9.884 × 96500 Mass of Ag oxidised = 0. 392 × 108 = 42. 41 g
Ampere hours = = 265 Amp. hr.
3600 Mass of electrode = 100 – 42. 41 = 57. 58 g

Sol 31: Cu2+ + 2e⁻ → Cu


Sol 34: Charge supplied per second
3
Moles of Cu deposited = = 0. 047 1.5 × 106
63.5 = = 15. 54 F
96500
Charge utilised = 2 × 0. 047 × F = 0. 094 F = 9071 C
Electrolysis:
Charge supplied = 3 × 2 × 3600 = 21600 C
2H2O → 2H2 + O2
Charge utilised 9071 2H2O → O2 + 4H+ + 4e⁻
∴ Efficiency = = = 0. 422
Charge supplied 21600
4 F charges electrolysed 2 moles of H2O.
∴ Efficiency = 42. 2 %
15.54
\ Moles of water electrolysed per second =
2
Sol 32: At cathode, = 7. 77
8.2 × 1012 × 103
Cu2+ + 2e⁻ → Cu Total moles of water =
18
0.4
Moles of Cu deposited = = 6. 3×10–3 8.2 × 1015
63.5 Time required in years = × 86400 × 365
18 × 7.77
Charge supplied = 2 × 6. 3 × 10–3 F = 1215. 74 C = 1. 9 million years
After deposition of copper,
1 Sol 35: Initial mass of electrolyte
H+ + e → H+ (as solution is acidic)
2 = 1. 261 × 1000 = 1261 g
Extra charge supplied = 1. 2 × 7 × 60
34.6
Wt. of H2SO4 = × 1261 = 436. 306
= 504 C = 5. 22 × 10–3 F 100
5.22 × 10−3 436.306
Moles of H2 evolved = = 2. 61 × 10–3 Moles of H2SO4 = = 4. 45
2 98
Volume of H2 evolved = 2. 61 × 10–3 × 22400 = 58. 46 mL Pb(s)+PbO2(s)+2H2SO4() → 2PbSO4(s)+2H2O()
At anode, t=0 4. 45
2H2O → O2 + 4H + 4e
+ –
t=t 4. 45–x x
Total charge,
we have, wt. of H2SO4 = 27
Q = 2 × 6. 3×10–3 × F + 5. 22 × 10–2 F = 1. 78 × 10–2 F
(4.45 − x)98
Q ∴ = 0. 27
Moles of O2 evolved = = 4. 45 × 10–3 12.61 × 436.606 + (4.45 − x)98 + x.18
4
Volume of O2 evolved = 4. 45 × 10–3 × 22400 = 99. 68 mL ⇒ 436. 608 – 98x = 0. 27(1261 – 80x)
Total volume = 158. 14 mL 463. 608 – 98x = 340. 47 –21. 6x
76. 4x = 96. 138
Sol 33: Ag → Ag + e
+ –
x = 1. 258
5 × 2 × 3600 Change in moles of SO42– = x = 1. 258
Total charge supplied = = 0. 373 F
96500
Pb + SO42– → PbSO4 + 2e
Now, since purity of electrode is 95%
Charge produced by 1 mole SO42– = 2F
Here, if charge will oxidise 0. 95 moles of Ag, rather
than 1 mole Charge produced by 1. 258 moles SO42–
= 2 × 1. 258 F = 2. 4 × 105 C
1 7 . 6 8 | Electrochemistr y

Sol 36: At anode, At cathode,


2H2O → O2 + 4H+ + 4e Cu → Cu2+ + 2e⁻
pH = 1 Final, [Cu2+] = 1 + 0. 9326 = 1. 9326
log[H+] = 1 Now, cell reaction,
[H+] = 0. 1 Zn + Cu2+ → Zn2+ + Cu
n = [H+] × v = 0. 1 × 10–1 = 10–2 E° = 1. 1 V, n = 2
H+

[H+] i = 10–7 0.0591 [Zn2+ ]  0.067 


E = E° – log = 1. 1 – 0. 0295 log  
2 2
[Cu ]+
 1.9326 
n = 10–7 × 10–1 = 10–8
H+
= 1. 1 – (0. 0295)(–1. 45)
Moles of H+ produced = 10–2 – 10–8
E = 1. 143 V
≈ 10–2

Charge needed = 10–2 F = 965 C Sol 38: At anode, for quinhydrone electrode,

Q 96.5 × 10 QH2 → Q + 2H+ + 2e⁻


Theoretical time = = = 1000 s
I 0.965 0.0591
E = E – log[H+] 2
Current efficiency = 80% 2

1000 × 5 Eº + 0. 0591 pH = –0. 699 + 0. 0591 pH


Therefore, actual time = s = 1250 s
4 (EºOP = – EºRP)
Now, at cathode
At cathode,
Cu2+(aq) + 2e– → Cu(s)
E = E = 0. 28
Current passed = 10 F –2

10−2 ∴Ecell = 0. 28 – 0. 699 + 0. 0591 pH


∴ Moles of copper reduced = = 5 × 10–3
2 Ecell = –0. 419 + 0. 0591 pH
After passing of current,
Equivalents of copper = equivalents of I2 (a) At pH = 5. 0,

= 2 equivalents of S2O3– Ecell = –0. 419 + (0. 0591) × (5) = –0. 124 V
Equivalents of copper (b) When Ecell = 0,
= 2 × 0. 04 × 35 × 10–3 0.419
pH = = 7. 1
Moles of copper = 31. 4 × 10 –3 0.0591
( n = 2 for Cu2+) (c) At pH = 7. 5

\ Total moles of Cu2+ = 6. 4 × 10–3 Ecell = 0. 0235 V


64 × 10−3 Since, Ecell is positive, reaction takes place in the given
Molarity = = 0. 064 M
100 × 10 −3 direction and cathode (Calomel electrode) is positive
electrode.
5 × 10 × 3600
Sol 37: Current passed = F = 1. 861 F
96500 Sol 39: We have, at anode
At anode
1
Zn2+ + 2e⁻ → Zn H → H+ + e–
Q 2 2
Moles of Zn2+ reduced = = 0. 9326
2 2H2 → 4H+ + 4e⁻
Final, [Zn2+] = 1 – 0. 9326 = 0. 067
E° = 0

E = –0. 0591 log [H+]


Chem i str y | 17.69

At cathode
[H+ ].[HS – ]
= k1
O2 + 2H2O + 4e → 4OH– [H2S]

Overall cell reaction k1 = 10–8, [H+] = 10–3, [H2S] = 0. 1

2H2 + O2 + 2H2O → 4H+ + 4OH– \[HS–] = 10–6M


1 HS– H+ + S2–
we have, H + H2O2 → H2O;∆H = –56. 7 kJ
2 2
10–6 10–3
2H2 + O2 → 2H2O;∆H= –2 × 56. 7 kJ = –113. 4 kJ
[S2− ].[H]+
H2O → H + OH ;∆H = 19. 05 kJ
+ – = k2
[HS – ]
4H2O → 4H+ + 4OH– [H+] = 10–3, [HS–] = 10–6, k2 = 1. 1 × 10–13
∆H = 4 × 19. 05 kJ = 76. 2 kJ [S2− ].10−3
= 1. 1 × 10–13
Adding, 10 −6
[S2–] = 1. 1 × 10–16 M
2H2 + O2 + 2H2O → 4H+ + 4OH–
E = –0. 64 – 0. 0295 log (1. 1 × 10–16)
∆H = –37. 2 kJ
= –0. 64 – 0. 0295(–15. 95)
 ∆E 
∆S = nF   = 4 × 96500×0. 001058 E = –0. 167 V
 ∆T P
∆S = 408. 38 1000
Sol 41: ∧eq = k ×
N
∆G = –nFEº = ∆H – T∆S
97.1 × 0.1
k= = 9. 71 × 10–3 Ω–1 cm–1
 ∆E  ∆H 1000
E° = T   −
 ∆T P ∆F 1
and, k =
E° = 0. 4414 V Ra
 0.5
R= =
Sol 40: Ag2S + 2e⁻ → 2Ag + S2– ka 9.71 × 10−3 × 1.5

Ag2S 2Ag2 + S2– R = 34. 32 Ω


V 5
∆G1 = –RT lnksp I= = Z
R 34.32
Ag+ × e⁻ → Ag; ∆G2 = –FEº, n = 1 I = 0. 1456 A
2Ag+ + 2e⁻ → 2Ag 6
V
Sol 42: E = = = 60 V/m = 0. 6 V/cm
∆G2 = –2FEº L 10 / 100
∧0
Ionic mobility (drift speed) = ∞ ×E
Ag2S + 2e⁻ → 2Ag + S2– F
73.52
∆G = ∆G1 + ∆G2 = –2FEº – RT ln ksp = ×0. 6 cm/s = 4. 57 × 10–4 cm/s
96500
–nFEº = –2FEº – RT ln ksp
Distance in 2 hours = 4. 57 × 10–4 × 2 × 3600 = 3. 29 cm
2.303 RT
E' = E + log ksp 1 
nF Sol 43: R =
k a
E' = –0. 64 V
 = k R a = 1. 342 × 170. 5 × 1. 86 × 10–4 = 0. 0425 m
0.0591
E = –0. 64 – log[S2–]
2  = 4. 25 cm
We have,
H2S H+ + HS–
1 7 . 7 0 | Electrochemistr y

0 0 0 500
Sol 44: ∧m SrSO4 = ∧m Sr2+ + ∧m SO42– nNaCl = = 8. 547
58.5
= 59. 46 + 79. 8 = 139. 26 ohm–1 cm2 mole–1
0.2346
k SrSO kNaCl+H = = 3. 08 × 10–5
0 2O 7600
∧m SrSO4 = 1000 × 4
C
kNaCl = kNaCl+H . kH
−4 2O 2O
1000 × 1.482 × 10
C= = (3. 08 – 2. 55) × 10–5
139.26
C = 1. 064 × 10–3 = 5. 3 × 10–6 Ω–1 cm–1

C = S = 1. 064 × 10–3 mole/L kNaCl × 1000


CNaCl =
∧m
= 1.064 × 10–3 × 183. 6 gm/L
5.3 × 10−6 × 1000
S = 0. 1953 gm/L = = 4. 190 × 10–5 mole/L
126.5
n
0
Sol 45: ∧m (Co2[Fe(CN)6] ) C=
V
0 0
= 2 ∧m (Co2+) + ∧m ([Fe(CN)6] +) n 8.547
V= = (1 L = 1 dm3)
C 4.19 × 10−5
= 2 × 86 + 444 = 616 Ω–1 cm–1 mol–1
V ≈ 2 × 105 dm3.
k Co [Fe(CN)6] = ksolution – kwater
2

= 2. 06 × 10–6 – 0. 41 × 10–6 Exercise 2


= 1. 65 × 10 Ω cm
–6 –1 –1
Single Correct Choice Type
= 1. 65 × 10–6 Ω–1 cm–1
Sol 1: (C) As E > EHg

> E
0 1000 Ag+ /Ag 2 /Hg Cu2 + /Cu
∧m =k×
C
Sol 2: (C) Mn3O4 + 16OH– → 3MnO42– + 8H2O + 10e⁻
k × 1000 1.65 × 10−6 × 1000
C= =
0
∧m 616 ∴ Charge required = 10 F

C = 2. 59 × 10–6 mol/L
Sol 3: (A) Only water will be oxidised and reduced at
S = C = 2. 59 × 10–6 mol/L anode and cathode respectively because SRP of SO42– is
very high (magnitude).
Co2[Fe(CN)6] 2Co2+ + [Fe(CN)6] 4–

ksp = (2s)2. S = 4S3 Sol 4: (C) At X

ksp = 7. 682 × 10–17 [A + ] a


pH = pka + log = pka + log
[HA ] b
0
Sol 46: For KCl, ∧m = 138 Ω–1 cm2 mol–1 1
H+ + e⁻ + H
2 2
1000 E1 = 0 + 0. 0591 log [H+] = –0. 0591 pH
∴ ∧m = k ×
C
E1 a
138 × 0.02 = –pka – log
k= = 2. 76 × 10–3 Ω–1 cm–1 0.0591 b
1000
At Y
G* = Rk
b
= 2. 76 × 10–3 × 85 = 0. 2346 cm–1 pH = pka + log
a
G* 0.2346 E2 = –0. 0591 pH
kwater = =
R 9200
E2 b a
= –pka – log = –pka + log
kwater = 2. 55 × 10–5 Ω–1 cm–1 0.0591 a b
Chem i str y | 17.71

E1 + E2 1
= –2pka H + Ag + Cl– → AgCl = H+
0.0591 2 2
E1 + E2 [H+ ]
E = Eº – 0. 0591 log
pka = – [Cl− ][PH ]1/2
0.118 2

k×t on increasing [H ] or decreasing [Cl–] , E will decrease.


+

Sol 5: (A) ∧eq =


C
9 × 10−6 Assertion Reasoning Type
C= × 10−3 = 6 × 10–5 M
1.5 × 10−4
Sol 12: (A) Cell Reaction:
Ag3PO4 3Ag+ + PO43– Zn(Hg) + HgO(s) → ZnO(s) + Hg()
[Ag+] = 3C = 1. 8 × 10–4 M
Sol 13: (D) E° = E°left – E°right
[PO43–] = 6 × 10–5 M
E° is intensive.
ksp = [Ag+] 3 [PO43–]
Sol 14: (A) These are facts.
ksp = 4. 32 × 10–18

Sol 6: (B) CH3COOH + NaOH → CH3COONa + H2O Comprehension Type

0.015 Paragraph 1
[CH3COONa] = = 0. 0075
2
Sol 15: (B) R = ρG*
1000
∧m = k ×
C for KCl, ∧m = 200 S cm2 mol–1
−4
6.3 × 10 × 1000 C ∧m 0.02 × 200
= = 84 S cm2 mol–1 k= =
0.0075 1000 1000
k = 4 × 10–3
Multiple Correct Choice Type G* = Rk = 100 × 4 × 10–3

Sol 7: (B, C) Eº > Eº > Eº > EºI G* = 0. 4


S2O2 /SO2
4
− Cl2 /Cl− Br2 /Br − 2 /I1
G* 0.4
species with higher E° can oxidise a species with lower E°. Sol 16: (C) kwater = = = 4 × 10–5
R 10 4

Sol 8: (B, C, D) In all case H2O will oxidise at anode to 585


give O2. Sol 17: (A) nNaCl = = 10
58.8
1 G* 0.4
Sol 9: (A, B) H2O → H2 + O kNaCl+H = = = 5 × 10–5
2 2 2O R 8000
270
nH = = 15 kNaCl = kNaCl+H – kH = 10–5
2O 18 2O 2O

VH = 15 × 22. 1 = 33. 6 L kNaCl × 1000


2 ∴CNaCl =
VO = 168 L, evolved at anode ∧m
2 −5
10 × 1000
VT = 504 L = = 8 × 10–5
125
10
Sol 10: (C, D) Refer text CNaCl =
V
10
Sol 11: (D, C) Ag + Cl– → AgCl + e V= = 1. 25 × 105 L
8 × 10−5
Cell reaction
1 7 . 7 2 | Electrochemistr y

Paragraph 2 1 –
Cl → Cl2 + e–
2
Sol 18: (B) NO3– + 4H+ → NO + 2H2O+ 3e(a)
PCl
NO3– + 2H+ + e → NO2 + H2O (b) E = E – 0. 06 log 2
[Cl− ]1/2
For (a), (B) → p, q
0.06 PNO
E=– log SEP of Na+ < SEP of H2O
3 [H ]4 [NO − ]
+
3 \ Water will get reduced to H2 at cathode
For (b),
PNO (C) → q, r
0.06 2
E = E° – log
Cl– will be oxidised as concentrated solution
1 [H+ ]2 [NO − ]
3
(D) → p, s
For (a), [NO3–] =[H+] = 1M, PNO = 10–3
SEP of Ag+ < SEP of H2O
0.06
ER = 0. 96 – log10−3 = 1. 02 ∴ Ag+ will be reduced to deposit Ag at cathode.
3
Cu → Cu2+ + 2e

EL = –0. 34 –
0.06
log[Cu2+ ] Previous Years’ Questions
2
= –0. 34 – 0. 03 log[Cu2+] Sol 1: (C) In electrolytic cell, electrolysis occur at the
cost of electricity :
EL = –0. 34 + 0. 03 log 10–1
At cathode : Mn+ + ne → M (electron gone in solution)
= –0. 31
At anode : Xn− → X + ne– (electron supplied to anode)
E = ER + EL ≈ 0. 71 V Therefore, electron is moving from cathode to anode
via internal circuit.
E for NO3 → NO,
10−3
E1 = 0. 65 – 0. 02 log Sol 2: (B) The cell reaction is :
[H+ ][NO3− ]
10−3 n + Fe2+ → Zn+ + Fe ; Ecell = 0.2905 V
E2 = 0. 48 – 0. 06 log
[H+ ]2 [NO3− ] 0.059 [Zn2+ ]
⇒ E = E – log
2 [Fe2+ ]
Sol 19: (C) E1 = E2 0.059 0.1
⇒ E = 0.2905 + log = 0.32 V
0. 65 – 0. 02(–3 – 5log[HNO3] ) 2 0.01
0.059
= 0. 48 – 0. 06(–3 – 3log[HNO3] ) Also, E = log K
n
0. 65 + 0. 06 + 0. 1 log[HNO3] 2E 0.32
⇒ log K = =
0.059 0.0295
= 0. 48 + 0. 18 + 0. 18 log[HNO3]
⇒ K = (10)0.32/0.0295
0. 08 log[HNO3] = 0. 71 – 0. 66 = 0. 05
5 Sol 3: (B) The net reaction is
log[HNO3] =
8 1
2H+ + O + Fe → H2O + Fe2+ + E = 1.67 V
[HNO3] = 100. 625 ≈ 100. 66 2 2
∆G  = –n E F
Match the Columns 2 × 1.67 × 96500
= kJ
1000
Sol 20 (A) → p, q
= –322.31 kJ
Cl– will not oxidise at low concentration.
Chem i str y | 17.73

Sol 4: (B) 0.01 mol H2 = 0.02 g equivalent Sol 10: (D) NH3 has no effect on the E° of glucose/
gluconic acid electrode.
⇒ Coulombs required = 0.02 × 96500 = 1930 C
⇒ Q = It = 1930 C Paragraph 2
1930 500
⇒t= = 19.3 ×104s Sol 11: (B) Moles of NaCl electrolysed = 4 × = 2.0
10 × 10 −3 1000
⇒ Moles of Cl2 produced = 1.0
Sol 5: (D) As AgNO3 is added to solution, KCl will be
2Cl– → + 2e–
displaced according to following reaction
AgNO3(aq) + KCl (aq) → AgCl(s) + KNO3(aq) Hg
Sol 12: (D) At cathode : Na+ + e– 
→ Na(Hg)
For every mole of KCl displaced from solution, one mole amalgam

of KNO3 comes in solution resulting in almost constant Two moles of Na formed during electrolysis would
conductivity. As the end point is reached, added AgNO3 produce two moles of Na(Hg) amalgam.
remain in solution increasing ionic concentration, hence ⇒ Mass of amalgam =2 × (23 + 200) = 446g
conductivity increases.

Sol 13: (D) Two Faraday of electric charge would be


Sol 6: (D) The half reactions are required for electrolysis of 2.0 moles of NaCl.
Fe(s) → Fe2+ (aq) + 2e– × 2 ⇒ total coulombs = 2 × 96500 = 193000 C
O2(g) + 4H+ → 2Fe2+ (aq) + 2H2O(l)
Paragraph 3
0.059 (10−3 )2
E =E –

log = 1.57 V
4 (10 −3 )4 (0.1) Sol 14: (C) For spontaneous redox reaction: Ecell > 0
For 2I– + Cl2 → 2Cl– + I2
Sol 7: (A, B, D) Metals with Eº value less than 0.96 V will
able to reduce NO3– in aqueous solution. Therefore, metals E° = 1.36 – 0.54 = 0.82 V > 0
V (E°= –1.19 V), i.e. Cl2 will spontaneously oxidize I–.
Fe(E° =–0.04 V), Hg(E° = 0.86 V) will all reduce NO3–
but Au (E° = 1.40V) cannot reduce NO3– in aqueous Sol 15: (D) In other cases Ecell < 0 , they are non-
solution. spontaneous.
For the reaction:
Paragraph 1
(i) 4Fe3+ + 2H2O → 4Fe2+ + 4H+ + O2;
Sol 8: (B) E for 2Ag+ + C6H12O6 + H2O → 2Ag(s) +

E = – 0.46 V
C6H12O7+ 2H+ is 0.75V
(ii) 4Mn3+ + 2H2O → 4Mn2+ + 4H+ + O2;
0.0592 E° = + 0.27 V
Also, E = log K
2
2Eº Sol 16: (A) As evidenced above, reaction (i) is non-
⇒ log K = = 25.33
0.0592 spontaneous, therefore, Fe3+ is stable in acid solution.
⇒ ln K = 2.303 log K = 58.35 However, reaction (ii) is spontaneous Mn3+ oxidises H2O
to O2 and itself reduced to Mn2+ in acidic medium.
Sol 9: (C) On increasing concentration of NH3, the Sodium fusion extract from aniline produces NaCN
concentration of H+ ion decreases, therefore, which reacts with Fe2+ to form [Fe(CN)6 ]4 − . The complex
ion then reacts with Fe3+ give blue precipitate of
0.0592
E=
red

Ered − log[H+ ]2 Prussian blue.
2
0.0592 Fe3+ + [Fe(CN)64– → Fe4 [Fe(CN)6 ]3
=0– × 2log 10 –11 =
0.65 V
2 Pr ussian blue

i.e. Ered increases by 0.65 V.


1 7 . 7 4 | Electrochemistr y

Paragraph 4 2
C  Λm  2
Ka1 0.01  1 
Sol 17: (B) M(s) + M+ (aq, 1 M) → M+ (aq, 0.05M) + M(s) =1 ×  2  = ×  = 0.001
Ka2 C2  Λ 0  0.1  10 
 m2 
2.303 RT 0.05
Ecell = 0 – log >0
F 1 pKa1 − pKa2 =
3
Hence, | Ecell | = Ecell = 0.70 V and ∆G < 0 for spontaneity
of reaction.
Sol 21: (D) Anode: H2 (s) → 2H+ + 2e−
0.0538
Sol 18: (C) Ecell = E – log 0.0025 = 0.139 V Mn+4 + 2e− → Mn+2
1 Cathode:
= 139 V Mn+4 + H2 → Mn+2 + 2H+

  +2   +  2 
Sol 19: X → Y. ∆rG0 = -193 kJ mol-1 0.059  Mn  H  
E= E − log10   
M+ → M3+ + 2e− E0 = −0.25V 2  Mn  PH 
+4
2
 
∆G0 for the this reaction is
∆G0 =−nFE0 =−2 × ( −0.25 ) × 96500 =48250 J / mol
0.092
= 0.151 −
0.059
2
( )
log10 10X

48.25 kJ / mole 0.059


0.092
= 0.151 − X
So the number of moles of M+ oxidized using X → 2
Y will be ⇒ X=
2
193
= = 4moles
48.25 Sol 22: (A) In a galvanic cell, the salt bridge does not
participate chemically in the cell reaction.
Sol 20: HK 

 +
H + X

H+   X − 
Ka =    
HX 

 + −
HY 
H +Y

H+   X − 
Ka =    
HX 

Λm for HX =
Λm
1

Λm for HX =
Λm
2

1
Λm = Λ
1 10 m2

Ka= C ∝2
2
Λ 
Ka= C ×  m1 
1 1  0 
Λ
 m1 
2
Λ 
Ka= C ×  m2 
2 2  0 
Λ
 m2 
2017-18 100 &
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Chemical Kinetics
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Questions recommended for revision
18. CHEMICAL KINETICS

1. INTRODUCTION
Chemical kinetics deals with the study of rate of chemical reactions. Rate of reaction is defined as change in
concentration of reactants or products per unit time. It is influenced by various factors such as nature of substance,
physical state of substance, temperature, concentration, presence of catalyst, etc.

2. RATE OF REACTIONS
The rate of reaction is expressed in mol L–1 s–1.
Change in the concentration of reactants or(Products)
Rate of reaction =
Time

2.1 Average Rate of Reaction


Average rate of reaction is defined as change in the concentration of reactants (or products) during large interval
of time. If ∆C is the change in the concentration of reactants and products in Dt time, then
Change in the concentration of reactants or(Products) ∆C C − C1
Average rate = = ± ± 2
=
Time ∆t t2 − t1
The graph shows the progress of reaction with respect to time.
Concentration

Product

Reactant

Time
Concentration vs Time
Figure 18.1: Concentration vs Time

Unit of concentration gram mole / Litre


Unit of average rate of reaction = = = g mol L–1 sec–1
Unit of time second
1 8 . 2 | Chemical Kinetics

PLANCESS CONCEPTS

For gases, pressure is replaced by concentration. Thus, unit will be atm sec–1
n
PV = nRT or P =   RT or P = CRT
V
∆[P] ∆[C]
= ⋅ RT or Rate in [atm/sec] = Rate in [molarity/sec] ×RT
∆t ∆t
Vaibhav Krishnan (JEE 2009, AIR 22)

2.2 Expression of Rate of Reaction


For the following reaction
n1A + n2B → m1C + m2D

1 ∆[A] 1 ∆[B] 1 ∆[C] 1 ∆[D]


rate of reaction = – –
= =
+ =
+
n1 ∆t n2 ∆t m1 ∆t m2 ∆t

For the reaction 2H2O2 → 2H2O + O2

∆[O2 ] 1 ∆[H2O2 ]
The rate of reaction = =–
∆t 2 ∆t

2.3 Instantaneous Rate of Reaction


Instantaneous rate of reaction is defined as the average reaction rate during a very
short interval of time or rate of reaction at a particular time.
∆c dc
Instantaneous rate = ± Lim
Concentration

=
∆t →0 ∆t dt
B
Note: For the reaction n1A + n2B → m1C + m2D

1 d[A] 1 d[B] 1 d[C] 1 d[D]


Instantaneous rate of reaction = – –
= =
+ =
+
n1 dT n2 dT m1 dT m2 dT
Time
Figure 18.2: Instantaneous Plot

PLANCESS CONCEPTS

Rate of reaction and rate of change of concentration of a reactant (or product) are two different terms,
except when stoichiometric coefficient involved is unity. On the other, rate of reaction is equal to the
rate of change of concentration of a reactant (or a product) divided by the corresponding stoichiometric
coefficient.
Nikhil Khandelwal (JEE 2009, AIR 94)

2.4 Reaction Life Time


It is defined as the time taken to complete 98% of the reaction. The shorter the life time, the faster the reaction. Half-
life period is defined as either the time taken to complete half of the reaction or during which the concentration of
the reactant is reduced to one half of its initial value. It is denoted by t1/2.
Chem i str y | 18.3

Illustration 1: For the reaction R → P, the concentration of a reactant changes from 0.03 M to 0.02 M in 25 min.
Calculate the average rate of reaction using units of time both in minutes and seconds.  (JEE MAIN)

∆[R ] [R] – [R]1 0.02M – 0.030M –0.01M


Sol: Average rate = – =– 2 =– =–
∆t t2 – t1 25minutes 25minutes

0.01M
= 4 × 10–4 mol L–1 min–1 = = 6.66 × 10–6 mol L–1 sec–1.
25 × 60s

1
Illustration 2: Decomposition of N2O5 is expressed by the equation, N2O5 → 2NO2 + O2
2
If, during a certain time interval, the rate of decomposition of N2O5 is 1.8 × 10 mol L min–1. Calculate the rates of
–3 –1

formation of NO2 and O2 during the same interval. (JEE MAIN)

Sol: Decomposition of N2O5 has the following rate expression:

∆[N2O5 ] 1 ∆[NO2 ] ∆[O2 ]


–= = 2
∆t 2 ∆t ∆t
∆[NO2 ] ∆[N2O5 ]
So, =2 = 2 × 1.8 × 10–3 = 3.6 × 10–3 mol L–1 min–1
∆t ∆t
∆[O2 ] 1 ∆[N2O5 ] 1
and
= = × 1.8 × 10–3 = 9× 10–4 mol L–1 min–1
∆t 2 ∆t 2
∆[N2O5 ]
(Rate is always positive and hence – is taken positive.)
∆t

Illustration 3: During the analysis of the products, even when a portion of the mixture is removed, the rate of
reaction in the remaining mixture is not affected. Explain.  (JEE ADVANCED)

Sol: The rate of reaction depends on concentration, which remains constant even if a portion of the mixture is
removed, i.e. amount of substance is independent of the concentration and hence remains unaffected.

Illustration 4: For the reaction A + B → C + D, the rate law equation = K1 [A] + K2 [A] [B], where K1 and K2 represent
two different constants and the products are formed by two different mechanisms. Explain the relative magnitudes
of the rates of two individual mechanisms?  (JEE ADVANCED)

Sol: The rate of formation of products for both the reaction mechanisms must be of the same order of magnitude.
Different magnitude reflects only the rate of reaction of the one which is faster among the two mechanisms. Also,
it involves rate of formation of product from A as well as product from A and B.

3. RATE CONSTANT
Consider a simple reaction A → B
dx dx
At a particular instant, if CA is the molar concentration or acitve mass of A, then ∝ CA or = kCA
dt dt
where k is a proportionality constant, called velocity constant or rate constant or specific reaction rate.
dx
At a fixed temperature, if CA = 1, then rate = = k …(i)
dt
Thus, rate constant can be defined as rate of reaction at unit concentration of the reactants. Let us consider a
general reaction aA + bB  Product
 dx 
Rate =   ∝ [A]a [B]b =k [A]a [B]b when [A] = [B] = 1 mol/L, then rate = k
 dt 
1 8 . 4 | Chemical Kinetics

PLANCESS CONCEPTS

For a particular reaction, rate constant is independent of the concentration of the reactants and
dependent only on temperature.
Neeraj Toshniwal (JEE 2009, AIR 21)

3.1 Units of Rate Constant


For reactions of different order, unit for rate constant is as follows:
n−1
 1 
Unit of rate constant =   × time–1
 unit of concentration 
n−1 n−1
 1   litre 
=  × sec = 
–1
 × sec–1 where, n = order of reaction.
 mol / litre   mol 

PLANCESS CONCEPTS

When order of reaction is not mentioned explicitly, then it can be determined using the unit of rate
constant. For example, if the unit of rate constant is M-1sec-1, then order = 1-(-1)=2.
Aman Gour (JEE 2012, AIR 230)

3.2 Rate of Reaction and Reaction Rate Constant


Table 18.1: Difference between rate of reaction and reaction rate constant

S.No. Rate of reaction Reaction rate constant


1. Speed at which reactants converts into products. Proportionality constant.

2. Measured as the rate of decrease in concentration of Equal to the rate of reaction when the concentration of
reactants or the rate of increase in concentration of each of the reactants is unity.
products with time.

3. Depends upon the initial concentration of reactants. Independent of the initial concentration of the reactants
and has a constant value at fixed temperature.

3.3 Factors Affecting Rate of Reaction


(a) Concentration: According to the law of mass action the greater the concentration of the reactants, the more
rapidly the reaction proceeds.
(b) Pressure (Gaseous reaction): Increasing the pressure, decreases the volume and simultaneously increases
the concentration. Therefore the rate of reaction increases.
(c) Temperature: Increase in temperature increases the reaction rate. It has been observed that rate either
k
doubles or triples for every 10°C rise in temperature. Temperature coefficient of reaction rate, T +10 ≈ 2 or 3,
kT
where k T +10 and kT are rate constants at two temperature, differing by 10°C.
(d) Nature of the reactants: The rate depends upon specific bonds of the reactants involved in the reaction and
hence on the nature of reactants.
Chem i str y | 18.5

(e) Surface area of the reactants: In heterogeneous reactions, if the reactants are in more powdered form, then
velocity is greater [as more active centres are available].
(f) Catalyst: It has an immense effect on the rate of reaction. Positive catalyst increases the rate of reaction by
decreasing the activation energy, while negative catalyst decreases the rate of reaction by increasing the
activation energy. Catalyst mainly affects the activation energy of reaction and hence the rate constant and
rate of reaction changes.
(g) Intensity of radiation: The rate of photochemical reactions generally increases with increase in intensity of
radiation.

Illustration 5: The rate law of a chemical reaction 2NO + O2 → 2NO2 is K[NO]2 [O2 ].If the volume of reaction vessel
is reduced to 1/4th of its original value, then what will be the change in rate of reaction? (JEE MAIN)

Sol: For, 2NO + O2 → 2NO2 Rate = K[NO]2 [O2]


Let us take a moles of NO and b moles of O2 to start a reaction at any time in a vessel with a capacity of V L.
2
 a  b 
r1 = K      …(i)
V V
V
if volume of vessel is reduced to ,then the rate for same number of NO and O2 moles.
4
2 2
 a   b   a  b 
r2 = K     = 64K      …(ii)
V / 4 V / 4 V V
r
Dividing equation (ii) by (i), 2 = 64 i.e. r2 is 64 times of r1
r1

Ilustration 6: Dinitrogen pentoxide decomposes as follows: (JEE ADVANCED)

1 −d[N2O5 ] d[NO2 ] d[O2 ]


N2O5 → 2NO2 + O2 If = K1[N2O5], = K2 [N2O5] and = 2 = K3 [N2O5]
2 dt dt dt
Derive a relation between K1, K2 and K3.

Sol: For the given reaction

d[N2O5 ] 1 d[NO2 ] d[O2 ]


= =2 Putting given values
dt 2 dt dt
1
or K1[N2O5] = K [N O ] = 2K3[N2O5] or 2K1 = K2 = 4K3
2 2 2 5

3.4 Rate Law


(a) It may not depend upon the concentration of each reactant or product of the reaction.
m n
Suppose, mA + nB → Product R ∝  A  B  .

(b) Rate of chemical reaction is directly proportional to the concentration of reactants.


(c) The rate law represents the experimentally observed rate of reaction, which depends upon the slowest step
of the reaction.
(d) Rate law cannot be deduced from the equation for a given reaction. It can be found out by experiments only.
(e) The rate law may not bear a simple relationship for the stoichiometric equation.
(f) It may not depend upon the concentration of species, which do not appear in the equation for the overall
reaction.
1 8 . 6 | Chemical Kinetics

4. ORDER OF REACTION
The order of any reaction may be defined as the sum of the powers to which the concentration terms are raised in
order to determine the rate of reaction.
For the reaction: mA+nB → product
The experimental data suggests that
Rate =k[A]p[B]q; then the order with respect to A = p and the order with respect to B = q and the total order of the
reaction = p + q.
Reactions having order equal to 0 are zero-order reactions.
Reactions having order equal to 1, are Ist order reactions.
Reactions having order equal to 2 are IInd order reactions.
Reactions having order equal to 3 are IIIrd order reactions

PLANCESS CONCEPTS

•• Order can be zero, fractional or integer.


•• Stoichiometric coefficients m and n of the reactants are always not equal to orders p and q.

B Rajiv Reddy (JEE 2012, AIR 11)

5. MOLECULARITY OF A REACTION
It is defined as the number of molecules, atom or radicals that participate in the reaction. Depending on the
number of participating molecules, the reaction can be unimolecular, bimocelular, trimolecular, etc.
Participating molecules Molecularity
One molecule unimolecular, 1
Two molecule bimolecular, 2
Three molecule trimolecular, 3

PLANCESS CONCEPTS

•• Molecularity of a reaction is moslty between 1 to 3, but never zero. It is rare that molecularity exceeds 3.
•• Misconception: Order and molecularity are one and the same. But order may or may not be equal to
molecularity of the reaction.
Rohit Kumar (JEE 2012, AIR 79)

Table 18.2: Differences between order and molecularity

S. No. Molecularity Order of reaction


1. It is the total number of reacting molecules It is the sum of powers of molar concentrations of the
(atoms or ions) leading to chemical change. reacting molecules in the rate equation of the reaction.
2. It is always a whole number. It may be a whole number, zero, fractional, positive or negative.
Chem i str y | 18.7

3. It is a theoretical concept. It is experimentally determined.


4. It is meaningful only for simple reactions or It is meant for the reaction and not for its individual steps.
individual steps of a complex reaction. It is
meaningless for overall complex reaction.

Illustration 7: Write the order of the following reactions? (JEE MAIN)


Reaction Exp. rate equ.
H2 + Cl2 → 2HCl r = k[H2]0[Cl2]0
H2 + Br2 → 2HBr r = k[H2][Br2]1/2

H2 + I2 → 2HI r = k[H2][I2]

Sol: Order is the number to which the concentration of the reactants/products are raised corresponding mostly to
the coefficients.

Reaction Exp. rate equ. Order


H2 + Cl2 → 2HCl r = k[H2]0[Cl2]0 0
H2 + Br2 → 2HBr r = k[H2][Br2]1/2 3/2
H2 + I2 → 2HI r = k[H2][I2] 2

Illustration 8: For the reaction 2NO + Cl2 → 2NOCl At 300 K, following data are obtained:  (JEE ADVANCED)

Initial Concentration
Expt. No. Initial Rate
[NO] [Cl2]
1. 0.010 0.010 1.2 × 10–4
2. 0.010 0.020 2.4 × 10–4
3. 0.020 0.020 9.6 × 10–4

What is the rate law for the reaction and the order of the reaction? Also calculate the specific rate constant.

Sol: Let the rate law for the reaction be


Rate = k [NO]x [Cl2]y
From expt. (1), 1.2 × 10–4 =k [0.010]x [0.010]y  ….(i)
From expt. (2), 2.4 × 10–4 =k [0.010]x [0.020]y  ….(ii)
Dividing Equation (ii) by Equation (i),
2.4 × 10−4 [0.020]y
= or 2 = (2)y y = 1
−4 y
1.2 × 10 [0.010]
From expt. (2), 2.4 × 10–4 = k [0.010]x [0.020]y
From expt. (3), 9.6 × 10–4 =k [0.020]x [0.020]y
9.6 × 10−4 [0.020]x
Dividing Equation (iii) by Equation (ii), = or 4 = 2x, x = 2
2.4 × 10−4 [0.010]x
Order of reaction = x + y = 2 + 1 = 3
Rate law for the reaction is
Rate = k[NO]2 [Cl2]
1 8 . 8 | Chemical Kinetics

Considering Equation (i) again, 1.2 × 10–4 = k[0.010]2[0.010]


1.2 × 10−4
k= = 1.2 × 102 mol–2 L2 s–1
[0.010]3

6. REACTION OF VARIOUS ORDERS

6.1 Zero-Order Reactions


Rate of the reaction proportional to zero power of the concentration of reactants is
known as zero-order reaction. Consider the reaction
d[R]

Concentration of R
-K =Slope
R → P Rate = =k[R]0
dt
As any quantity raised to power zero is unity
d[R]
Rate = = k × 1 ; d[R] = – k dt
dt
Integrating on both sides [R] = – k t + I ....(i)
O
Time(t)

where I is the constant of integration. Figure 18.3: Zero order plot

At t = 0, the concentration of the reactant R = [R]0, where [R]0 is initial concentration of the reactant.
Substituting in equation (i)
[R]0 =– k × 0 + I [Rl0]=I
Substituting the value of I in the equation (i)
[R] = – kt + [R]0 ...(ii)
Equation of a straight line, y = mx + c. We get a straight line with slope = –k and intercept equal to [R]0, when [R]
is plotted against t.
[R ] – [R]
Simplifying equation (ii), we get the rate constant k = k = 0 ...(iii)
t
Zero-order reactions occur only under special conditions and hence they are uncommon. Some enzyme catalyzed
reactions and reactions which occur on metal surfaces are a few examples of zero-order reactions. Another example
of zero-order reaction is decomposition of gaseous ammonia on a hot platinum surface at high pressure.
1130K
2NH3(g) 
Pt catalyst
→ N2(g) + 3H2(g) ; Rate = k[NH3]0 = k

Here, platinum acts as a catalyst. The metal surface reacting with gas molecules under high pressure gets saturated.
So, a further change in reaction conditions does not alter the amount of ammonia on the surface of the catalyst
making rate of the reaction independent of its concentration. The thermal decomposition of HI on gold surface is
another example of zero-order reaction.

[R]0 [R]
(A) Unit of rate constant: k = k mol L−1 sec−1
t
Unit of rate of reaction and unit of rate constant are the same.

(B) Half-life period (t1/2): It is the time taken to complete half of the reaction.

R0 R0
At t = t1/2 ; R= t1/2 = or t1/2 ∝ R0
2 2K

It is directly proportional to the initial concentration of the reactant.


Chem i str y | 18.9

6.2 First-Order Reactions


Rate of the reaction is proportional to the first power of the concentration of the reactant. For example, R → P
d[R] d[R]
Rate = – = k [R] or – = –kdt
dt [R]
Integrating the above equation, we get ln [R] = – kt +I ...(iv)
I is the integration constant ; hence its value can be determined easily.
When t = 0, R= [R]0, where [R]0 is the initial concentration of the reactant.
Therefore, equation (iv) can be written as ln [R]0 = – k × 0 + I = I
Substituting I in equation (iv)
ln [R] = – kt + ln[R]0  ...(v)
[R] 1 [R]
Rearranging this equation ln = – kt or k = ln 0  ...(vi)
[R]0 t [R]
At time t1, from equation (iv) ln[R]1 = – kt1 + ln[R]0  …(vii)
At time t2, ln[R]2 = – kt2 + ln[R]0  ...(viii)
where [R]1 and [R]2 are the concentrations of the reactants at time t1 and t2 respectively. Subtracting (viii) from (vii)
[R]
ln[R]1 – ln[R]2 = – kt1 – (–kt2) ln 1 = k(t2 – t1)
[R]2
1 [R]1
k= ln  …(ix)
(t2 − t1 ) [R]2
[R]
Equation (v) can also be written as ln 1 = –kt
[R]2
Taking antilog on both sides [R] = [R]0 e–kt
When ln [R] is plotted against t ,we obtain a straight line with slope = –k and intercept equal to ln [R]0.
The first-order rate equation (vi) can also be written in the form

2.303 [R]
k= log 0 ...(x)
t [R] 
[R]0 kt
log =
[R] 2.303
If we plot a graph between log [R]0/[R] and t, the slope = k/2.303
Hydrogenation of ethene is an example of first-order reaction.
C2H4(g) + H2(g) → C2 H6(g)
Rate = k [C2H4]
All natural and artificial radioactive decay of unstable nuclei takes place by first-order kinetics.

In[R]
log ([R]0/[R])

K = -Slope
In[R]

Slope = k/2.303

O t O Time
Fig.: A plot between In[R] and t Fig.: Plot of log [R]0/[R] vs time
for a first-order reaction for a first-order reaction

Figure 18.4: First order plot


1 8 . 1 0 | Chemical Kinetics

Examples:
226
(a) 88 Ra →24 He + 86
222
Rn ; Rate = k[Ra]

(b) Decomposition of N2O5 and N2O are few more examples of first-order reactions.
2.303 [R]
(i) Unit of rate constant: K = log 0 = sec–1
t [R]
(ii) Half-life period (t1/2):

R0 2.303 R0 2.303 0.693


At t = t1/2, R = , K= log = × log 2 =
2 t1/2 R0 / 2 t1/2 t1/2
0.693
t1/2 =
K

6.3 Pseudo-Order Reactions


Reactions whose actual order is different from that expected using rate law expression are called pseudo-order
reactions, e.g
RCl + H2O → ROH + HCl
Expected rate law:
Rate = k [RCl][H2O]; expected order = 1+1 = 2
Actual rate law: Rate = k’ [RCl] Actual order = 1
Water is taken in excess; therefore, its concentration may be taken constant. The reaction is, therefore, pseudo first
order. Similarly, the acid catalyzed hydrolysis of ester, viz.,
RCOOR’ + H2O → RCOOH + R’OH
follows first order kinetics: Rate = k [RCOOR’]
It is also a pseudo first-order reaction.

6.4 Some Examples of First-Order Reactions and Their Rate Constants


(a) For Gas Phase Reaction
Let us consider a typical first-order gas phase reaction
A(g) → B(g) + C(g)
Let pi be the initial pressure of A and pt the total pressure at time ‘t’. Integrated rate equation is as follows:
Total pressure pt = pA + pB + pC (pressure units)
pA,, pB and pC are the partial pressures of A, B and C, respectively
Decreasing x atm pressure of A at time t to form one mole of B and C each.. The increase in pressure of B and C
will also be x atm each.
A(g) → B(g) + C(g)
At time, t = 0 pi atm 0 atm 0 atm
At time t (pi – x) atm x atm x atm
Where pi is the initial pressure at time t = 0.
Pt = (pi – x) + x + x = pi + x
x = (pt – pi), where pA= pi – x = pi – (pt – p i ) = 2pi – pt
Chem i str y | 18.11

 2.303   pi 
k=    log   ...(xi)
 t  pA 
2.303 pi
= log
t 2pi – pt

(b) Pseudo-Unimolecular Reaction:


Inversion of cane sugar
H +
C12 H22O11 + H2O → C6 H12O6 + C6 H12O6
Sucrose Glucose
Fructose
The progress of the reaction can be studied using a polarimeter. Cane sugar and glucose are dextrorotatory while
fructose is laevorotatory. Let q0 is polarimetric reading at t = 0; qt is polarimetric reading after time t and θ∞ is
polarimetric reading after infinite time.
2.303 θ − θ∞
k= log 0
t θt − θ∞

(c) (i) Decomposition of H2O2


Pt 1
H2O2 → H2O + O
2 2
The progress of the reaction can be studied by two methods. (1)Volume of oxygen gas at different intervals of
times is measured and or (2) definite amount of reaction mixture is titrated with standard KMnO4 at different
intervals of time. If V0 represent the initial volume of KMnO4 and Vt final volume of KMnO4 at any time t
Then, R0 ∝ V0 ,R ∝ Vt
2.303 V
Therefore, K =– log 0
t Vt

(ii) Decomposition of Ammonium Nitrite


NH4NO2 → N2 + 2H2O
If Vt is the volume of N2 evolved at any time t and V∞ is the volume of N2 evolved when the decomposition is
complete. Then,
2.303 V∞
K= log
t V∞ − Vt

(d) Hydrolysis of Ethyl Acetate (Ester)


H +
CH3COOC2H5 + H2O → CH3COOH + C2H5OH

Kinetics of this reaction is studied by titrating a definite volume of the reaction mixture with standard alkali solution.
If V0 ,Vt and V∞ are volumes of standard alkali needed to neutralize a definite amount of x, will be proportional to
Vt – V0 and a, will be proportional to V∞ – V0
2.303 V − V0
Hence, K = log ∞
t V∞ − Vt

(e) Oxide Layer Formation


1 τmax
K= ln where tmax is the thickness of oxide layer after ∞ times and τ is the thickness of oxide layer at
t τmax − τ
time ‘t’.
1 a+x
(f) Bacterial Growth: K = ln
t a
1 8 . 1 2 | Chemical Kinetics

6.5 Second-Order Reaction


A reaction is said to be of second order if its reaction rate involves two different concentrations.
The kinetics of second-order reactions are given as follows:
(a) When concentrations of both reactants are same or two molecules of the same reactant are involved in the
change, i.e.
dx
A + B → Products or 2A → Products; = k(a – x)2,
dt
1 x
k= ⋅
t a(a − x)
Where a is the initial concentration of the reactant or reactants and x is the concentration of the reactant
changed in time t.
(b) When the initial concentrations of the two reactants are different, i.e.,
A + B → Products
Initial conc. a   b
dx 2.303 b(a − x)
= k(a – x)(b – x) ; log10
dt t(a − b) a(b − x)
(a - x)and (b - x) are the concentrations of A and B, respectively, after time interval, t.

Characteristics of the second-order reactions


(a) The value of k (velocity constant) depends on the unit of concentration.
The unit of k is expressed as (mol/litre)–1 time–1 or litre mol–1 time–1.
1
When ‘t’ is plotted against the resultant slope is a straight line.
(a − x)
1 1
Rearranging equation for k. t = .

Time

k(a − x) ka
1
The slope of the line is , where ‘k’ can be evaluated.
k
1/(a-x)
1 0.5a 1
(b) Half-life period (t1/2) = ⋅ = Figure 18.5 Second order plot
k a × 0.5a ka
Thus, half-life period is inversely proportional to initial concentration.
(c) Second-order reaction confirms to the first order when one of the reactants is present in large excess.
2.303 b(a − x)
Consider, k = log . If a >>> b, then (a – x) ≈ a and (a – b) ≈ a
t(a − b) 10 a(b − x)
2.303 ba 2.303 b
Hence, k= log10 or ka = k’ = log10
ta a(b − x) t (b − x)
here since ‘a’ being very large is a constant after the change. Thus, the reaction follows first-order kinetics with
respect to the reactant taken relatively in small amount.

Examples of second-order reactions


(a) Hydrolysis of ester by an alkali (saponification).
CH3COOC2H5 + NaOH → CH3COONa + C2H5OH
(b) The decomposition of NO2 into NO and O2. 2NO2 → 2NO + O2
(c) Conversion of ozone into oxygen at 100°C. 2O3 → 3O2
(d) Thermal decomposition of chlorine monoxide. 2Cl2O → 2Cl2 + O2
Chem i str y | 18.13

6.6 Third-Order Reaction


Reaction is said to be of third order if its reaction rate involves three different concentrations. When the concentration
of all the three reactants is same or three molecules of the same reactant are involved, the rate expression is given as:
dx
3A → Products; A + B + C → Products; = k(a – x)3
dt
1 x(2a − x)
Therefore k= ⋅
t 2a2 (a − x)2

Characteristics of third-order reactions

1 0.5a(2a − 0.5a) 1 0.5a × 1.5a 3


•• Half-life period = ⋅ = =
k 2
2a (0.5a) 2 k 2a × 0.5a × 0.5a 2a2k
2

Thus, half-life is inversely proportional to the square of initial concentration.


•• The change in the unit of concentration changes the numerical value of k.
•• The unit of k is expressed in (mol/litre)–2 time–1 or L2 mol–2 sec–1.

Examples of third-order reactions


•• Reaction between nitric oxide and oxygen. 2NO + O2 → 2NO2

•• Reaction between nitric oxide and chlorine. 2NO + Cl2 → 2NOCl

Examples
For a zero-order reaction, as shown in the following figure, the plot of [A] versus time is a straight line with
k = -ve slope. Other graphs are curved for a zero-order reaction.
[A] vs time In [A] vs time 1/[A] vs time
0.20 150
-2.0
0.15 In[A] 100
[A] k = - slope -3.0 1
mol A
L
-4.0 50
0.05

0.00 -5.0 0
20 40 60 0 20 40 60 20 40 60
Time (sec) Time (sec) Time (sec)
Figure 18.6: Plot of [A] versus time

For a first-order reaction, as shown in the following figure, the plot of the logarithm of [A] versus time is a straight
line with k = - slope of the line. Other graphs are curved for a first-order reaction.
[A] vs time In[A] vs time 1/[A] vs time
0.20
-2.0
k = - slope 60
0.15
In[A]
[A] 40
mol -3.0
L 1
[A]
0.05 -4.0 20

0.00 -5.0 0
5 10 15 20 0 5 10 15 20 5 10 15 20
Time sec. Time sec Time sec.

Figure 18.7: Plot of the logarithm of [A] versus time


1 8 . 1 4 | Chemical Kinetics

For a second-order reaction, as shown in the following figure, the plot of 1/[A] versus time is a straight line with
k =-ve slope of the line. Other graphs are curved for a second-order reaction.

[A] vs time In[A] vs time 1/[A] vs time


0.20 50
-2.0
0.15 40
In[A]
k = - slope
[A]
mol -3.0 1
L [A]
0.05 -4.0
10

0.00 -5.0 0
100 200 300 0 100 200 300 100 200 300
Time sec. Time sec Time sec.

Figure 18.8: Plot of 1/[A] versus time

6.7 Parallel Reactions

k1 B
[A]0 [B] k1
A ln = (k1 + k2)t =
[A]t [A] k 2
k2 C
k1 [A]0 k 2 [A]0
[A] = [A0] e–kt [B] = (1 – e–kt) [C] = (1 – e–kt)
k1 + k 2 k1 + k 2
Variation of concentration A, B and C with time may be graphically represented as,

Examples:

OH

NO2 B
k1
OH (Main)
C
Conc.
HNO3 OH

A
k2 Time
(Side)

NO2
Figure 18.9: Parallel reactions

6.8 Consecutive Reactions


k k
A → B 
1 2→ C
k1 [A]0  −k1t
– e 2 
−k1t −k t
[A]t = [A0] e ; [B]t =  e
[k 2 − k1 ]  
k2
 k  k2 −k1
[C]t = [A0] – ([A]t + [B]t) ; [B]max = [A0] .  1 
 k2 
1 K
tmax = ln 1
K1 − K 2 K 2
Chem i str y | 18.15

Conc.
[C]

[B]
[A]

Time

Figure 18.10: Consecutive reactions

Examples: (i) Decomposition of ethylene oxide:


k
(CH2)2O → CH3CHO
1

k
CH3CHO 
2→ CO + CH4

6.9 Reversible Reactions


1 k

A ← →B

k 2
Initial state (t = 0) a 0
Conc. at time (t) a – x x
2.303  x  xeq K
Equilibrium conc. (a – xe) xe ; k1 + k2 = log10  e  = f
t x
 e − x  a − x eq K b

Illustration 9: If the time required to decompose SO2Cl2 to half of its initial amount is 60 minutes and the
decomposition is a first-order reaction, then calculate the rate constant of the reaction. (JEE MAIN)
0.693
Sol: For a first-order reaction. k =
t1/2
0.693 0.693 0.693
= = = 1.925 × 10−4 s–1
t1/2 60 minutes 60 × 60 seconds

Illustration 10: Consider a first-order reactions, if it takes 5 minutes for the initial concentration of 0.6 mol L–1 to
become 0.4 mol L–1 Then how long will it take for the initial concentration to become 0.3 mol L–1? (JEE MAIN)

2.303 [A]
Sol: For a first-order reaction k = log 0
k [A]t

We have, [A]0 = 0.6 mol L–1 [A]t = 0.4 mol L–1 t = 5 min

2.303 0.6 2.303 2.303 × 0.1761


So, k = × log =log 1.5 min–1 = min–1 = 8.1 × 10–2 min–1
5min 0.4 5 5

2.303 [A] 2.303 0.6 2.303


For, [A]t = 0.3 mol L–1 ; t = log 0 = log = log 2 = 8.5min.
k [A]t 8.1 × 10 −2 0.3 8.1 × 10−2

Illustration 11: The following were obtained during the first order thermal decomposition of N2O5 (g) at constant
volume:
2N2O5(g) → 2N2O4(g) + O2(g)
1 8 . 1 6 | Chemical Kinetics

S.No. Time (sec) Total Pressure (atm)


1. 0 0.5
2. 100 0.512

Calculate the rate constant. (JEE ADVANCED)

Sol: Let the pressure of N2O5(g) decrease by 2x atm when two moles of N2O5 decompose to give two moles of N2O4
(g) and one mole of O2(g). Therefore pressure of N2O4(g) increases by 2x atm and that of O2(g) increases by x atm.

2N2O5(g) → 2N2O4(g) + O2(g)


At t = 0 0.5 atm 0 atm 0 atm
At time t (0.5 × 2x) atm 2x atm x atm
Pt = PN2O5 + PN2O4 + PO2 = (0.5 × 2x) + 2x + x = 0.5 + x
x = pt – 0.5 = 0.5 – 2(pt – 0.5)= 1.5 – 2pt
At t = 100 s; pt = 0.512 atm
PN2O5 = 1.5 – 2 x 0.512 = 0.476 atm
2.303 P 2.303 0.5atm 2.303
Using equation (11) k = log i = log = × 0.0216 = 4.98 × 10–4 s–1
t PA 100s 0.476 atm 100s

Illustration 12: In a second-order reaction, in which both the reactants have same concentration, consider 20% of
the reaction is completed in 500 sec. What is the time required for 60% completion? (JEE ADVANCED)

Sol: The equation for second order with both the reactants having same concentration is
1 x
k= ⋅ If a = 100 , x = 20, t = 500 sec.
t a(a − x)
1 20
So, k = × When a = 100, x = 60, t = ?
500 100 × (100 – 20)

1 60
t= ⋅
k 100 × 40
Substituting the value of k,
500 × 100 × 80 60
t= × or t = 3000 sec
20 100 × 40

7. THE REACTION MECHANISM

7.1 Elementary Reactions


Elementary reaction are single step reactions in which order and molecularity are always the same. In another
words, rate law and the law of mass action have the same expression.

7.2 Complex Reactions


These are multi-step reactions in which order and molecularity may or may not be same.
(a) In these types of reactions, intermediates are formed during the reaction which is different from the reactants
and the products formed.
(b) Each step involved in this reaction is an elementary reaction.
Chem i str y | 18.17

(c) The overall rate of reaction will be equal to the rate of slowest step. Hence the slowest step is called the rate
determining step (RDS) of reaction. A reaction can have more than one RDS.
(d) The overall molecularity of reaction and the molecularity of the RDS are the same . However, it has no
significance.
(e) The order of reaction and the overall order of reaction may not be the same. It depends on the concentrations
involved in the rate law expression of RDS. If it is not overall order, it may be determined by equilibrium
approach or by steady state approximation.
For a complex reaction, order is not equal to molecularity.

7.3 Reaction Mechanism


The steps involved in a reaction and determining which step is the slowest or rate determining is called mechanism.
A series of steps (known as elementary processes) leading to the formation of products or by which the overall
chemical reaction occurs is called the reaction mechanism.
For e.g.
The reaction between H2 and I2 to form hydrogen iodide was originally postulated as a simple one-step reaction.
H2 + I2 = 2HI
  Rate = k[H2][I2]
But, the formation of HI has been explained on the basis of the following mechanism:
I2 → 2I (fast)  ….(i)
H2 + I → H2I (fast)  ...(ii)
H2I + I → 2HI (slow)  ...(iii)

Overall reaction: H2 + I2 → 2HI

8. DETERMINATION OF RATE LAW FOR A COMPLEX REACTION

8.1 Equilibrium Approach


The concentration of intermediate can be determined from equilibrium constant of the reaction involved.
For example, let the mechanism of reaction A + 2B → C + D is
1 k
Step I: 
A + B ← → I

k 2

k
Step II: I + B 
2→ C+D
Overall rate of reaction, r = rate of step II = k2[I][B]  ....(i)
But this cannot be considerd as correct because the overall rate of reaction should be in terms of concentrations
of A and B (reactants). The concentration of I can be related with the concentrations of A and B with the help of
first equilibrium.
k1 [I] k1
For step I, equilibrium constant, Keq = = \ [I] = [A][B]
k −1 [A][B] k −1
k
Putting this value in equation (i), r = k2 k1 [A][B].[B] = k[A][B]2, where, k = 1
k −1 k −1

Hence, the overall rate of reaction is 1 + 2 = 3


1 8 . 1 8 | Chemical Kinetics

8.2 Steady State Approach


In this method, we assume that the intermediates formed are so reactive that after some time from initiation of
reaction (called induction period), the net rate of their formation becomes zero. They react with the same rate of
their formation. For example, let the mechanism of reaction
A +2B → C + D is
1 k
Step I: 
A + B ← → I

k 2
k
Step II: I + B 
2→ C+D

d[C]
The rate of reaction may be given as r = + = k2 [I] [B] …(ii)
dt
d[I]
Now, from steady state approximation on the intermediate, I – =0
dt
k1 [A][B]
or k1 [A][B] – k–1[I] – k2[I][B] = 0 or, [I] =
k −1 + k 2 [B]
k1 [A][B] k1k 2 [A][B]2
Substituting this value in equation (ii), r = k2 · ·[B] =
k −1 + k 2 [B] k −1 + k 2 [B]

PLANCESS CONCEPTS

•• When the intermediate is less stable, better results are obtained by steady state approximation, when the
intermediate is more stable, better results are obtained by eqilibrium approach. More stable intermediate
reacts very less and hence, the concentration of intermediate at any time remains nearly equal to its
equilibrium concentration.
•• When conditions of equilibrium approach are applied on the result obtained from steady state
approximation, the same rate law expression is obtained. For the above reaction, step I is faster than step
II. As step I is at equilibrium,
r1 = r–1 >> r2 or,k–1[I]>>k2[I][B] or, k–1>>k2[B]
therefore, k–1+k2[B] ≈ k–1
Now,the rate expression obtained from steady state is
k 2k1 [A][B]2
r= ≈ [A][B]2
k −1 + k 2 [B]
Which is exactly same expression obtained from equilibrium approach.

Aishwarya Karnawat (JEE 2012, AIR 839)

Illustration 13: The reaction 2NO + Br2 → 2NOBr obeys the following mechanism:
fast
Step I: 
NO + Br2 ← → NOBr
 2

Slow
Step II: NOBr2  → 2NOBr

Suggest the rate expression. (JEE MAIN)

Sol: The slowest step is the Rate determining step.


Chem i str y | 18.19

Step II is the step that determines the rate of the reaction and hence, r = k[NOBr2][NO] …(i)
However, NOBr2 is an intermediate and thus its concentration is determined step I.
[NOBr2 ]
For step I, equilibrium constant keq = \ [NOBr2] = keq[NO] [Br2]  …(ii)
[NO][Br2 ]
Thus, by equations (i) and (ii), r = k. keq[NO]2[Br2] or, r = k’[NO]2 [Br2]
where k’ = k. keq

Illustration 14: The following mechanisms are proposed for the reaction
CO + NO2 → CO2 + NO at low temperature:
(a) 2NO2 → N2O4 (fast) N2O4 + 2CO → 2CO2 + 3NO (slow)
(b) 2NO2 → NO3 + NO (slow) NO3 + CO → NO2 + CO2 (fast)
d[CO2 ]
Which of the above mechanism are consistent with the observed rate law: + = k[NO2]2 (JEE ADVANCED)
dt

Sol: For mechanism (a), r = rate of step II = k[N2O4][CO]2  ....(i)


[N2O 4 ]
Now, from step I: keq = or, [N2O4] = keq[NO2]2
2
[NO2 ]
Hence from (i). r = k.keq [NO2]2 [CO]2, but it is not the given rate law
Hence, the mechanism is not consistent with the rate law.
For mechanism (b), r = rate of step, I = k[NO2]2, which is the given rate law.

9. COLLISION THEORY OF REACTION RATE/ARRHENIUS THEORY


Postulates:
•• Collision of reactant molecules leads to chemical reaction. The number of collisions taking place per unit time
per unit volume of the reaction mixture is known as collision frequency (Z). The value of collision frequency is
very high (of the order of 1025 to 1028) in case of binary collisions.
•• Not every collision brings a chemical change. Only effective collisions bring about a chemical change to form
products. The effective collisions are less when compared to the total number of collisions. Collisions that
do not form a product are ineffective elastic collisions, i.e. molecules just collide and disperse in different
directions with different velocities. For effective collision, the following two barriers are to be cleared.

9.1 Energy Barrier


The minimum energy required by colliding molecules for the chemical reaction to take place is known as threshold
energy.
Fraction of molecules

Fraction of molecules
capable of bringing
effective collisions

Energy E

Figure 18.11: Threshold Plot


1 8 . 2 0 | Chemical Kinetics

The minimum amount of energy required by reactant molecules to participate in a reaction is called activation
energy.
Activation energy = threshold energy – average kinetic energy of reacting molecules.
Threshold energy = initial potential energy of reactant molecules + activation energy.
Collision of high energy molecules that overcomes the forces of repulsion and forms an unstable molecule cluster
is called an activated complex. Its life span is very less. Thus, the activated complex breaks to either form reactants
again or form new substances, i.e. products. The activation energy (Ea) depends upon the nature of chemical bonds
undergoing rupture and is independent of enthalpies of reactants and products.
The following graphs show the energy changes during exothermic and endothermic reactions versus the progress
of the reaction.
Activated Activated
Complex Complex

Ea
Ea

E C + D Products

Energy
Energy

Reactants Reactants
A+B E A+B

Products
C+D
Progress of the reaction Progress of the reaction
(Exothermic) (Endothermic)

Figure 18.12: Energy profile diagram for exothermic and endothermic reaction

(a) Every reaction, whether exothermic or endothermic, needs to overcome an energy barrier for reactants to get
converted to products.
(b) Lower the activation energy, higher will be the fraction of effective collisions leading to faster reaction and
vice versa.
(c) Activation energy Ea = E(activated complex) – E(ground state)
∆H = activation energy of forward reaction – activation energy of backward reaction.
(i) When Ea,f < Ea,b ; ∆E = –v and, ∆H = –ve
Thus, when the activation energy for the forward reaction is less than that for the backward reaction,
energy is released.
(ii) When Ea,f > Ea,b ; ∆E = + ve and, ∆H = + ve
Thus, when the activation energy for the forward reaction is more than that for the backward reaction,
energy is absorbed.

9.2 Orientation Factor


•• To form products reactants should have a proper orientation in addition to sufficient energy.
•• Rate of reaction is directly proportional to the number of effective collisions.
dx
Rate = – = collision frequency × fraction of effective collisions
dt
= Z × f
Chem i str y | 18.21

A A
A A A A

B B
B B
B B
Reactants Products
Figure 18.13: Collision theory

9.3 Temperature Dependance of Rate Constant


The temperature dependence of the rate of a chemical reaction can be accuratly explained by Arrhenius Equation
k = Ae-Ea/RT ...(i)
where, k=Arrhenius factor, Ea=activation energy, R=gas constant, T=temperature
According to the Arrhenius equation, for most reactions, the rate constant increases with increase in temperature. :
The parameters A and Ea for a given reaction are collectively called Arrhenius parameters. Value of Ea is determined
1
from the graph for and ln k is determined experimentally. Value of A inturn is calculated once Ea is known.
T
In the Arrhenius equation (i), the factor e–Ea/RT corresponds to the fraction of molecules with kinetic energy greater
than Ea.
Ea
Taking natural logarithm of both sides of equation (i), we get ln k = ln A –  ....(ii)
RT
The plot of ln k versus 1/T gives a straight line according to the equation (ii) as shown in the below figure.

Intercept = ln

In k Slope = -Ea/R
A A
log log
R R

0 1/T 1
T
A plot between In k vs 1/T T

Figure 18.14: Plot of ln k versus 1/T

Thus, it has been found from Arrhenius equation (i) that increase in temperature or decrease in activation energy
results in an increase in the rate of the reaction and an exponential increase in the rate constant.
Ea
In the plot, slope = – and intercept = ln A. So we can calculate Ea and A using these values.
R
Ea
At temperature T1, equation (ii) becomes ln k1 = – + ln A  ….(iii)
RT1
Ea
At temperature T2, equation (ii) becomes ln k2 = – + ln A  ….(iv)
RT2
(since A is constant for a given reaction)
k1 and k2 are the values of rate constants at temperatures T1 and T2 respectively. Subtracting equation (iii) from (iv),
we obtain

Ea Ea k2 Ea  1 1  k2 Ea  1 1 
ln k2 – ln k1 = – ; ln =  –  ; log =  – 
RT1 RT2 k1 R  T1 T2  k1 2.303R  T1 T2 
1 8 . 2 2 | Chemical Kinetics

Maxwell’s–Boltzmann Distribution Curve:


The peak of the curve corresponds to the most probable kinetic energy, i.e. kinetic energy of maximum fraction of
molecules. Number of molecules decreases with energies higher or lower than this value. When the temperature
is raised, the maximum of the molecules moves to the higher energy value (figure) and the curve broadens out,
i.e. spreads to the right such that there is a greater proportion of molecules with much higher energies. The area
under the curve must be constant since total probability should always be unity at any given time. We can mark
the position of Ea on Maxwell Boltzmann distribution curve.

t
Fraction of molecules

(t + 10) Energy of
activation
This area shows fractional
This area shows of additional molecules
fraction of which react at (t + 10)
molecules
reacting at t

Kinetic energy
Figure 18.15: Distribution curve showing temperature dependence of rate of a reaction

Increase in the temperature of the substance increases the fraction of molecules, which collide with molecules with
energies greater than Ea. It is clear from the diagram that in the curve at (T +10), the area showing the fraction of molecules
having energy equal to or greater than activation energy gets doubled leading to doubling the rate of a reaction.

9.4 Effect of Catalyst


A catalyst is a substance which alters the rate of a reaction without undergoing any permanent chemical change.
For example, MnO2 catalyses the following reaction so as to increase its rate considerably
2KClO3 
MnO
2 → 2KCl + 3O
2

Reaction path
without catalyst Energy of
activation
Energy of
Potential Energy

without
activation
Reaction catalyst
with
Reactants path with catalyst
catalyst

Products

Reaction coordinate

Figure 18.16: Effect of catalyst on activation energy

Catalytic Mechanism: The mechanism of the catalyst can be explained by intermediate complex theory. According
to this theory a catalyst reacts with the reactant to form temporary bonds resulting in an intermediate complex.
This has a transitory existence and decomposes to yield products and the catalyst.
It is believed that the catalyst provides an alternate pathway or reaction mechanism by reducing the activation
energy between reactants and products and hence lowering the potential energy barrier.
−Ea /RT
According to Arrhenius equation, k = Ae , the lower the value of activation energy, the faster will be the rate
of a reaction.
Chem i str y | 18.23

PLANCESS CONCEPTS

For catalysts
•• Even a small amount of the catalyst has the ability to catalyze a large amount of reactants.
•• Gibbs energy, ∆G, of a reaction is independent of the catalyst.
•• It has an effect on spontaneous reactions but does not catalyse non-spontaneous reactions.
•• Catalyst does not change the equilibrium constant of a reaction, rather it helps to attain equilibrium
faster, i.e. it catalyses the forward as well as the backward reaction to the same extent so that the
equilibrium state remains same and is reached earlier.

For collision theory


•• Activation energy and proper orientation of the molecules together determine the criteria for an
effective collision and hence the rate of a chemical reaction.
•• It considers atoms/molecules to be hard spheres and ignores their structural aspect.
•• Comparing the equation (vi) with Arrhenius equation, we can say that A is related to collision
frequency.
Saurabh Chaterjee (JEE Advanced 2013, AIR)

Note: In the following reaction formation of methanol from bromo-ethane depends upon the orientation of
reactant molecules. Only proper orientation of reactant molecules lead to bond formation, else it simply bounce
back and no products are formed.
CH3 +OH– → CH3OH + Br –

H + -
Improper -
H C Br OH Products
Orientation
H + - H
-
H C Br OH
H H H
Proper - + -
-
Orientation HO C Br OH C H + Br

H H H
Intermediate

Steric Factor: For effective collisions, the probability or steric factor (P) is introduced. It helps the molecules for a
−E /RT
proper oriented i.e., Rate = PZAB e a

Illustration 15: What will be the effect of temperature on rate constant? (JEE MAIN)

Sol: Rate constant of a reaction is nearly doubled with rise in temperature by 10°C. The dependence of the rate
−Ea /RT
constant on temperature is given by Arrhenius equation, k = Ae , where A is called frequency factor and Ea is
the activation energy of the reaction.

Illustration 16: How is the value of activation energy calculated from the rate constants at two different
temperatures. If the value of activation energy is 50 kJ/mol then show that by increasing the temperature from 300
K to 310 K, rate constant becomes nearly double. (JEE MAIN)
Ea 1
Sol: We know that Arrhenius equation can be written as log k = log A –
2.303R T
1 8 . 2 4 | Chemical Kinetics

If k1 and k2 are the rate constants at two different temperature T1 and T2 then Arrhenius equation at both the
temperatures can written as
Ea 1 Ea 1
log k1 = log A – ; log k2 = log A –
2.303R T1 2.303R T2
Ea 1 1  k Ea  1 1 
Subtracting equation (i) from (ii), we get log k2 – log k1 =  −  or =log 2  − 
2.303R  T1 T2  k1 2.303R  T1 T2 

From the values of k1 and k2 at temperature T1 and T2, Ea can be calculated.


Given T1 = 300K, T2 = 310 K, Ea = 50 kJ or 50,000 J
k 50000  1 1  50000  310 − 300 
Put these values =
in eq. (iii), log 2  −  =  
k1 2.303 × 8.314  300 310  2.303 × 8.314  310 × 300 
k2
or log = 0.2808 = Antilog 0.2808 = 1.91 ≈ 2
k1
It is clear that by increasing the temperature from 300 K to 310 K doubles the rate constant.

Illustration 17: Even an exothermic reaction has activation energy. Why? (JEE ADVANCED)
Sol: A reaction can either be endothermic or exothermic, but it possesses a minimum energy level for the molecules
to cross the energy barrier for the reaction to take place. Also
Threshold energy = ΣER + Ea and ∆H = ΣEP – ΣER (∆H may be + ve or – ve)
For example, burning of carbon is highly exothermic process, yet it does not start of its own. The activation energy
of combustion of carbon is quite high and thus, in spite of exothermic nature, the reaction starts only when flame
is applied to the heap of carbon contents.

Illustration 18: A first-order reaction is 50% complete in 30 min at 27°C and in 10 min at 47°C. Calculate the rate
constants, and the energy of activation of the reaction in kJ/mol. (JEE ADVANCED)
Sol: Time for the completion of 50% reaction means t1/2.
It means t1/2 of the reaction at 27°C is 30 min and at 47°C is 10 min.
0.693 0.693 0.693
We know that k = or k= = 0.0231 min–1(at 27°C) and k = = 0.0693 min–1(at 47°C)
t1/2 30 10

k Ea  1 1 
We know that
= log 2  − 
k1 2.303R  T1 T2 

k2 = 0.0693 min–1, k1 = 0.0231 min–1, T1 = 27 + 273 = 300 K, T2 = 47 + 273 = 320 K,



R = 8.314 JK–1 mol–1, E = ? a

0.0693 Ea  1 1 
log =  – 
0.0231 2.303 × 8.314  300 320 

Ea  320 − 300 
or log 3 =  
2.303 × 8.314  300 × 320 

Ea  20 
0.4771 =  
2.303 × 8.314  300 × 320 

 0.4771 × 2.303 × 8.314 × 300 × 320 


or Ea =   = 43848.49 J mol = 43.85 kJ mol
–1 –1

 20 
Chem i str y | 18.25

10. METHODS OF DETERMINATION OF ORDER OF REACTION

10.1 Method of Integration (Hit and Trial Method)


The most simple method is the one in which the quantities a, x and t are determined and substituted in the kinetic
equations of various orders. The equation which gives the most constant value for the specific rate constant (k) for
a series of time intervals is the one corresponding to the order of reaction. If all the reactants are at the same molar
concentrations, the kinetic equations are:
2.303 a
k= log10 , for first-order reactions;
t (a − x)

1 1 1
k=  −  , for second-order reactions;
t  (a − x) a 

1  1 1
k=  −  , for third-order reactions;
2t  (a − x)2
a2 

10.2 Graphical Method


A graphical method based on the respective rate laws can also be used to determine the order of reaction.
If the plot of log (a – x) versus ‘ t’ is a straight line, the reaction follows first order.
1
If the plot of versus ‘ t’ is a straight line, the reaction follows second order.
(a − x)
1
If the plot of versus ‘t’ is a straight line, the reaction follows third order.
(a − x)2
1
In general, for a reaction of nth order, a graph of versus ‘t ‘ must be a straight line.
(a − x)n−1

10.3 Half-Life Method


1
A general expression for the half-life, (t1/2 ), is given by t1/2 ∝
n−1
a

Zero order 1st order 2nd order 3rd order
t1/2

t1/2

t1/2

t1/2

2
Conc. Conc. 1/a 1/a
1 −n
Figure 18.17: Plots of half-lives versus concentration (t1/2 ∝ a )

This relation can be used to determine order of reaction ‘n’.

10.4 Van’t Hoff Differential Method


Relationship between velocity V of nth order reaction and concentration of reactants C is given by
log(V1 / V2 )
Van’t Hoff, n =
log(C1 / C2 )
Where, C1 and C2 are two different concentrations, while V1 and V2 are their velocities.
1 8 . 2 6 | Chemical Kinetics

10.5 Ostwald Isolation Method


This method is used to find out the order of complex reactions. If nA, nB and nC molecules of substance A, B and C,
respectively are present in a reaction, then nA + nB + nC will be the order of reaction:
When B and C are in excess, the order of reaction will be nA.
When A and B are in excess, the order of reaction will be nC.
When A and C are in excess, the order of reaction will be nB.

PROBLEM-SOLVING TACTICS

(a) To determine the average rate for change in concentration over a time period.
Average rate of reaction is the change in concentration of reactants (or products) during large interval of time.
[reactant at t2 ]–[reactant at t1 ]
Rate = –
t2 –t1

Square brackets denote concentration.


Negative sign in the above equation is used to make the rate of reaction positive. Minus sign can be ignored
when calculating average rates from products.

∆[reactant ] ∆[product ]
Rate = – or rate=
∆t ∆t
0.20
(b) To determine instantaneous rate from a plot of concentration
versus time: Instantaneous rate at time t is determined as follows: 0.15 Rate = -Slope =
-2
1.06 x 10 M/sec
(i) Calculate the negative slope of the curve between concentration mol
of a reactant and time at t. 1

0.10
(ii) Calculate the slope of the curve between concentration of a
product and time at t.
(c) Problem-solving tactics to determine the initial rate from a plot 0.05
of concentration versus time: The initial rate of a reaction is the
instantaneous rate at the start of the reaction (i.e., when t = 0). 0.00
Initial rate is equal to the negative slope of the curve between 5 10 15 20 25
reactant concentration and time at t = 0. Time, sec.

Figure 18.18: Plot of concentration


(d) To determining the order of a reaction from its rate law
versus time
Rate law of a reaction is used to determine:
•• The order of the reaction with respect to one or more reactants.
•• The overall order of the reaction.
rate = k[A]n[B]m[c]p
For the rate law: Order with respect to A = n; order with respect to B = m, order with respect to C = p
Reaction or overall order = n + m + p
Note: The stoichiometric coefficient in the balanced equation for a chemical reaction is usually different
from the order.
Chem i str y | 18.27

Reaction Experimental Rate Law Order

NO2 + CO → NO+ CO2 rate = k[NO2]2 2nd order reaction 2nd order in NO2 0 order in CO

CH3CHO → CH4+ CO rate = k[CH3CHO]2 2nd order reaction 2nd order in CH3CHO

(e) To determining rate laws from graphs of concentration versus time (integrated rate laws).
To determine the rate law for a reaction for different concentration (or the values of some function of
concentration) versus time, make three graphs.
[A] versus t (linear for a zero-order reaction)
ln [A] versus t (linear for a 1st order reaction)
1 / [A] versus t (linear for a 2nd order reaction)
The graph that is linear indicates the order of the reaction with respect to A. Then, you can choose the correct
rate equation:

For a zero-order reaction, Rate = k (k = -ve slope of line)

For a first order reaction, rate = k[A] (k = -ve slope of line)

For a second order reaction, rate = k[A]2 (k = slope of line)

(f) Regarding questions of half lives:


For a zero-order reaction A → products, rate = k , t½ = [A0] / 2k
For a first-order reaction A → products, rate = k[A], t½ = 0.693 / k
For a second-order reaction 2A → products or A + B → products (when [A] = [B]), rate = k[A]2 , t½ = 1 / k [A0]
Graphical Relations and half-lives: Differences in half-lives for reactions of different orders (0, 1st, or 2nd) are
determined by plotting graphs between reactant [A] and time (t). Change in time changes the concentration
of a reactant to half.
(i) For a zero-order reaction, half-life decreases with decreasing concentration.
(ii) For a 1st order reaction, half-life is constant.
(iii) For a second-order reaction, half-life increases with decreasing concentration.

[A] vs time for a [A] vs time for a [A] vs time for a


Zero order reaction First order reaction Second order reaction
0.20 0.20 0.20
Half life decreases Length of half life Length of half life
with decreasing is constant increases with decreasing
0.15 concentration 0.15 0.15 concentration
mol mol
[A],M
L st st L st
1 half life 1 1
0.10 rd
0.10 half life 0.10 half
3
nd half life nd life
2 2
0.05 half life 0.05 half life 3rd 0.05
rd
3
half life half life
0.00 0.00 0.00
20 40 60 80 0 5 10 15 20 25 100 200 300 400
Time sec. Time (sec) Time (sec)
Figure 18.19: Plot of concentration versus change in time

For a first-order reaction: For a second-order reaction:


A → products, rate = k A → products, rate = k[A] 2A → products/A + B → products
(when [A] = [B], rate = k[A]2
1 8 . 2 8 | Chemical Kinetics

POINTS TO REMEMBER

Topic Formula
Average rate of
reaction
Change in the concentration of reactants or(Products) ∆C C − C1
Average rate = = ± ± 2
=
Time ∆t t2 − t1

Instantaneous
∆C dC
rate of reaction Instantaneous rate = L im =
∆t → 0 ∆t dt

For the reaction n1A + n2B → m1C + m2D


1 d[A] 1 d[B] 1 d[C]
= – = +
n1 dT n2 dT m1 dT
1 d[A] 1 d[B] 1 d[C] 1 d[D]
Instantaneous Rate of reaction = – = – = + =
= +
n1 dT n2 dT m1 dT m2 dT
1 d[D]
= +
m2 dT
Factors affecting •• Nature of reactants and products
rate of reaction •• Effect of temperature
•• Concentration of Reactants
•• Presence of catalyst
•• Effect of Sunlight
Law of mass The rate at which a substance is directly proportional to its active mass and the rate at which a reaction
action and rate proceeds is proportional to the product of the active masses of the reacting substances
constant
 dx   dx 
For a reaction, aA + bB → product rate =   ∝ [A] [B] ;   = k[A] [B]
a b a b

 dt   dt 
where k is rate constant or velocity constant.
dx
When [A] = [B] = 1 mol/L, then =k
dt

Unit of rate n−1


constant  litre 
Unit of rate constant =   × sec–1
 mol 
When n = order of reaction.

Various types of Type of Integrated rate equation Unite of rate t1/2 Half-life t3/4 period
reactions reaction constant period
Zero-order Concentration
d[A] A0
reaction – = k0[A]0 time–1
dt 2k
dx
Differential form =k
dt
Chem i str y | 18.29

First-order Time–1
reaction k1= 2.303 a 0.693 0.693 1.382
log10 2× =
t (a − x) K1 K1 k1

dx
Differential form
dt
= k(a - x)

Second-order Mole–1 litre


2.303 b(a − x)
reaction k2 = log time–1
t(a − b) a(b − x) 1 3
dx K 2a K 2a
Differential form
dt
= k(a – x)2
Third-order Litre2 mole–2 _____
1(2a − x) 1 3
reaction k3 = time–1
t2a2 (a − x)2 2 K 2a
dx
Differential form
dt
= k(a – x)3
Relationship Zero Order First Order Second Order Third Order
between Rate
of reaction and
rate constant
r r r r

0 1 2 3
(conc) (conc) (conc) (conc)
1/(a - x)

2
(conc)

log[A]

1/(a -x)

t t t t

t1/2 t1/2 t1/2 t1/2

0 1
(conc) (conc) 1/a 1/a

Half-Life
1
t1/2 ∝ where n = order of reaction
n−1
a

Arrhenius
k Ea  1 1 
theory log 2
=  − 
k1 2.303R  T1 T2 
−Ea /RT
k = Ae where k1 and k2 are rate constant at temperatures T1 and T2, respectively (T2 > T1).
1 8 . 3 0 | Chemical Kinetics

Solved Examples

JEE Main/Boards Example 3: In a reaction 2N2O5 → 4NO2 + O2, the rate


can be expressed as
Example 1: The half-life period of a first-order reaction d[N2O5 ]
is 30 min. Calulate the specific reaction rate of the (i) – = k1[N2O5]
dt
reaction. What fraction of the reactant remains after 70
d[NO2 ]
min? (ii) = k2[N2O5]
dt
0.6932 0.6932
Sol: k1 = = = 0.0231 min–1. d[O2 ]
t1 30 (iii) = k3[N2O5]
dt
2

Let the reaction be A → Product How are k1, k2 and k3 related?

Initial concentration a Sol: The rate law reaction is rate =


Concentration after (a – x) x
1 d[N2O5 ] 1 d[NO2 ] d[O2 ]
70 min − = = = k N2O5 
2 dt 4 dt dt
∴ Fraction of the reaction remained unreacted
d[N2O5 ]
(a − x) 2.303 a ∴– = 2k[N2O5] = k1[N2O5]
= Now, k1 = log or 0.0231 dt
a . t a−x d[NO2 ]
2.303 a = 4k[N2O5] = k2[N2O5]
= log dt
70 a−x
d[O2 ]
a 0.0231 × 70 = k [N2O5] = k3[N2O5]
log = = 0.7021 dt
a−x 2.303
a k1 = 2k
Taking antilog, we get = 5.036  k k
a−x ∴ k 2 = 4k or k = 1 = 2 = k
k = k 2 4
a−x 1  3
∴ = ≈ 0.2
a 5.036
or 2k1 = k2 = 4k3.

Example 2: For the reaction 2NO + Cl2 → 2NOCl,


when the concentration of both reactants is doubled Example 4: The reaction 2N2O5 → 4NO2 + O2 forms
the rate increased by a factor of 8, but when only the NO2 at the rate of 0.0072 mol L-1s-1 after a certain time.
concentration of Cl2 concentration is doubled, the rate
(a) What is the rate of change of [O2] at this time?
doubles. What is the order of the reaction with respect
to NO and Cl2? (b) What is the rate of change of [N2O5] at this time?
(c) What is the rate of reaction at this time ?
Sol: Rate = k [NO]m [Cl2]n
Let the concentrations of NO and Cl2 be x and y, Sol: The rate of the reaction is expressed as
respectively.
1 d[N2O5 ] 1 d[NO2 ] d[O2 ]
rate = – = + = +
R1 = kxm yn and, R2 = k (2x)m (2y)n 2 dt 4 dt dt
R2 and given that
∴ = 2m + n = 8 = 23. (given)
R1
d[NO2 ]
∴ m + n = 3 Again, R3 = k(x)m (2y)n =0.0072 molL-1s-1.
dt
R3
= k xmyn. 2n. ∴ = 2n = 2 (given) (a) Rate of appearance of
R1
∴ n = 1; m = 3 – 1 = 2. 1
O2 = × rate of appearance of NO2
4
Chem i str y | 18.31

d[O2 ] 1 d[NO2 ] 1 At zero time, no CH3COOH is formed. Hence,alkali used


= × = × 0.0072 = 0.0018 mole/L/s. at zero time is only for HCl. Thus we have
dt 4 dt 4
1 Time(min) : 0 20 119 ∞
(b) Rate of disappearance of N2O5 = × rate of
appearance of NO2 2 Vol. of alkali

(mL)used 
d[N2O5 ] 1 d[NO2 ] 1  : 19.24 20.73 26.6 42.03
– = × = × 0.0072 against 
dt 2 dt 2
CH3COOH 
= – 0.0036 mole /L/s.
−19.24 −19.24 −19.24 −19.24
1 d[NO2 ]
(c) Rate of reaction = × = 0= 1.49 = 7.36 = 22.79
4 dt (x) (x) (a)
1
= × 0.0072 = 0.0018 (mole/L)s-1.
4 For t – 20;

Example 5: The activation energy for the reaction 2.303 22.79


k1= log =0.0033 min–1
O3 (g) + NO (g) → NO2 (g) + O2 (g) is 9.6 kJ/mol. Prepare 20 22.79 – 1.49
an activation energy plot it ∆H° for this reaction is -200 For t = 119 ;
kJ/mole. What is the energy of activation for the reverse 2.303 22.79
reaction? k 1= log =0.0032 min–1
119 22.79 – 7.36
Sol: Energy of activation for reverse reaction The constancy of k1 shows that the reaction is of first
= 9.6 + 200 kJ = 209.6 kJ. order.

Example 7: For the reaction


k k
[Cr[H 2 O] 4 Cl 2 ] + (aq) → [Cr(H 2 O) 5 Cl 2 ] 2+ (aq) 
1 2→
9.6kJ
E [Cr(H2O)6]3+(aq)
k1 = 1.76 × 10–3 s–1 and k2 = 5.8 × 10–5 s–1 for the initial
Energy

200kJ concentration of [Cr(H2O)5Cl2]+ is 0.0174 mol/L at 0°C.


Calculate the value of t at which the concentration of
[Cr(H2O)5Cl2]2+ is maximum.
Reaction coordinate
2.303(logk1 – logk 2 )
Sol: We have, t =
Example 6: 1 mL of methyl acetate was added to 20 mL k1 – k 2
of 0.5 N HCl and 2mL of the mixture was withdrawn from
time tc during the progress of hydrolysis of the ester and 2.303(log1.76 × 10−3 – log5.8 × 10−5 )
= = 2005 seconds.
titrated with a solution of alkali. The amount of alkali 1.76 × 10 −3 − 5.8 × 10 −5
needed for titration at various intervals is given below:

Time: 0 20 119 ∞ (min) Example. 8: The complexation of Fe2+ with the chelating
agent dipyridyl has been studied kinetically in both
Alkali used: 19.24 20.73 26.6 42.03 (mL)
forward and reverse directions.
Establish that the reaction is of first order. Fe2+ + 3 dipy → Fe (dipy)32+

Sol: Rate (forward) = (1.45 × 1013) [Fe2+][dipy]3and rate


HCl
CH3COOCH3 + H2O 
[H]
→ CH3COOH + CH3OH  (reverse) = (1.22 × 10–4 [Fe (dipy)32+ ].
Ini.Conc. a Find the stability constant for the complex.
Conc. after t (a-x) x
Sol: At dynamic equilibrium, Rate of formation of
HCl acts as a catalyst. The alkali used against HCl is
complex = Rate of its decomposition
subtracted from the total alkali used (given in the data)
to get the volume of alkali used only against CH3COOH. (1.45 × 1013) [Fe2+][dipy]3 = (1.22 × 10–4 [Fe (dipy)32+ ]
1 8 . 3 2 | Chemical Kinetics

= 1.25 × 104 × 1.987 × 10–3 kcal mol–1 = 24.84 kcal mol–1


[Fe(dipy)32+ ] 1.45 × 1013
ka = = = 1.19 × 1017. (b) ln K = 14.34 – [(1.25 × 104)/500]
[Fe2+ ][dipy]3 1.22 × 10−4
(∵ T = 500 K)

Example 9: Bicyclohexane was found to undergo two ∴ K = 2.35 × 10–5 sec–1


parallel first order rearrangements. At 730 K, the first 0.693
order rate constant for the formation of cyclohexene (c) K = (for first order)
256 × 60
was measured as 1.26 × 10–4 sec-1, and for the formation
of methyl cyclopentane the rate constant was 3.8 × 0.693 1.25 × 10 4
∴ log = 14.34 –
10–5sec–1. What is the percentage distribution of the 256 × 60 T
rearrangement products? ∴ T = 513 K

Sol:
Example 2: The specific reaction rate of a first-order
k1
Cyclohexene reaction is 0.02 sec–1. The initial concentration of the
Bicyclohexane reactant is 2 molL–1. Calculate (a) initial rate, and (b) rate
after 60 sec.
k2 Methylcyclopentane
Sol: For a first-order reaction:
k1
Percentage of cyclohexene = × 100 Rate of a reaction = k × molar concentration of the
k1 + k 2
1.26 × 10 −4 reactant.
= × 100 = 77%
1.26 × 10−4 + 3.8 × 10−5 (a) ∴ Initial rate = k × initial concentration

∴ Percentage of methyl cyclopentane = 23%. = 0.02 × 2 = 0.04 mol/L–1sec–1.


2.303
(b) Concentration of the reactant after 60 sec k =
Example 10: A first-order reaction has a specific 2 60
reaction rate of 10–2 sec–1. How much time will it take log = 0.02.
concentration after 60 s
for 10 g of its reactant to be reduced to 2.5 g?
∴ Concentration of the reactant after 60 sec = 0.60 M.
Sol: Rate constant, k = 10–2 sec–1
∴ Rate after 60 sec = k × concentration of the reactant
Initial reactant conc. [A]0= 10 g after 60 sec.
Final reactant conc. [A]t = 2.5 g = 0.02 × 0.60 = 0.012 molL–1sec–1
Time required, t = ?
Example 3: The rate constant is numerically the same
For a first-order reaction.
for first, second and third order reaction, the unit of
t = 2.303 × 102log 4s = 230.3 × 0.6020s = 138.6s. concentration being in moles per litre. Which reaction
should be the fastest and is this true for all ranges of
concentrations ?
JEE Advanced/Boards
Sol: Suppose R1, R2 and R3 are the rates of reactions of
Example 1: The rate constant of a reaction is given by: ln first, second and third order, respectively, and k is the
K(sec–1) = 14.34 – (1.25 × 104)/T. Calculate (a) the energy rate constant, which is the same for the three reactions,
of activation and (b) the rate constant at 500 K. (c) At ∴ R1 = k[A]1 ; R2 = k[A]2 ; R3 = k[A]3
what temperature will its half-life period be 256 min?
[A] being the concentration of the reactant A in moles
Sol: Given: per litre.

ln K = 14.34 – [(1.25 × 104)/T] ….(i) Now if, [A] = 1, R1 = R2 = R3 ;

Arrhenius equation, ln K = ln A–(Ea/RT)..(ii) [A] < 1, R1 > R2 > R3 ; and

(a) Comparing equations (i) and (ii), [A] > 1, R1< R2 < R3.

(Ea/R) = 1.25 × 104 ∴ Ea = 1.25 × 104R


Example 4: For a reaction at 800°C
Chem i str y | 18.33

2NO + 2H2 → N2 + 2H2O, the following data were At ∞ time, i.e. when the reaction is complete, the whole
obtained: of C6H5N2Cl converts into N2. Hence volume of N2 at ∞
time corresponds to the initial concentration ‘a’ while
[NO]×10–4 mole/L [H2]×10–3 mole/L d[NO]/dt×10–4
volumes of N2 at different time intervals correspond to x
mole/L min
as shown above. substituting the given data in equation
(i) 1.5 7.0 4.4
of first-order reaction, we get the following results.
(ii) 1.5 3.5 2.2
(iii) 1.5 2.0 0.24 For t = 20 min
What is the order of this reaction with respect to NO 2.303 162
k1 = log = 0.0032 min–1
and H2 ? 20 162 − 10
For t = 50 min,
Sol: From the data (i) and (ii), we see that when the
concentration of H2 is halved, the rate is also halved at 2.303 162
k1 = log = 0.0033 min–1
constant concentration of NO. Hence the reaction is of 50 162 − 25
first order with respect to H2 Let us now consider the For t = 70 min,
data (ii) and (iii) to determine the order with respect to
2.303 162
NO as [H2] is constant. k1 = log = 0.0032 min–1
70 162 − 33
The rate law of the above reaction is
The consistency of k1 shows that the decomposition of
1 d[NO] C6H5N2Cl is a first-order reaction.
rate = – × = k[NO]m[H2]1
2 dt
Example 6: From the following reaction scheme, write
where, m is the order with respect to NO
the rate law for the disappearance of A, B and C.
d[NO] k
Or – = 2k[NO]m[H2] (1) A + B →C + D
1
dt k
(2) C + D 
2→A + B
Substituting data (ii) and (iii), we get k
(3) B + C →E + D
3
2.2 × 10 = 2k(1.5 × 10 )m. (2 × 10 ) 
–4 –4 –3
...(i)
0.24 × 10–4 = 2k(0.5 × 10–4)m. (2 × 10–3)  …(ii) Sol.: The reaction A is removed in step 1 and produced
in step 2
Dividing (i) by (ii),
d[A]
2.2 (1.5 × 10−4 )m 220 ∴– = k1[A] [B] – k2[C][D] Similarly
= = 3m or = 3m dt
0.24 (0.5 × 10−4 )m 24
d[B]
– = k1[A][B] + k3[B][C] – k2[C][D] and
Taking log, log 220 – log 24 = m log 3 dt
2.4324 – 1.3802 = m × 0.4771 d[C]
– = k2[C][D] + k3[B][C] – k1[A][B].
dt
0.9622
Or 0.9622 = 0.4771 m or m = = 2.
0.4771
Example 7: At a certain temperature, the half change
Hence the reaction is of second and first order with period for the catalytic decomposition of ammonia
respect to NO and H, respectively. were found as follows:
Pressure (Pascals): 6667 13333 26666
Example 5: From the following data for the de-
composition of diazobenzene chloride, show that the Half life period in hours: 3.52 1.92 1.0
reaction is of first order Calculate the order of reaction.
Time 20 50 70 ∞ (min) n−1
(t1/2 )1 a 
Vol.of N2 10 25 33 162 (mL) Sol: =  2 
(t1/2 )2  a1 
Sol: C6H5N2Cl → C6H5Cl + N2
where, n is order of reaction
Initial concentration    a n−1
3.52  13333 
From the given data, = 
After time t   (a – x) x 1.92  6667 
(a ∝ initial pressure) = (2)n –1
1 8 . 3 4 | Chemical Kinetics

3.52 The rate constant and activation energy for reaction


log = (n – 1) log 2 = 0.3010 × (n – 1) (i) are 2.79 × 10–3 min–1 at 237°C and 12.0 kcal mol–1
1.92
respectively. These values for reaction (ii) are 1.52 × 10–4
0.2632 = 0.3010 × (n – 1) ; n = 1.87 ≈ 2 min–1 at 237°C and 24.5 kcal mol–1 respectively. Find out
Similar calculations are made between first and third the temperature at which equimolar quantities of H2O,
observations, n comes equal to 1.908 (≈ 2). CO, CO2 and H2 are formed (R = 2 cal).
Thus, the reaction is of second order. −Ea /RT
Sol: For reaction (a) K1 = A1e
Example 8: The optical rotation of can sugar in 0.5 N 12×103

acid at 25°C at various time intervals are given below: or 2.79 × 10–3 = A1e RT  ……(i)
−Ea /RT
Time (min): 0 1435 11360 ∞ For reaction (b): K2 = A2e
24.5×103
Rotation(°): 34.50° 31.10° 13.98° – 10.77° –
1.52 × 10–4 = A2e RT  …(ii)
Show that the reaction is of first order.
Sol: 2.79 × 10−3 2.79 × 10−3
By equation (i) A1 = =
Lactic acid –
12×103 7.8 × 10−6
C12H22O11 
→ C6H12O6 + C6H12O6 e 2×510

+ H2O Glucose Fructose = 3.58 ×10 2

Sucrose (excess) Dextro Laevo 1.52 × 10−4 1.52 × 10−4


By equation (ii) A2 = =
rotatory rotatory 24.5×103 − 11
– 3.7 × 10
Since in this reaction dextro form clianges to laevo
e 2×510
= 4.11 ×106
form, the optical rotation decreases with the progress
of the reaction. Thus change in rotation is proportional If rate constants of two reactions are same, the reactions
to the amount of sugar remaind after different time will give equimolar mixture of products. Let these be
intervals. We now have, same at temperature T, i.e.
−Ea /RT −Ea /RT
Time 0 1435 11360 ∞ A1e 1 = A2e 2

(min)
Ea −Ea [24.5 −12.0]×103
2 1 A2 A2
Change in 34.50 – 31.10 – 13.98 – – 10.77– ∴ e RT = or e RT =
rotation(°) (–10.77) (–10.77) (-10.77) (–10.77) A1 A1
= 45.27 =41.87 =24.75 =0 4.11 × 106
(a – x)
= = 1.15 × 104
(a) (a – x) 3.58 × 102
Substituting the data in equation, 103 12.5 × 103
Or 9.35 \T =
× 12.5 = = 668 K
for t = 1435 min RT 9.35 × 2
2.303 45.27 ∴ T = 668 K = 395°C
k1 = log = 5.442 × 10–5
1435 41.87
and for t = 1136 min Example 10: For the reversible reaction in equilibrium:
k
2.303 45.27 
A ←
1
→ B. The values of K and K are 2 × 10–3 mol L–1
k1 = log = 5.311 × 10–5 k
 1 2
1435 41.87 2
sec–1 and 3 × 10–3 mol L–1 sec–1 respectively. If we add 0.5
The values of k are fairly constant and so the reaction mol of B in the equilibrium mixture, initially containing
is of first order . 2 mol of A. Calculate the time taken for concentration
of B to become equal to 3/4 of the concentration of A
Example 9: The catalytic decomposition of formic acid at initial equilibrium. The volume of mixture is 1 L and
may take place in two ways: remains constant.
(i) HCOOH → H2O + CO  1
→ B
k
Sol: A ← 
k
(ii) HCOOH → H2 + CO2 2

t=0 2 mol L –1
0
Chem i str y | 18.35

At eq. (2 – X) mol L–1 X or – 2.303 log (0.66 – X) = K2 . t + C


K1 = 2 × 10–3 mole L–1 sec–1 (zero order)
at t = 0, X = 0 ∴ C = – 2.303 log 0.66
K2 = 3 × 10 –3sec–1 (Ist order)
0.66
dX ∴ K2 . t = 2.303 log
= K1[A]0 – K2[B]1 0.66 – X
dt
2.303 0.66
dX ∴t= log = 89.24 sec
At equilibrium =0 3 × 10−3 0.66 – 0.155
dt
(a) Partial pressure becomes half of initial in every 100
K1 2 × 10−3
∴ 0=K1–K2[X]eq ; \[X]eq = = min, therefore, order = 1.
K2 3 × 10−3
800
= 0.66 mol L–1 = Kc (b) k × 100 = ln
400

A ←→B
 k × 100 =ln 2
Initial eq. 1.34    0.66 ⇒ k = 6.93 × 10–3 min–1
Moles added 1.34    0.66+0.5= 1.16 (c) For 75% reaction; time required
At eq. at time t (1.34 +X) (1.16 –X) = 2 × half-life = 200 min
(The reaction will obey back ward direction on addition (d) 2X(g) → 3Y(g) + 2Z(g)
of B) 3
800 – x x
3 3 2
∵ [B] = [A]eq = × 1.34 = 1.005 3
4 4 Total pressure = 800 + x
2
(1.16 – X) = 1.005; ∴ X = 0.155 Also 800 – x = 700 ⇒ x = 100
3
⇒ Total pressure = 800 + × 100 = 950 mm
dX 2
Now, = K1 – K2[X] = 0.66K2 –K2 X
dt
dX
= K2[0.66 – X] ; ∴ = K2 . dt
(0.66 – X)

JEE Main/Boards

Exercise 1 Q.3 The decomposition of a compound P at temperature


T according to the equation
Q.1 A solution of A is mixed with an equal volume of 2P(g) → 4Q(g) + R(g) + S(l)
a solution of B containing the same number of moles,
is the first order reaction. After 30 minutes from the
and the reaction A + B → C occurs. At the end of 1h,
start of decomposition in a closed vessel the total
A is 75% reacted. How much of A will be left unreacted
pressure developed is found to be 317 mm Hg and
at the end of 2h if the reaction is (a) first order in A and
after a long period of time the total pressure observed
zero order in B; (b) first order in both A and B; and (c)
to be 617 mm Hg. Calculate the total pressure of the
zero order in both A and B?
vessel after 75 minute, if volume of liquid S is supposed
to be negligible ,also calculate the tiny fraction t1/8.
Q.2 The reaction CH3–CH2–NO2+ OH– → CH3–CH–NO2-
+H2O obeys the rate law for pseudo first order kinetic Given: Vapor pressure of S () at temperature T = 32.5
in the presence of a large excess of hydroxide ion . If mm Hg.
1% of nitro ethane undergoes reaction in half minute
when the reaction concentration is 0.002 M, What is the Q.4 A certain reactant Bn+ is getting converted to
pseudo first order rate constant? B(n + 4)+ in solution. The rate constant of this reaction is
measured by titrating a volume of the solution with a
1 8 . 3 6 | Chemical Kinetics

reducing reagent which only reacts with Bn+ and B(n+4)+. Q.11 Two reactions
In this process, it converts Bn+ to B(n – 2)+ and B(n +4)+ to
(i) A → products
B(n – 1)+. At t = 0 the volume of the reagent consumed is
25 ml and at t = 10 min, the volume used up is 32 ml. (ii) B → products,
Calculate the rate constant of the conversion of Bn+ to follow first order kinetics. The rate of the reaction (i)
B(n + 4)+ assuming it to be a first order reaction. is doubled when the temperature is raised from 300
K to 310 K. The half-life for this reaction at 310 K is 30
Q.5 Decomposition of H2O2 is a first order reaction. A minutes. At the same temperature B decomposes twice
solution of H2O2 labelled as 20 volumes was left open as fast as A. If the energy of activation for the reaction
due to this, some H2O2 decomposed. To determine is half of that of reaction, calculate the rate constant of
the new volume strength after 6 hours 10 mL of this the reaction (ii) at 300 K
solution was diluted to 100 mL .10mL of this diluted
solution was titrated against 25mL of 0.025 M KMnO4 Q.12 A certain organic compound A decomposes by
solution under acidic conditions. Calculate the rate two parallel first order mechanism
constant for decomposition of H2O2.
k1 B
Q.6 A metal slowly forms an oxide film which completely A
protects the metal when the film thickness is 3.956 k2 C
thousand times of an inch. If the film thickness is 1.281
thou. in 6 weeks, how much longer will it be before it If k1: k2 = 1: 9 and k1 = 1.3 × 10–5s–1.
is 2.481 thou.? The rate of film formation follows first Calculate the concentration ratio of C to A, if an
order kinetics. experiment is started with only A and allowed to run
for one hour.
Q.7 An optically active compound A upon acid catalyzed
k
hydrolysis yield two optically active compound B and C + 
Q.13 The reaction cis – Cr(en)2 (OH)2 ←
1
→ trans–

by pseudo first order kinetics. The observed rotation of k 2
the mixture after 20 min was 5° while after completion Cr(en)2 (OH)+ is first order in both directions. At 25°C
of the reaction it was – 20°. If optical rotation per mole 2

of A, B & C are 60°,40° & – 80°. Calculate half-life of the the equilibrium constant is 0.16 and the rate constant
reaction. k1 is 3.3 × 10–4 s–1. In an experiment starting with the
pure cis form, how long would it take for half the
Q.8 A vessel contains dimethyl ether at a pressure of equilibrium amount of the Trans isomer to be formed?
0.4atm. Dimethyl ether decomposes as CH3OCH3(g)
→ CH4(g) + CO(g) + H2(g). The rate constant of Q.14 For a reversible first-order reaction
k1
k1
decomposition is 4.78 × 10–3 min–1. Calculate the ratio k2

of initial rate of diffusion to rate of diffusion after 4.5 = 10–2 s–1 and [B]eq /[A]eq = 4. If [A]0 = 0.01 mole L–1 and
hours of initiation of decomposition. [B]0 = 0, what will be the concentration of B after 30 s?

Q.9 At room temperature (20°C) orange juice gets Q.15 For the system A ( g) → B ( g) , ∆H for the forward
spoilt in about 64 hours. In a refrigerator at 3°C juice reaction is –33kJ/mol (Note. ∆H = ∆E in this case).
can be stored three times as long before it gets spoilt.
Estimate (a) the activation energy of the reaction that Show that equilibrium constant
causes the spoiling of juice (b) How long should it take [B]
K= = 5.572 × 105 at 300 K. If the activation energies
for juice to get spoilt at 40°C? [A]
Er and Eb are in the ratio 20: 31. Calculate Er and Eb at this
Q.10 A first order reaction, A → B, requires activation temperature .Assume that the pre-exponential factor is
energy of 70 kJ mol–1.When a 20% solution of A was the same for the forward and backward reactions
kept at 25°C for 20 minutes, 25% decomposition took
place. What will be the percent decomposition in the Q.16 The complex [Co(NH3)5F]2+ reacts with water
same time in a 30% solution maintained at 40°C ? according to the equation
Assume that activation energy remains constant in this
range of temperature. [Co(NH3)5F]2+ + H2O → [Co(NH3)5(H2O)]3+ + F–
Chem i str y | 18.37

The rate of the reaction = rate const. x[complex]a x[H+]b. The initial pressure in a container of capacity V litres is
The reaction is acid catalysed i.e. [H+] does not change 1 atm. Pressure at time t = 10 sec is 1.4 atm and after
during the reaction. infinite time it becomes 1.5 atmosphere. Find the rate
constant k1 and k2 for the appropriate reaction.
Thus rate = k[Complex]a where k’ = k[H+]b calculate ‘a’
and ‘b’ given the following data at 25°C.
Q.21 A first order reaction takes 69.3 minutes for 50%
[Complex]M [H+ ]M T1/2hr T3/ 4hr completion. How much time will be needed for 80%
0.1 0.01 1 2 completion?

0.2 0.02 0.5 1


Q.22 The specific rate constant for a reaction increases
k
by a factor 4 of the temperature is changed from 27°C
Q.17 For the two parallel reactions A → B and
1
to 47°C. Find the activation energy for the reaction
k
2
A  → C , show that the activation energy E’ for the
disappearance of A is given in terms of activation Q.23 The reaction 2A+ B + C → D + 2 E is of first order
k E + k 2E2 with respect to A and of second order with respect to B
energies E1 and E2 for the two paths by E’ = 1 1 and is of zero order with respect to C
k1 + k 2
(i) Write down the rate law for the reaction
Q.18 For the mechanism
(ii) What will be the effect of doubling concentration of
k

A + B ←
1 k3
→ C ; C  →D
 A, B and C.
k

2

(a) Derive the rate law using the steady-state Q.24 A first order reaction is 50% completed in 30 min
approximation to eliminate the concentration of C. at 27°C and in 10 minutes at 47°C. Calculate the rate
(b) Assuming that k3 << k2, express the pre-exponential constant at 27°C and the energy- of activation of the
factor A and Ea for the apparent second order rate reaction in kJ per mole
constant in terms of A1, A2 and A3 and Ea , Ea and Ea
1 2 3
for the three steps. Q.25 The optical rotation of sucrose in 0.5 M HCl at 35°
C at different time intervals are given below. Show that
Q.19 The reaction of formation of phosgene from CO the reaction follows first order kinetics
and Cl2 is CO + Cl2 → COCl2 Time (min) 0 10 20 30 40 ∞
The proposed mechanism is Rotation +32.4 +28.8 +25.5 +22.4 +19.6 –11.1
k1 (degrees)

(i) Cl2 ← →
 2Cl (fast equilibrium)
k −1
k

(ii) Cl + CO ←
2 →
 COCl (fast equilibrium) Q.26 t1/2 of a reaction is halved as the initial concentration
k −2
of the reaction is doubled, find out the order of the
(iii) COCl + Cl2 
k3
→ COCl2 +Cl (slow)
 reaction.

Show that the above mechanism leads to the following Q.27 The rate constant of a reaction is 1.5 × 10–7 sec–1
d[COCl2 ] at 50°C and 4.5 × 10–7 sec–1 at 100°C. Evaluate the
rate law = K[CO][Cl2]3/2.
dt Arrhenius parameters A and Ea.
1/2
k  k  Q.28 A substance reacts according to the law of first
Where K = k 3 ⋅ 2  1  .
k − 2k −1 order reaction the velocity constant of the reaction is
1.0 × 10–2 sec–1. If initial conc. of the substance is 1.0 M
Q.20 For the following first order gaseous reaction (a) Find out the initial rate
k1 (b) Find out the rate after 1 min.
2B(g
A(g)
Q.29 What will be initial rate of a reaction if its rate
k2
C(g) constant is 10–3 min–1 and concentration of reactant is
0.2 mol dm–3. How much of reactant will be converted
into products in 200 minutes.
1 8 . 3 8 | Chemical Kinetics

Q.30 A first order reaction is 20% complete in 10 Q.5 t1/4 can be taken as the time taken for the
minutes. Calculate concentration of a reactant to drop to 3/4 of its value.
If the rate constant for a first order reaction is k, the t3/4
(a) Specific rate constant of the reaction and
can be written as
(b) Time taken for the reaction to go to 75 % completion
(A) 0.69/k (B) 0.75/k (C) 0.10/k (D) 0.29/k

Exercise 2 Q.6 A reaction was found to be second order with


respect to the concentration of carbon monoxide. If
Single Correct Choice Type the concentration of carbon monoxide is doubled, with
everything else kept the same, the rate of reaction will
Q.1 For the reaction A + B → C; starting with different
initial concentration of A and B, initial rate of reaction (A) Double (B) Remain unchanged
were determined graphically in four experiments.
(C) Triple (D) Increase by a factor of 4
S. No. [A]0/M (Initial [B]0/M (Initial rate/ (M sec )
–1

conc.) conc.) Q.7 For a hypothetical reaction,


1 1.6×10–3 5×10–2 10–3
A + 3B → P ∆H = –2x kJ/mole of A
2 3.2×10–3 5×10–2 4×10–3
3 1.6×10–3 10–1 2×10–3 and M → 2Q + R ∆H = –x kJ/mole of M
4 3.2×10–3 10–1 8×10–3 If these reactions are carried simultaneously in a
reactor such that temperature is not changing. If rate of
Rate law for reaction from above data is
disappearance of B is y M sec–1 then rate of formation
(A) r = k[A]2W2 (B) r = k[A]2[B] (in M sec–1) of Q is:
(C) r = k[ A] [B]2 (D) r = k[A][B] 2 3 4 3
(A) y (B) y (C) y (D) y
3 2 3 4
Q.2 The rate law for a reaction between the substances
A and B is given by rate = k [A]n [B]m On doubling the Q.8 Gaseous reaction A → B + C follows first order
concentration of A and halving the concentration of kinetics. Concentration of A changes from 1M to 0.25
B, the ratio of the new rate to the earlier rate of the M in 138.6 minutes. Find the rate of reaction when
reaction will be as concentration of A is 0.1 M.
(A) 2(n – m) (B) 1/2m + n (C) (m + n) (D) (n – m) (A) 2 × 10–3M min–1 (B) 10–3M min–1
(C) 10–4M min–1 (D) 5 × 10–4M min–1
Q.3 In a first order reaction, the concentration of the
reactant, decreases from 0.8 to 0.4 M in 15 minutes. The
time taken for the concentration to change from 0.1 M Q.9 The initial rate of zero-order reaction of the
to 0.025 M is gaseous reaction A(g) → 2B(g) is 10–2 M min–1. If the
initial concentration of A is 0.1M. What would be the
(A) 30 minutes (B) 15 minutes concentration of B after 60 sec?
(C) 7.5 minutes (D) 60 minutes
(A) 0.09 M (B) 0.01 M

Q.4 The rate equation for the reaction (C) 0.02 M (D) 0.002 M

2A + B → C is found to be: rate=k [A] [B] The correct


Q.10 Consider the following first order competing
statement in relation to this reaction is
reactions:
(A) Unit of k must be s–1 k k
X  → A + B and Y 
1 → C + D if 50% of the reaction
2

(B) t1/2 is a constant of X was completed when 96% of the reaction of Y was
(C) Rate of formation of C is twice the rate of completed the ratio of their rate constants (k2/k1) is
disappearance of A (A) 4.06 (B) 0.215 (3) 1.1 (D) 4.65
(D) Value of k is independent of the initial concentration
of A and B
Chem i str y | 18.39

Q.11 At certain temperature, the half-life period for Q.16 The reaction A (g) → B(g) + 2C (g) is a first order
the thermal decomposition of a gaseous substance reaction with rate constant 3.465 × 10–6s–1.Starting with
depends on the initial partial pressure of the substance 0.1 mole of A in 2 litre vessel, find the concentration of
as follows A after 200 sec, when the reaction is allowed to take
place at constant pressure and temperature
P(mm Hg) 500 250
t1/2(in min) 235 950 (A) 0.05 M (B) 0.025 M

Find the order of reaction (C) 0.0125 M (D) None of these


[Given log(23.5) = 1.37; log (95)= 1.97; log 2 = 0.30]
Q.17 In respect of the equation k = A exp (– Ea / RT),
(A) 1 (B) 2 (C) 2.5 (D) 3 which one of the following statements is correct?
(A) R is Rydberg’s constant
Q.12 Consider the reaction: A → B + C
(B) k is equilibrium constant
Initial concentration of A is 1M. 20 minutes time is
required for completion of 20% reaction. (C) A is adsorption factor
d[B] (D) Ea is the energy of activation
If =k[A], then half life (t1/2) is
dt
(A) 55.44 min (B) 50 min Q.18 Rate of a reaction can be expressed by Arrhenius
(C) 62.13 min (D) None of these equation as k = Ae–E/RT In this equation, E represents
(A) The fraction of molecules with energy greater than
Q.13 If decomposition reaction A(g) → B (g) follows the activation energy of the reaction
first order kinetics then the graph of rate of formation (B) The energy above which all the colliding molecules
(R) of B against time t will be will react
(A) R (B) R (C) The energy below which colliding molecules will not
react
(D) The total energy of the reacting molecules at a
temperature T.
t t

(C) R (D) R
Q.19 The rate constant, the activation energy and
the Arrhenius parameter (A) of a chemical reaction at
25°C are 3.0 × 10–4 s–1, 104.4 kJmol–1 and 6.0 × 104 S–1
t
respectively. The value of the rare constant at T → ∞
t
(A) 2.0 × 10–18s–1 (B) 6.0 × 1014s–1
(C) Infinity (D) 3.6 × 1030s–1
Q.14 The rate constant for the forward reaction A(g) →
2B(g) is 1.5 × 10–3 s–1 at 100 K. If 10–5 moles of A and 100
moles of B are present in a 10 litre vessel at equilibrium Q.20 A first order reaction is 50% completed in 20
then rate constant for the backward reaction at this minutes at 27°C and in 5 min at 47°C. The energy of
temperature is activation of the reaction is
(A) 1.50 × 104L mol–1 s–1 (B) 1.5 × 1011L mol–1 s–1 (A) 43.85kJ/mol (B) 55.14kJ/mol
(C) 1.5 × 1010L mol–1 s–1 (D) 1.5 × 10–11L mol–1 s–1 (C) 11.97kJ/mol (D) 6.65kJ/mol

Q.15 Reaction A + B → C + D follows following rate law: Q.21 For the first order reaction A → B + C, carried out
rate = k[A]1/2[B]1/2. Starting with initial conc. of 1 M of A at 27°C if 3.8 × 10–16 % of the reaction molecules exists
and B each, what is the time taken for concentration of in the activated state, the Ea(activation energy) of the
A to become 0.25 M. reaction is [log 3.8 = 0.58]
Given: k = 2.303 × 10–3 sec–1 (A) 12 kJ/mole (B) 831.4kJ/mole
(A) 300sec. (B) 600 sec. (C) 900 sec. (D) 1200 sec. (C) 100 kJ/mole (D) 88.57kJ/mole
1 8 . 4 0 | Chemical Kinetics

Q.22 In a reaction carried out at 400 K , 0.0001% of the Q.6 The half-life period of a first order chemical reaction
total number of collisions are effective. The energy of is 6.93 minutes. The time required for the completion of
activation of the reaction is 99% of the chemical reaction will be (log 2 = 0.301)
(2009)
(A) Zero (B) 7.37k cal/mol
(A) 230.3 minutes (B) 23.03 minutes
(C) 9.212 k cal/mol (D) 11.05k cal/mol
(C) 46.06 minutes (D) 460.6 minutes

Previous Years’ Questions Q.7 A reaction involving two different reactants  (2005)

1 (A) Can never be a second order reaction


Q.1 For a reaction A → 2B, rate of disappearance
2 (B) Can never be a unimolecular reaction
of ‘A’ is related to the rate of appearance of B’ by the
(C) Can never be a bimolecular reaction
expression  (2008)
(D) Can never be a first order reaction
d[A] 1 d[B] d[A] d[B]
(A) – = (B) – =
dt 4 dt dt dt
Q.8 A reaction was found to be second order with
d[A] d[B] d[A] 1 d[B] respect to the concentration of carbon monoxide. If
(C) – =4 (D) – =
dt dt dt 2 dt the concentration of carbon monoxide is doubled with
everything else kept the same, the rate of reaction will
Q.2 The rate of a chemical reaction doubles for every  (2006)
10° C rise of temperature. If the temperature is raised (A) Remain unchanged (B) Triple
by 50° C, the rate of the reaction increases by about (C) Increase by a factor of 4 (D) Double
 (2011)
(A) 10 times (B) 24 times Q.9 For the reaction A + 2B → C, rate is given by R = [A]
[B]2 then the order of the reaction is  (2002)
(C) 32 times (D) 64 times
(A) 3 (B) 6 (C) 5 (D) 7
Q.3 In a first order reaction the concentration of
reactant decreases from 800 mol/dm3 to 50 mol/dm3 Q.10The following mechanism has been proposed for
in 2 × 102 sec. The rate constant of reaction in sec–1 is the reaction of NO with Br2 to from NOBr: NO(g) +
 (2003) 
Br2 (g) ← → NOBr (g) NOBr (g) + NO(g) → 2NOBr
 2 2
(A) 2 × 104 (B) 3.45 × 10–5 (g) If the second step is the rate determining step, the
order of the reaction with respect to NO(g) is (2006)
(C) 1.386 × 10–2 (D) 2 ×10–4
(A) 1 (B) 0 (C) 3 (D) 2
Q.4 Consider the reaction, 2 A + B → Products When
concentration of B alone was doubled, the half-life did Q.11 Consider the reaction Cl2(aq) + H2S(aq) → S(s) + 2H+(aq)
not change. When the concentration of A alone was + 2Cl–(aq) The rate equation for this reaction is rate =
doubled, the rate increased by two times. The unit of
k[Cl2][H2S] Which of these mechanisms is/are consistent
rate constant for this reaction is  (2007)
with this rate equation
(A) L mol–1 s–1 (B) No unit
A. Cl2 + H2S → H+ +Cl– + Cl– + HS– (slow)
(C) mol L s
–1 –1
(D) s–1
Cl++ HS– → H+ + Cl– + S (fast)
Q.5 The rate constant for the reaction, 
B. H2S ←→ H+ + HS– (fast equilibrium)

2N2O5 → 4NO2 + O2 is 3 ×10–5 sec–1. If the rate is Cl2 + HS– → 2Cl– + H+ + S (slow)  (2010)
2.40 × 10–5mol litre–1 sec–1.
Then the concentration of N2O5 (in mol litre–1) is(2001) (A) A only (B) B only

(A) 1.4 (B) 1.2 (C) 0.04 (D) 0 (C) Both A and B (D) Neither A nor B
Chem i str y | 18.41

Q.12 The time for half life period of a certain reaction Q.18 The time for half-life period of a certain reaction A
A → Products is 1 hour. When the initial concentration → products is 1 hour. When the initial Concentration
of the reactant ‘A’ is 2.0 mol L–1, how much time does it of the reactant ‘A’, is 2.0 mol/L, how much time does
take for its concentration to come for 0.50 to 0.25 mol it take for its concentration to come from 0.50 to
L–1 if it is a zero order reaction  (2010) 0.25 mol/L if it is a zero order reaction? (2010)
(A) 1 h (B) 4h (C) 0.5h (D) 0.25 h (A) 4 h (B) 0.5 h (C) 0.25 h (D) 1 h

Q.13 The energies of activation for forward and reverse Q.19 Consider the reaction: Cl2(aq) + H2S(aq) →
reactions for A2 + B2 → 2AB are 180kJ mol–1 and S(s) + 2H+(aq) + 2Cl– (aq) The rate equation for this
200kJ mol–1 respectively. The presence of catalyst lowers reaction is rate = k [Cl2] [H2S]
the activation energy of both (forward and reverse)
Which of these mechanisms is/are consistent with this
reactions by 100 kJ mol–1. The enthalpy change of the
rate equation? (2010)
reaction (A2 + B2 → 2AB) in the presence of catalyst will
be (in kJ mol–1) (2007) (A) Cl2 + H2 → H+ + Cl– + Cl+ + HS–(slow)
(A) 300 (B) -120 (C) 280 (D)- 20 Cl+ + HS– → H+ + Cl– + S (fast)
(B) H2S ⇔ H+ + HS– (fast equilibrium)
Q.14 Consider an endothermic reaction X → Y with
Cl2 + HS– → 2Cl– + H+ + S (slow)
the activation energies Eb and Ef for the backward and
forward reactions, respectively, in general (2005) (A) B only (B) Both A and B
(A) Eb < Ef (C) Neither A nor B (D) A only
(B) Eb >Ef
Q.20 The rate of a chemical reaction doubles for every
(C) Eb =Ef 10oC rise of temperature. If the temperature is raised by
(D) There is no definite relation between Eb and Ef 50oC, the rate of the reaction increases by about:
 (2011)
Q.15 If ‘I’ is the intensity of absorbed light and C is the (A) 24 times (B) 32 times
concentration of AB for the photochemical process
(C) 64 times (D) 10 times
AB + hυ → AB*, the rate of formation of AB* is directly
proportional to  (2001)
Q.21 For a first order reaction, (A) → products, the
(A) C (B) I (C) I2 (D) C.I concentration of A changes from 0.1 M to 0.025 M in 40
minutes. The rate of reaction when the concentration of
1
Q.16 For a reaction A → 2B , rate of disappearance A is 0.01 M is: (2012)
2
of ‘A’ is related to the rate of appearance of ‘B’ by the (A) 1.73 x 10–5 M/ min (B) 3.47 x 10–4 M/min
expression (2008)
(C) 3.47 x 10–5 M/min (D) 1.73 x 10–4 M/min
d[A] 1 d[B] d[A] 1 d[B]
(A) − = (B) − =
dt 2 dt dt 4 dt Q.22 The rate of a reaction doubles when its temperature
d[A] d[B] d[A] d[B] changes from 300 K to 310 K. Activation energy of
(C) − = (D) − 4
= such a reaction will be : (R = 8.314 JK-1 mol-1 and log
dt dt dt dt
2 = 0.301) (2013)

Q.17 The half-life period of a first order chemical (A) 53.6 kJ mol-1 (B) 48.6 kJ mol-1
reaction is 6.93 minutes. The time required for the (C) 58.5 kJ mol-1 (D) 60.5 kJ mol-1
completion of 99% of the chemical reaction will be
(log 2 = 0.301) (2009)
Q.23 . For the non-stoichiometry reaction 2A + B → C
(A) 230.3 minutes (B) 23.03 minutes + D, the following kinetic data were obtained in three
(C) 46.06 minutes (D) 460.6 minutes separate experiments, all at 298 K. (2014)
1 8 . 4 2 | Chemical Kinetics

Initial Initial Initial rate of Q.24 Decomposition of H2O2 follows a first order
Concentration (A) Concentration (A) formation (C) reaction. In fifty minutes the concentration of
(mol L-1s-1) H2O2 decreases from 0.5 to 0.125 M in one such
decomposition. When the concentration of H2O2
0.1 M 0.1 M 1.2 × 10-3
reaches 0.05 M, the rate of formation of O2 will be:
0.1 M 0.2 M 1.2 × 10-3 (2016)
0.2 M 0.1 M 2.4 × 10-3
(A) 6.93 × 10–4 mol min–1 (B) 2.66 L min–1at STP
The rate law for the formation of C is
(C) 1.34 × 10–2 mol min–1 (D) 6.93 × 10–2 mol min–1
dC dC
(A) = k[A][B] (B) = k[A]2 [B]
dt dt
dC dC
(C) = k[A][B]2 (D) = k[A]
dt dt

JEE Advanced/Boards

Exercise 1 Q.5 At 27°C it was observed during a reaction of


hydrogenation that the pressure of hydrogen gas
Q.1 Ammonia and oxygen reacts at higher temperatures decreases from 2 atmosphere to 1.1 atmosphere in 75
as 4NH3(g) + 5O2(g)→ 4NO(g) + 6H2O(g) minutes. Calculate the rate of reaction (in M sec–1) and
rate of reaction in term of pressure.
In an experiment, the concentration of NO increases by
1.08 × 10–2 mol litre–1 in 3 seconds. Calculate
Q.6 For the elementary reaction 2A + B2 → 2AB.
(i) Rate of reaction (ii) Rate of disappearance of Calculate how much the rate of reaction will change if
ammonia (iii) Rate of formation of water the volume of the vessel is reduced to one third of its
original volume?
Q.2 In the following reaction 2H2O2 → 2H2O + O rate of
formation of O2 is 3.6 M min–1 Q.7 For the reaction 3BrO– → BrO–3 +2Br– in an alkaline
(i) What is rate of formation of H2O? aqueous solution the value of the second order
(in BrO–) rate constant at 80°C in the rate law for
(ii) What is rate of disappearance of H2O2?
∆[BrO − ]
– was found to be 0.056L mol–1 s–1. What is the
∆t
Q.3 In a catalytic experiment involving the Haber rate constant when the rate law is written for
process N2 + 3H2 → 2NH3, the rate of reaction was
∆[BrO3− ] ∆[Br − ]
measured as (a) (b) ?
∆t ∆t
∆[NH3 ]
Rate = = 2 × 10 mol L s .
–4 –1 –1
∆t Q.8 Dinitropentoxide decomposes as follows:
If there were no side reactions, what was the rate of 1
N2O5(g) → 2NO2(g) + O2(g)
reaction expressed in terms of (a) N2, (b) H2? 2
Given that – d [N2O5]/dt = k1[N2O5]
Q.4 The reaction 2A + B + C → D + E is found to be d[NO2]/dt = k2[N2O5] ; d[O2]/dt = k3[N2O5]
first order in A second order in B and zero order in C. (1)
What is the relation between k1, k2 and k3?
Give the rate law for the reaction in the form of
differential equation.
Q.9 Suppose that the Sun consist entirely of hydrogen
(ii) What is the effect in rate of increasing concentrations atom and releases the energy by the nuclear reaction.
of A, B, and C two times?
Chem i str y | 18.43

4 Q.19 A first order reaction has a rate constant is


411 H →2 He with 26 MeV of energy released. If the
1.5 × 10–3 sec–1. How long will 5.0 g of this reactant take
total output power of the Sun is assumed to remain to reduce to 1.25 g?
constant at 3.9 × 1026 W find the time it will take to burn
all the hydrogen. Take the mass of the Sun as 1.7 × 1030 kg.
Q.20 A drug is known to be ineffective after it has
decomposed 30%. The original concentration of a
Q.10 The reaction A(g) + 2B(g) → C(g) + D(g) is an sample was 500 units/ml. When analyzed 20 months
elementary process. In an experiment, the initial partial later, the concentration was found to be 420units/ml.
pressure of A & B are PA = 0.6 and PB = 0.8 atm. Calculate Assuming that decomposition is of first order, what will
the ratio of rate of reaction relative to initial rate when be the expiry time of the drug?
PC becomes 0.2 atm.

Q.21 A viral preparation was inactivated in a chemical


Q.11 In the given reaction, A → B rate constant is 1.2 × bath. The inactivation process was found to be first
10–2 M s–1. What is concentration of B after 10 and 20 order in virus concentration. At the beginning of the
min, if we start with 10 M of A. experiment 2.0% of the virus was found to be inactivated
per minute. Evaluate k for inactivation process.
Q.12 For the following data for the zero order reaction
A → products. Calculate the value of k. Q.22 If a reaction A → Products, the concentrations of
Time(min) [A] reactant A are C0, aC0, a2C0, a3C0 .........after time interval
0, t, 2t, 3t,........... where a is a constant. Given 0 < a < 1.
0.0 0.10 M Show that the reaction is of first order. Also calculate
1.0 0.09 M the relation between k,a and t.
2.0 0.08 M
Q.23 The reaction SO2Cl2(g) → SO2(g) + Cl2(g) is a first
order gas reaction with k = 2.2 × 10–5 sec–1 at 320°C.
Q.13 The rate constant for a zero order reaction is
What % of SO2Cl2 is decomposed on heating this gas
2 × 10–2 mol/L sec–1, if the concentration of the reactant
for 90 min?
after 25 sec is 0.25 M, calculate the initial concentration.

Q.24 Two substances A(t1/2 = 5 mins) and B(t1/2 = 15 mins)


Q.14 A drop of solution (volume 0.10 ml) contains
follow first order kinetics are taken in such a way that
6 × 10–6 mole of H+, if the rate constant of disappearance
initially [A]= 4 [B]. Calculate the time after which the
of H+ is 1 × 107 mole liter–1 sec–1. How long would it take
concentration of both the substance will be equal.
for H+ in drop to disappear?

Q.25 At 800° C the rate of reaction


Q.15 A certain substance A is mixed with an equimolar
quantity of substance B. At the end of an hour A is 75% 2NO + H2 → N2 + H2O
reacted Calculate the time when A is 10% unreacted. Changes with the concentration of NO and H2 are
(Given: order of reaction is zero)
[NO] in M [H2] in M
1 d[NO]
− in M sec–1
Q.16 A first order reaction is 75% completed in 72 min. 2 dt
How much time will it take for (i) 50% completion
(i) 1.5×10–4 4 × 10–3 4.4 × 10–4
(ii) 87.5% completion.
(ii) 1.5×10–4 2 × 10–3 2.2 × 10–4
Q.17 A first order reaction is 20% complete in 10 min. (iii) 3.0×10–4 2 × 10–3 8.8 × 10–4
Calculate (i) the specific rate constant. (ii) the time taken
for the reactions to go to 75% completion. (a) What is the order of this reaction?
(b) What is the rate equation for the reaction?
Q.18 Show that in case of unimolecular reaction, the (c) What is the rate when
time required for 99.9% of the reaction to take place in
ten times that required for half of the reaction. [H2] = 1.5 × 1–3 M and [NO] = 1.1 × 1–3M?
1 8 . 4 4 | Chemical Kinetics

Q.26 The data below are for the reaction if NO and Cl2 Q.32 A → B + C
to form NOCl at 295 K
Time 0 t
Concentration of Concentration Initial Rate
Volume of reagent V1 V2
Cl2 [M] of NO (M s–1)
The reagent reacts with A, B and C. Find k.
0.05 0.05 1×10–3
0.15 0.05 3×10–3
[Assuming n-factor of A B & C are same]

0.05 0.15 9×10–3


Q.33 A → 2B + 3C
(a) What is the order w. r.t. NO and Cl2 in the reaction.
Time t ∞
(b) Write the rate expression
Volume of reagent V2 V3
(c) Calculate the rate constant
The reagent reacts with A, B and C.
(d) D
 etermine the reaction rate when concentration of
Cl2 and NO are 0.2 M & 0.4 M respectively. Find k. [Assuming n-factor of A B & C are same]

Q.27 The catalytic decomposition of N2O by gold at 900 Q.34 S → G + F


°C and at an initial pressure of 200 mm is 50% complete
Time t ∞
in 53 minutes and 73% complete in 100 minutes
Rotation of Glucose & Fructose r1 r∞
(i) What is the order of the reaction?
(ii) Calculate the velocity constant Find k.
(iii) How much of H2O will decompose in 100 min. at the
3
same temperature but at initial pressure of 600 mm? Q.35 The reaction AsH3(g) → As(s) + H (g) was
2 2
followed at constant volume at 310°C by measuring
Q.28 The pressure of a gas decomposing at the surface the gas pressure at intervals. Show from the following
of a solid catalyst has been measured at different times figures that reaction is of first order.
and the results are given below
Time (in hrs) 0 5 7.5 10
t (sec) 0 100 200 300
Total pressure (in min) 758 827 856 882
Pa(Pascal) 4×103 3.5×103 3×103 2.5×103

Determine the order of reaction, its rate constant. Q.36 The thermal decomposition of dimethyl ether as
measured by finding the increase in pressure of the
Q.29 The half -life period of decomposition of a reaction.
compound is 50 minutes. If the initial concentration is (CH3)2O(g) → CH4(g)+H2(g)+CO(g) at 500°C is as follow:
halved, the half life period is reduced to 25  minutes.
What is the order of reaction? Time (sec.) 390 1195 3155 ∞

Pressure increase 96 250 467 619


Q.30 In this case we have A → B + C (mm Hg)

Time t ∞ The initial pressure of ether was 312 mm Hg. Write the
rate equation for this reaction and determine the rate
Total pressure of A + B +C P2 P3
constant.
Find k.
Q.37 From the following data show that decomposition
Q.31 A → B + C of H2O2 in aqueous media is first order.

Time t ∞ Time in (minutes) 0 10 20

Total pressure of ( B +C) P2 P3 Volume (in c.c. of KMnO4) 22.8 13.3 8.25

Find k.
Chem i str y | 18.45

Q.38 The following data were obtained in experiment Q.43 The reaction A(aq) → B (aq) + C (aq) is monitored
on inversion of cane sugar by measuring optical rotation of reaction mixture
as different time interval .The species A, B and C are
Time 0 60 120 1805 360 ∞
optically active with specific rotations 20°, 30° and – 40°
(minute)
respectively. Starting with pure A if the value of optical
Angle of +13.1 +11.6 +10.2 +9.0 +5.87 –3.8 rotation was found to be 2.5° after 6.93 minutes and
rotation optical rotation was –5° after infinite time. Find the rate
(degree) constant for first order conversion of A into B and C.

Show that the reaction is of first order. After what time


would you expect a zero reading in polarimeter? Q.44 For a reaction k1 y
x
Q.39 At 100°C the gaseous reaction A → 2B + C was k2 zt
observed to be of first order. On starting with pure
A it is found that at the end of 10 minutes the total [x]t
Calculate value of ratio, at any given instant.
pressure of system is 176 mm Hg and after a long time [y] + [z]
270 mm Hg. From these data find (a) initial pressure
of A (b) the pressure of A at the end of 10 minutes B
k1
(c) the specific rate of reaction(d) the half-life period of Q.45 A
the reaction?
k2 C
[C]
Q.40 The decomposition of N2O5 according to the k1 = x hr–1; k1: k2 = 1: 10. Calculate after one hour
[A]
equation 2N2O5 (g) → 4 NO2(g) + O2(g) is a first order
reaction. After 30 min, from start of decomposition in a from the start of the reaction. Assuming only A was
closed vessel the total pressure developed is found to present in the beginning.
be 284.5 mm Hg. On complete decomposition, the total
pressure is 584.5 mm Hg. Calculate the rate constant of
Q.46 How much time would be required for B to reach
the reaction. k
maximum concentration for the reaction A →B
1
k
Q.41 A definite volume of H2O2 undergoing spontaneous
2
 → C.
decomposition required 22.8 c.c. of standard ln2 ln2
Given k1 = k =
permanganate solution for titration. After 10 and 20 4 2 2
minutes respectively the volumes of permanganate
required were 13.8 and 8.25 c.c. Q.47 For first order parallel reaction k1 and k2 are 8 and
(a) Find order of reaction. How may the result be 2 min–1 respectively at 300 K. If the activation energies
explained? for the formation of B and C are respectively 20 and
28.314 kJ/ mol respectively find the temperature at
(b) Calculate the time required for the decomposition
which B and C will be obtained in molar ratio of 2:1.
to be half completed.
k1 B
(c) Calculate the fraction of H2O2 decomposed after
A
25 minutes.
k2 C

Q.42 Hydrogen peroxide solution was stored in a mild [Given: ln4 = 1.4]
steel vessel. It was found, however, that the hydrogen
peroxide decomposed on the wall of the vessel Q.48 In gaseous reactions important for understanding
(a first order reaction) .An experiment with 100 ml of a the upper atmosphere, H2O and O react bimolecularly
solution gave 10.31 ml oxygen (corrected to 1 atm & to form two OH radicals. ∆H for This reaction is 72 kJ
273 K) after 5.1 days. Find how long the peroxide can at 500 K and Ea = 77 kJ mol–1, then calculate Ea for the
be stored before the loss of 20.00 ml oxygen occurs bimolecular recombination of 2OH radicals to form
(per 100 ml solution) under similar storage conditions H2O and O at 500 K.
if complete decomposition of the H2O2sample gave
46.34 mL oxygen.
1 8 . 4 6 | Chemical Kinetics

Q.49 The energy of activation of a first order reaction Q.58 Deduce rate law expressions for the conversion of
is 104.5 kJ mole–1 and pre - exponential factor (A) is H2 and I2 to HI at 400°C corresponding to each of the
5 × 1011 sec–1. At what temperature, will the reaction following mechanisms:
have a half-life of 1 minute?
(a) H2 + I2 → 2HI (one step)

Q.50 The specific rate constant for a reaction increases (b) I2 → 2I


by a factor of 4. If the temperature is changed from 27°C 2I + H2 → 2HI (slow)
to 47°C. Find the activation energy for the reaction.
(c) I2 → 2I
Q.51 The energy of activation and specific rate I + H2 → IH2
constant for a first order reaction at 25°C are 100 kJ/
IH2 + I → 2HI (slow)
mole and 3.46 × 10–3 sec–1 respectively. Determine the
temperature at which half life of the reaction is 2 hours. (d) Can the observed rate law expression
rate = k[H2][I2] distinguish among these mechanisms?
Q.52 A catalyst lowers the activation energy for a
certain reaction from 75 kJ to 25 kJ mol–1. What will be (e) If it is known that ultraviolet light causes the reaction
the effect on the rate of reaction at 25°C after things of H2 and I2 to proceed at 200°C with the same rate law
being equal? expression, which of these mechanisms becomes most
improbable?
Q.53 Given that the temperature coefficient for the
saponification of ethyl acetate by NaOH is 1.75.
Calculate activation energy for the saponification of
Exercise 2
ethyl acetate.
Single Correct Choice Type

Q.54 At 380°C the half-life period for the first order


Q.1 The rate of a reaction is expressed in different ways
decomposition of H2O2 is 360 min. The energy of
as follows:
activation of the reaction is 200 kJ mol–1. Calculate the
time required for 75% decomposition at 450°C. 1  d[C]  1  d[D]  1  d[A]   d[B] 
+   =–  = +  =– 
2  dt  3  dt  4  dt   dt 
Q.55 The reaction 2NO + Br2 → 2NOBr, is supposed to The reaction is:
follow the following mechanism
fast
(A) 4A + B → 2C + 3D
(i) NO + Br2 
  NOBr2

(B) B + 3D → 4A + 2C
slow
(ii) NOBr2 + NO  → 2NOBr
(C) A + B → C + D
Suggest the rate law expression.
(D) B + D → A +C

Q.56 For the reaction 2H2 + 2NO → N2 + 2H2O, the


Q.2 For the reaction system
following mechanism has been suggested 2NO → N2O2
equilibrium constant K1 (fast) 2NO (g) + O2 (g) → 2NO2(g) volume is suddenly
k2 reduced to half of its value by increasing the pressure
N2O2 + H2 
→ N2O + H2O (slow)
k
on it. If the reaction is first order with respect to O2 and
N2O + H2 → H2 + H2O (fast)
3
second order with respect to NO the reaction rate will
Establish the rate law for given reaction. (A) Increase to four times of its initial value
(B) Diminish to one-fourth of its initial value
Q.57 Reaction between NO and O2 to form NO2 is
2NO + O2 → 2NO2 follows the following mechanism (C) Diminish to one-eight of its initial value

K (D) Increase to eight times of its initial value


NO + NO  N2O2 (in rapid equilibrium)
1 

k −1

N2O2 + O2  Q.3 The energies of activation for forward and reverse


→ 2NO2 (slow)
k2

reactions for A2 + B2 
  2AB are 180 kJ mol–1 and

1  d[NO2 ]  200 kJmol respectively. The presence of catalyst lower
–1
Show that the rate of reaction is given by  
= K [NO]2[O2] 2  dt  the activation energy of both (forward and reverse)
Chem i str y | 18.47

reactions by 100 kJ mol–1. The magnitude of enthalpy Q.7 For the first order decomposition of SO2Cl2(g).
change of the reaction (A2 + B2 → 2AB) in the presence
SO2Cl2(g) → SO2(g) + Cl2(g) a graph of log (a0 – x) vs t is
of catalyst will be (in kJ mol–1).
shown in figure. What is the rate constant (sec–1)?
(A) 300 (B) 120 (C) 20 (D) –20
Time (min)
(0, 0) 2 4 6 8 10
Q.4 Which graph represents zero order reaction
-1

log(a0 - x)
[A(g) → B(g)]
-2
(A) (B)
d[B] -3
[B]
dt

(A) 0.2 (B) 4.6 × 10–1


t t
(C) 7.7 × 10–3 (D) 1.15 × 10–2
(C) (D)
Q.8 Decomposition of H2O2 is a first order reaction.
t1/2 t1/4
A solution of H2O2 labelled as “16.8 V” was left open
due to this, some H2O2 decomposed. To determine the
[A]0 [A]0 new volume strength after 2.303 hours. 20 mL of this
solution was diluted to 100 mL. 25 mL of this diluted
Q.5 Consider the reaction A → B, graph between solution was titrated against 37.5 mL of 0.02 M KMnO4
half-life (t1/2) and initial concentration (a) of the reaction is solution under acidic conditions [Given: STP is 1 atm
and 273 K].
The rate constant (in hr–1) for decomposition of H2O2 is:
t1/2 (A) 0.15 (B) 0.30 (C) 0.60 (D) 1.3

a Q.9 The variation of concentration of A with time in


two experiments starting with two different initial
d[A] concentration of A is given in the following graph. The
Hence graph between – and time will be
dt reaction is represented as A (aq) → B(aq).
What is the rate of reaction (M/min) when concentration
(A) (B)
of A in aqueous solution was 1.8 M?
d[A] d[A]
dt dt
Concentration (M)

1.5
t
1.2
1
(C) (D)
0.8 Experiment-1
d[A] d[A] 0.6 Experiment-2
dt dt 5 10 15 20
time (min)
t t (A) 0.08 M min–1 (B) 0.036 M min–1

Q.6 The reactions of higher order are rare because (C) 0.13 M min–1 (D) 1 M min–1

(A) Many body collisions involve very high activation


Q.10 The following mechanism has been proposed for
energy
the exothermic catalyzed complex reaction.
(B) Many body collisions have a very low probability fast k k
A+B 

 IAB → AB+I 
1 2→ P+A
(C)Many body collisions are not energetically favoured
If k1 is much smaller than k2. The most suitable
(D) Many body collisions can take place only in the qualitative plot of potential energy (PE.) versus reaction
gaseous phase. coordinate for the above reaction.
1 8 . 4 8 | Chemical Kinetics

(A)
(1) (2) (3) (4)
(A) ∆E for Ea for ∆Eoverall Ea for
P.E.

E+S→ES ES→EP for S®P EP→E+P


A+B A+P
IAB (B) Ea for ∆E for Ea for ∆Eoverall
AB+I
E+S→ES E+S→ES ES→EP for S®P
reaction coordinate
(B) (C) Ea for Ea for ∆Eoverall ∆E for
ES→EP EP→E+P for S®P EP→E+P
(D) Ea for Ea for Ea for ∆Eoverall
E+S→ES ES→EP EP→E+P for S®P
P.E.

AB+I A+P
A+B
IAB (E) ∆E for ∆Eoverall ∆E for Eafor
E+S→ES for S®P EP→E+P EP→E+P
reaction coordinate

(C)
Multiple Correct Choice Type

Q.13 SO3 gas is entering the environment at a constant


P.E.

rate of 6.93 × 10–5 gm/L/day due to the emission of


A+B AB+I
A+P
polluting gases from thermal power plant but at the
IAB
same time it is decomposing & following first order
reaction coordinate kinetics with half-life of 100 days.
Based on above information select the true statement (s).
(D)
(A) Concentration of SO3 in Kota is 1.25 × 10–5 M
(Assume SO3 present in air reaches steady state)
P. E.

A+B AB+I (B) If 103 L of air is passed through 1L pure water


IAB A+P (assuming all SO3 to be dissolved in it) & resulting
reaction coordinate solution is titrated against 1 N NaOH solution, 15 ml is
required to reach end point
Q.11 The following mechanism has been proposed for
(C) An industry is manufacturing H2SO4 at the rate of
the reaction of NO with Br2 to form NOBr
980 kg per day with the use of SO3 in air it should use
NO(g) + Br2(g) 
 NOBr2(g)

 8 × 105 litre air/day
NOBr2(g) + NO(g) → 2NOBr(g) (D) If SO3 emission is stopped then after 1000 days its
concentrations will reduce to ≈ 1.2 × 10–3 M.
If the second step is the rate determining step, the
order of the reaction with respect to NO(g) is
Q.14 For the reaction A → B. The rate law expression is
(A) 2 (B) 1 (C) 0 (D) 3
d[A]
– = k[A]1/2. If initial concentration of [A] is [A]0, then
dt
Q.12 Choose the correct set of indentifications.
2
(A) The integrated rate expression is k= (A1/2 − A1/2 )
t 0
Potential energy

(B) The graph of A vs t will be


K
(4) (C) The half-life period t1/2 =
(1)
(2) (3)
2[A]1/2
0
(D) The time taken for 75% completion of reaction
reaction coordinate
[A]0
t3/4 =
k
t1/2

a
Chem i str y | 18.49

2
k1=6.93 x 10 min
-1
B Q.19 Which of the following is/are correct statement?

Q.15 Consider the reaction, A (A) Stoichiometry of a reaction tells about the order of
C the elementary reaction.
k2=13.85 x 10 min-1
(B) For a zero-order reaction, rate and the rate constant
A, B and C all are optically active compound. If optical are identical
rotation per unit concentration of A, B and C are 60°, (C) A zero-order reaction is controlled by factors other
–72°, 42° and initial concentration of A is 2 M then than concentration of reactants.
select write statements(s).
(D) A zero-order reaction is always elementary reaction
(A) Solution will be optically active and dextro after
very long time
Assertion Reasoning Type
(B) Solution will be optically active and laevo after very
long time (A) S
 tatement-I is true, statement-II is true and
statement-II is correct explanation for statement-I
(C) Half life of reaction is 15 min
(B) Statement-I is true, statement-II is true and
(D) After 75% conversion of A in to B and C angle of statement-II is NOT the correct explanation for
rotation of solution will be 36° statement-I
(C) Statement-I is true, statement-II is false.
Q.16 Which of the following statement is incorrect?
(D) Statement-I is false, statement-II is true.
(A) The order of reaction is the sum of powers of all the
concentration terms in the rate equation.
Q.20 Statement-I: A fractional order reaction must be
(B) The order of reaction with respect to one reactant
a complex reaction.
is the ratio of the change of logarithm of the rate of
the reaction to the change in the logarithm of the Statement-II: Fractional order of RDS equals to overall
concentration of the particular reactant, keeping the order of a complex reaction.
concentrations of all other reactants constant.
Q.21 Statement-I: Temperature coefficient of a one
(C) Orders of reactions cannot be fractional.
step reaction may be negative
(D) The order of a reaction can only be determined
Statement-II: The rate of reaction having negative
from the stoichiometric equation for the reaction.
order with respect to a reactant decreases with the
increase in concentration of the reactant.
Q.17 Select incorrect statement(s)
(A) Unit of pre-exponential factor (A) for second order Q.22 Statement-I: The overall rate of a reversible
reaction is mol L–1 s–1 reaction may decrease with the increase in temperature.

(B) A zero-order reaction must be a complex reaction Statement-II: When the activation energy of forward
reaction is less than that of backward reaction, then the
(C) Molecularity is defined only for RDS in a complex increase in the rate of backward reaction is more than
reaction that of forward reaction on increasing the temperature
(D) Decay constant (λ) of radioactive substance is
affected by temperature Q.23 Statement-I: In a reversible endothermic reaction
Ea of forward reaction is higher than that of backward
E reaction.
1
Q.18 In a consecutive reaction system A → B
E Statement-II: The threshold energy of forward reaction
→ 2 C when E1 is much greater than E2, the yield of is more than that of backward reaction.
B increase with
(A) Increase in temperature Q.24 Statement-I: The time of completion of reaction
of type A → product
(B) Decreases in temperature
(order < 1) may be determined.
(C) Increase in initial concentration of A
Statement-II: Reactions with order ≥ 1 are either too
(D) Decrease in initial concentration of A slow or too fast and hence the time of completion
cannot be determined
1 8 . 5 0 | Chemical Kinetics

Q.25 Statement-I: A catalyst provides an alternative Q.30 What will be the concentration of A at time t, if
path to the reaction in which conversion of reaction n1 = 1 and n2 = 2 ?
into products takes place quickly  e−kt 
(A) [A0] .e–kt (B) [A0 ]  
Statement-II: The catalyst forms an activated complex  2 − e−kt 
 
of lower potential energy with the reactants by which
 e−kt 
more number of molecules are able to cross the barrier (C) [A0 ]   (D) [A0](1 – 2 . e–kt)
per unit of time.  1 − e−kt 
 

Paragraph 3
Comprehension Type
For the reaction sequential reaction
Paragraph 1 k k
k1 B A → B 
1 2→ C
For a hypothetical elementary reaction A
the concentration of A, B & C at anytime ‘t’ is given by
k2 C
k1 1 k1 [A]0 −k1t −k 2t
where = . Initially only 2 moles of A is present. [A]1 = [A]0e–kt ; [B]1 = [e −e ]
k2 2 (k 2 – k1 )
[C]1 = [A0] – ([A]1 + [B]1)
Q.26 The total number of moles of A, B & C at the end
of 50% reaction are Q.31 The time at which concentration of B is maximum is
(A) 2 (B) 3 (C) 4 (D) 5 k1 k
1
(A) (B) ln 1
k 2 − k1 k 2 − k1 k 2
Q.27 Number of moles of B are
(A) 2 (B) 1 (C) 0.666 (D) 0.33 1 k k2
(C) ln 1 (D)
k1 − k 2 k 2 k 2 − k1
Paragraph 2
The gaseous reaction: n1 A(g) → n2B (g) is first order Q.32 Select the correct option if k1 = 1000s–1 and
with respect to A. The true rate constant of reaction is k2 = 20s–1.
k. The reaction is studied at a constant pressure and
temperature. Initially, the moles of A were ‘a’ and no B (A) [C]1 (B) [C]1

were present.
Conc.

Conc.

[B]1
[A]1 [B]1 [A]1
Q.28 How many moles of A are present at time, t? time time
−n1kt
(A) a ⋅ e-kt (B) a ⋅ e
(C) [C]1 (D) [C]1
−n2kt −n2kt
(C) a ⋅ e (D) a(1 − e )
Conc.
Conc.

[B]1

Q.29 If the initial volume of system were v 0° then the [B]1 [A]1 [A]1
volume of system after time t will be time time

n1 v 0
(A)
n2 Paragraph 4

n2 v 0 Oxidation of metals is generally a slow electrochemical


(B) reaction involving many steps. These steps involve
n1
electron transfer reactions. A particular type of oxidation
n  involve overall first order kinetics with respect to fraction
n  −n kt 
(C) v 0  2 +  1 − 2  ⋅ e 1  of unoxidised metal (1 – ƒ) surface thickness relative to
 n1  n1   maximum thickness (T) of oxidised surface, when metal
surface is exposed to air for considerable period of time
n  n  −n kt 
(D) v 0  2 +  2 – 1  ⋅ e 2  Rate law: = k(1 – ƒ), where f = x/T,
 n1  n1  
Chem i str y | 18.51

x = thickness of oxide film at 200 hrs Match the Columns


0 t
time ‘t' and Q.37 For the reaction of type A(g) → 2B(g)
T = thickness of oxide film at Column I contains four entries and column II contains
t=∞ four entries. Entry of column I are to be matched with
A graph of ln( 1 – ƒ) vs t is
-3 only one entry of column II
shown inthe adjacent figure. In(1-)
Column I Column II
Q.33 The time taken for thickness to grow 50% of T is
(p)
d[B] −d[A]
(A) 23.1 hrs (B) 46.2hrs (A) vs
dt dt
(C) 100 hrs (D) 92.4 hrs for first order

Q.34 The exponential variation of ‘f' with t(hrs) is given by


(A) [1 – e–3t/200] (B) e–3t/200–1
(B) [A] vs t for first (q)
(C) e–3t/200 (D) e3t/200
order

Paragraph 5
A reaction is said to be first order if it's rate is
proportional to the concentration of reactant. Let us
consider a reaction
A(g) B(g) + C(g) (C) [B] vs t for first (r)
order
At t = 0 a 0 0
At time t a-x x x
dx
The rate of reaction is govern by the expression
dt
= k(a – x) and integrated rate equation for a given
reaction is represented as (D) [A] vs t for zero (s)
 a  order
1
k= ln  a − x  where a = initial concentration and
t  
(a – x) = concentration of A after time t.

Q.35 Thermal decomposition of compound X is a first


order reaction .If 75% of X is decomposed in 100 min.
How long will it take for 90% of the compound to Q.38 Column-I and column-II. Entry of column-I are
decompose? Given: log 2 = 0.30 to be matched with one or more than one entries of
(A) 190 min (B) 176.66 min column-II and vice versa.

(C) 166.66 min (D) 156.66 min Column-I (Graphs Column-II (Co-ordinates)
reaction A → Products)
(A) (p) ln [A] (y-axis), t(x-axis)
Q.36 Consider a reaction A(g) 3B(g) + 2C(g) with
(order = 1)
rate constant 1.386 × 10–2 min–1. Starting with 2 moles
of A in 12.5 litre vessel initially, if reaction is allowed to
takes place at constant pressure & at 298 K then find
the concentration of B after 100 min.
(A) 0.04 M (B) 0.36 M
(C) 0.09 M (D) None of these
1 8 . 5 2 | Chemical Kinetics

Q.4 Which one of the following statements is incorrect


(B) (q) t1/2(y-axis), [A0] (x-axis)
about order of reaction?  (2005)
(order = 1)
(A) Order of reaction is determined experimentally
(B) Order of reaction is equal to sum of the power of
concentration terms in differential rate law
(C) It is not affected with stoichiometric coefficient of
(C) (r) r(y-axis), t(x-axis)(order > 0) the reactants
(D) Order cannot be fractional

Q.5 Plots showing the variation of the rate constant


(k) with temperature (T) are given below. The plot that
follows Arrhenius equation is  (2010)
(A) (B)
(D) (s) r(y-axis), t(x-axis)(order = 0)
(t) t 1/2(y-axis), [A0] (x-axis) (order K K
> 1)

1 T T
(u)  (y-axis), t(x-axis)
[A] (C) (D)
(order = 2)
K K
(v) r (y-axis), [A](x-axis)(order = 1)

Previous Years’ Questions T T


Comprehension (Q.6), (Q. 7), (Q.8)
Q.1 The rate constant of a reaction depends on(1981) Carbon-14 is used to determine the age of organic
(A) Temperature material. The procedure is based on the formation of
14
C by neutron capture in the upper atmosphere.
(B) Initial concentration of the reactants
14
14
(C) Time of reaction 7 N +0 n1 →6 C +1 p1
(D) Extent of reaction 14
C is absorbed by living organisms during
photosynthesis. The 14C content is constant in living
Q.2 A catalyst is a substance which  (1983) organism once the plant or animal dies, the uptake
(A) Increases the equilibrium concentration of the of carbon dioxide by it ceases and the level of 14C in
product the dead being, falls due to the decay which C–14
14
14
(B) Changes the equilibrium constant of the reaction undergoes 6 C →7 N + β–
(C) Shortens the time to reach equilibrium The half-life period of 14C is 5770 yr.
(D) Supplies energy to the reaction The decay constant (λ) can be calculated by using the
following formula
Q.3 If I is the intensity of absorbed light and C is the 0.693
λ=
concentration of AB for the photochemical process. t1/2
AB + hv → AB*, the rate of formation of AB* is directly The comparison of the β– activity of the dead matter
proportional to  (2001) with that of the carbon still in circulation enables
measurement of the period of the isolation of the
(A) C (B) I (C) I2 (D) C.I
material from the living cycle. The method however,
ceases to be accurate over periods longer than 30,000
yr. The proportion of 14C to 12C in living matter is
1: 1012.  (2006)
Chem i str y | 18.53

Q.6 Which of the following option is correct? Q.11 A first order gas reaction has A’ = 1.5 × 10–6 per
second at 200° C. If the reaction is allowed to run for 10
(A) In living organisms, circulation of 14C from
h, what percentage of the initial concentration would
atmosphere is high so the carbon content is
have change in the product? What is the half-life of this
constant in organism
reaction? (1987)
(B) Carbon dating can be used to find out the age of
earth crust and rocks
Q.12 An experiment requires minimum beta activity
(C) Radioactive absorption due to cosmic radiation is produced at the rate of 346 beta particles per minute.
equal to the rate of radioactive decay, hence the The half-life period of 42Mo99 which is a beta emitter is
carbon content remains constant in living organisms 66.6 h. Find the minimum amount of 42Mo99 required to
carry out the experiment in 6.909 h.  (1989)
(D) Carbon dating cannot be used to determine
concentration of 14C in dead beings.
Q.13 The gas phase decomposition of dimethyl ether
follows first order kinetics
Q.7 What should be the age of fossil for meaningful
determination of its age? CH3–O–CH3(g) → CH4(g)+ H2(g)+CO(g)
(A) 6 yr The reaction is carried out in a constant volume
container at 500°C and has a half-life of 14.5 min.
(B) 6000 yr
Initially only dimethyl ether is present at a pressure of
(C) 60,000 yr 0.40 atm. What is the total pressure of the system after
(D) It can be used to calculate any age 12 min? Assume ideal gas behaviour. (1993)

Q.8 A nuclear explosion has taken place leading to Q.14 (a) The rate constant of a reaction is 1.5 × 107 s–1 at
increase in concentration of C14 in nearby areas. C14 50° C and 4.5 × 107 s–1 at 100°C. Evaluate the Arrhenius
concentration is C1 in nearby areas and C2 in areas far parameters A and Ea.  (1998)
1
away. If the age of the fossil is determined to be T1 and (b) For the reaction, N2O5 (g) → 2NO2 (g) + O2 (g)
T2 at the places respectively then 2
calculate the mole fraction N2O5(g) decomposed at a
(A) The age of fossil will increase at the place where constant volume and temperature, if the initial pressure
1 C is 600 mm Hg and the pressure at any time is 960 mm
explosion has taken place and T1 – T2 = ln 1
λ C2 Hg. Assume ideal gas behaviour.
(B) The age of fossil will decrease at the place where
1 C Q.15 2X(g) → 3Y(g) + 2Z(g)
explosion has taken place and T1 – T2 = ln 1
λ C2
Time (in min) 0 100 200
(C) The age of fossil will be determined to be the same
Partial pressure of X (in mm of Hg) 800 400 200
T1 C1
(D) =
T2 C2 Assuming ideal gas condition. Calculate (2005)
(A) Order of reaction
Q.9 The concentration of R in the reaction
(B) Rate constant
R → P was measured as a function of time and the
(C) Time taken for 75% completion of reaction.
following data obtained:
(D) Total pressure when px = 700 mm
[R] (molar) 1.0 0.75 0.40 0.10
t (min) 0.0 0.05 0.12 0.18 Q.16 Consider a reaction aG + bH → Products.
When concentration of both the reactants G and H is
The order of the reaction is  (2010)
doubled, the rate increases by eight times. However,
when concentration of G is doubled keeping the
Q.10 Radioactive decay is a first order process. Radioactive concentration of H fixed, the rate is doubled. The
carbon in wood sample decays with a half-life of 5770 yr. overall order of the reaction is  (2007)
What is the rate constant (in yr–1) for the decay? What
fraction would remain after 11540 yr?  (1984) (A) 0 (B) 1 (C) 2 (D) 3
1 8 . 5 4 | Chemical Kinetics

Q.17 Under the same reaction conditions, initial


concentration of 1.386 mol dm-3 of a substance [Q]0
becomes half in 40 seconds and 20 seconds through [Q]
first order and zero order kinetics, respectively. Ratio 1
 k1 
  of the rate constants for first order (k1) and zero
 k0 
order (k0) of the reactions is  (2008) Time

(A) 0.5 mol-1 dm3 (B) 1.0 mol dm-3 (A) 2 (B) 3 (C) 0 (D) 1
(C) 1.5 mol dm-3 (D) 2.0 mol-1 dm3
Q.20 For the elementary reaction M → N, the rate
of disappearance of M increases by a factor of 8 upon
Q.18 An organic compound undergoes first-order
doubling the concentration of M. The order of the
decomposition. The time taken for its decomposition
reaction with respect to M is  (2014)
to 1/8 and 1/10 of its initial concentration are t1/8 and
[t ] (A) 4 (B) 3 (C) 2 (D) 1
t1/10 respectively. What is the value of 1/8 × 10? (take
[t1/10 ]
log102=0.3) (2013) Q.21 According to the Arrhenius equation,  (2015)
(A) A high activation energy usually implies a fast
Q.19 In the reaction, P + Q → R + S the time reaction
taken for 75% reaction of P is twice the time taken for (B) Rate constant increases with increase in temperature.
50% reaction of P. The concentration of Q varies with This is due to a greater number of collisions whose
reaction time as shown in the figure. The overall order energy exceeds the activation energy
of the reaction is  (2013)
(C) Higher the magnitude of activation energy, stronger
is the temperature dependence of the rate constant
(D) The pre-exponential factor is a measure of the rate
at which collisions occur, irrespective of their energy.

PlancEssential Questions
JEE Main/Boards JEE Advanced/Boards

Exercise 1 Exercise 1
Q.1 Q.4 Q.7 Q.9 Q.7 Q.9 Q.20 Q.36

Q.12 Q.19 Q.24 Q.43 Q.58(e)

Exercise 2 Exercise 2
Q.2 Q.10 Q.16 Q.8 Q.12 Q.28 Q.29
Q.33 Q.34 Q.37

Previous Years’ Questions


Previous Years’ Questions
Q.9 Q.14 Q.15
Q.12 Q.15
Chem i str y | 18.55

Answer Key

JEE Main/Boards d(D) k1k 3 (A)(B)


Q.18 (a) =
dt k 2 + k3
Exercise 1 A1 A3
(b) Ea = Ea1 + Ea3 – Ea2 A =
Q.1 (a) 6.25 ; (b) 14.3; (c) 0 % A2
Q.2 2 × 10–2 min–1 Q.20 0.0805

Q.3 P1 = 379.55 mmHg, t7/n = 399.96 min Q.21 161 minutes

Q.4 0.0207 min–1 Q.22 55.33 kJ mole–1

Q.5 k = 0.022 hr–1 Q.23 Rate = K(A][13]2 rate will became 8 times

Q.6 15.13 week Q.24 K27 = 3.85 × 10–4 sec–1

Q.7 20 min K47 = 11.55 × 10–4 sec–1.

Q.8 0.26: 1 E = 43.78 kJ/mol

Q.9 (a) 43.46 kJ mol–1 (b) 20.47 hour Q.25 It is first order kinetics with

Q.10 % decomposition = 67.21 % k = 8.64 × 10–1

Q.11 k = 0 0327 min–1 Q.26 2

Q.12 0.537 Q.27 Ea = 2.2 × 104

Q.13 4.83 mins



A = 5.42 × 1010

Q.14 0.0025 m Q.28 (a) = 1 × 10–2 mol l–1 s–1

Q.15 Er=6 × 104 J; Eb = 9.3 × 104 J (b) = 5.495 × 10–3 mol–1 l–1 s–1

Q.16 a = b= 1 Q.29 Rate = 2 × 10–4 mol dm–3 min–1 x = 18.12%


E1k1 + E2k 2 Q.30 k = 0.02231 min–1 t = 62.07 min
Q.17 E=
k1 + k 2

Exercise 2

Single Correct Choice Type

Q.1 B Q.2 A Q.3 A Q.4 D Q.5 D Q.6 D


Q.7 C Q.8 B Q.9 C Q.10 D Q.11 D Q.12 C
Q.13 C Q.14 D Q.15 B Q.16 A Q.17 D Q.18 C
Q.19 B Q.20 B Q.21 C Q.22 D

Previous Years' Questions


Q.1 A Q.2 C Q.3 C Q.4 A Q.5 D Q.6 C
Q.7 B Q.8 C Q.9 A Q.10 D Q.11 A Q.12 D
Q.13 D Q.14 A Q.15 B Q.16 B Q.17 C Q.18 C
Q.19 D Q.20 B Q.21 B Q.22 A Q.23 D Q.24 A
1 8 . 5 6 | Chemical Kinetics

JEE Advanced/Boards Q.24 15 min

Q.25 (a) Third order, (b) r = k[NO]2[H2],


Exercise 1
(c) 8.85 ×10–3 M sec–1
1 d[NO]
Q.1 (i) r= = 9 × 10–4 mol litre–1 sec–1 Q.26 (a) Order w.r.t. NO = 2 and w.r.t. Cl2 = 1,
4 dt
(b) r = K[NO]2[Cl2],
(ii) 36 × 10–4 mol litre–1 sec–1
(c) K = 8 L2 mol–2s–1,
(iii) 54 × 10–4 mol litre–1 sec–1
(d) Rate = 0.256 mole L–1 s–1
Q.2 (i) 7.2 mol litre min ,
–1 –1

Q.27 (i) First order


(ii) 7.2 mol litre–1 min–1
(ii) k = 1.308 × 10–2 min–1
Q.3 (a) 1 × 10–4 mol L–1 s–1, (iii) 73%
(b) 3 × 10 mol L s
–4 –1 –1

dx Q.28 (i) Zero order, (ii) K = 5 Pa/s


Q.4 (i) = k [A][B]2
dt
Q.29 Zero order
(ii) Rate increases by 8 times
1 P3
Q.5 7.23 × 10–6 Ms–1, 0.012 atm min–1 Q.30 k = ln
t 2(P3 − P2 )
Q.6 Rate increases by 27 times
1 P3
Q.31 k = ln
Q.7 (a) 0.019 mol L s ,
–1 –1 t (P3 − P2 )

(b) 0.037 mol L–1 s–1 1 V1


Q.32 k = ln
t (2V1 − V2 )
Q.8 2k1= k2 = 4k3
1 4V3
Q.33 k = ln
Q.9 2.72 × 10 sec
18
t 5(V3 − V2 )

Q.10 1/6 1 r
Q.34 k = ln ∞
t (r∞ − r1 )
Q.11 (i) 7.2 M, (ii) 10 M
Q.35 First order
Q.12 K= 0.01 M min –1
Q.36 (i) r = K[(CH3)2O]2 0.000428 sec–1
Q.13 0.75 M Q.37 First order
Q.14 6 × 10–9 sec Q.38 966 min

Q.15 1.2 hr Q.39 (a) 90 mm,


(b) 47 mm,
Q.16 (i) 36 min (ii) 108 min
(c) 6.49 × 10–2 per minutes,
Q.17 (i) 0.0223 min , (ii) 62.17 min
–1
(d) 10.677 min.
Q.19 924.362 sec Q.40 k1 =2.605 × 10–3 min–1

Q.20 Expiry time = 41 months Q.41 (a) first order,


(b) 13.75 minutes,
Q.21 3.3 × 10–4 s–1
(c) 0.716 0.180 atm, 47.69 sec
2.303 1
Q.22 k = log
t a Q.42 11.45 days
Q.23 11.2% Q.43 0.1 min–1
Chem i str y | 18.57

1 Q.51 306 K
Q.44
e
(K1 +K2 )
t −1 Q.52 Rate of reaction increases 5.81 × 108 times

[C] 10 11x Q.53 10.757 k cal mol–1


Q.45 = (e – 1)
[A] 11 Q.54 t=20.4 minutes 56. 2000 K
Q.46 t = 4 min Q.55 r = K’ [NO]2 [Br2]
Q.47 0379.75 K Q.56 k = k'2
Q.48 5 kJ mol–1 Q.57 r = K[NO]2 [H2], where K=k2 × K1/k-1
Q.49 349.1 K Q.58 (d) No, (e) mechanism (a) is incorrect
Q.50 55.33 kJ mole –1

Exercise 2

Single Correct Choice Type

Q.1 B Q.2 D Q.3 C Q.4 D Q.5 C Q.6 B

Q.7 C Q.8 C Q.9 A Q.10 A Q.11 A Q.12 B

Multiple Correct Choice Type

Q.13 A, D Q.14 A,B,D Q.15 A, D Q.16 C, D Q.17 A, C, D Q.18 A, C

Q.19 A, B, C

Comprehension Type

Q.20 C Q.21 D Q.22 A Q.23 C Q.24 C Q.25 A

Q.26 B Q.27 C Q.28 B Q.29 D Q.30 B Q.31 C

Q.32 C Q.33 B Q.34 A Q.35 C Q.36 B

Match the Columns

Q.37 A → s; B → r; C → p; D → q Q.38 A → p; B → q, s; C → r, t; D → v

Previous Years’ Questions

Q.1 A Q.2 C Q.3 D Q.4 D Q.5 A Q.6 A

Q.7 B Q.8 A Q.9 0 Q.10 0.25 Q.11 128.33h

Q.12 3.56x10–16 Q.13 0.75 atm Q.14 4.15x103 s–1, 0.375

Q.15 (a) 1 (b) 693x10-3 min-1 (c) 200 min (d) 950 mm Q.16 D

Q.17 A Q.18 9 Q.19 D Q.20 C Q.21 B, C, D


1 8 . 5 8 | Chemical Kinetics

Solutions

JEE Main/Boards 3
⇒k=
[A0 ]
Exercise 1
Now, at time t = 2 hours,
Sol 1: (a) A + B → C −1 1 3 −6
+ = –2 × =
We have, first order in A and 0 order in B. [A] [A0 ] [A0 ] [A0 ]
−d[A] −d[A] 1 7 [A] 1
Rate = = k[A] 1[B] 0 = = – k[A] ⇒ = ⇒ =
dt dt [A] [A0 ] [A0 ] 7
For first order reaction, we know
100
A left is % or 14. 3 %
[A] = [A0] e–kt 7
We have, at t = 1 hour
(c) If the reaction is 0 order
75% of A reacted
d[A]
1 Rate = =k
[A] = A0 – 0. 75; A = A0 dt
4 [A] t
1 ⇒ ∫ d[A] = ∫ k dt
[A ] = [A0] e–kt ⇒ k = ln 4
4 0 [A0 ] 0

Now t = 2 hour, ⇒ [A] – [A0] = –kt


[A] 1
= e–2×ln 4 = ⇒ [A] = [A0]-kt
[A0 ] 16
Now, at time t = 1 hour
[A] = 6. 25 % of A0 [A0 ]
[A] =
∴6. 25% of A will be left unreacted. 4
[A0 ]
– [A0] = –k
(b) Here, reaction is first order in both A and B 4
3
d[A] ⇒k= [A ]
∴Rate = = k[A] [B] 4 0
dt
We see that, if t or [A] = 0
Since the initial concentration of A and B is the same
and they have the same coefficient, their concentration [A0 ] 4
t= = hours < 2 hours
will remain same at any time. k 3
−d[A] The reactions will be finished before 2 hours and 6 % of
= k[A] 2 A will be left after 2 hours.
dt
[A] t −
d[A]
⇒ ∫ = ∫ −kdt Sol 2: CH3CH2NO2 + OH– → CH3 CHNO2 + H2O
2
[A0 ] [A] 0 (A)
Since this is a first order reaction
1 1 [A] = [A0] e–kt
⇒− + = –k(t – 0) = kt
[A] [A0 ] 1
Now, we have at time t = minute,
2
[A0 ]
At time t = 1 hour, [A] = [A] = 0. 99[A0]
4
4 1 (1 % of nitroethane reacted)
∴− + = –k
[A0 ] [A0 ] ∴0. 99[A0] = [A0] e–k. 1/2
Chem i str y | 18.59

⇒ P0 – 2x = 158. 22
⇒ −k = loge(0. 99)
2 233.8 − 158.22
−k ⇒x= = 37. 78
⇒ = 0. 01 min. 2
2
Now, total pressure at t = 75 min
⇒ k = 0. 02 min–1
Pt = P0 + 3x + 32. 5
k = 2 × 10–2 min–1
= 233. 8 + (3 × 37. 78) + 32. 5

Sol 3: Here, since the volume of liquid is negligible and Pt = 379. 55 mm Hg


as the liquid begins to form, pressure due to liquid will
7
Time fraction, t7/8 is time at which th of reaction gets
always be equal to 32. 5 mm Hg. Now, let initial pressure 8
P
of P(g) be P0 mm Hg, then according to stoichiometry completed, ie. P∆ = 0
8
P0 2.303
2P(g) → 4Q(g) + R(g) + S() Using rate law, = P0e –kt ⇒ t = log 8
8 R
at time t = 399. 96 min.
t = 0 min P0 0 0 0
Sol 4: We have, the reaction as,
t = 30 min P0 – 2x 4x x 32. 5
Bn+ → B(n-2)+ + 4e

t = ∞ 0 2P0 P0 32. 5
At time t = 0 V0 0
2
Now, we are given, Pt = 317 mm Hg at t=30 min. total time
∴P0 – 2x + 4x + x + 32. 5 = 317 t = 10 min   V0 – x x
⇒ P0 + 3x = 284. 5  …….(i) Now, for titration we have
At time, t = ∞ (very long time), Pt = 617 mm Hg Bn+ + 2e → B(n–2)+
P0 From this, we see that for volume V0 of Bn+, 2V volume
∴2P0 + + 32. 5 = 617
2 of titrant is used.
5P0 at time t = 0, volume of titrant used = 25 mL
⇒ = 584. 5
2
⇒ 2V0 = 25 mL
⇒ P0 = 233. 8 mm Hg
⇒ V0 =12. 5 mL
Putting this in (i), we get,
For titration of B(n–1)+, we have
3x = 284. 5 – 233. 8
B(n+4)+ + 5e → B(n–1)-
⇒ x = 16. 9
i.e. for volume V of Bn+ + B(n+4), 5V volume of titrant is
Now, since this is first order reaction, we have used.
at t = 30 min a = 233.8 x = 16.9 ∴ At time t = 10 min,
2.303 P 2.303 233.8 Volume of titrant used = 32 mL
k= log 0 = log
t Pp 30 233.8 − (2 × 16.9) ⇒ 2(V0 – x) + 5x = 32
⇒ k = 5.2 × 10–3 min–1
⇒ 2V0 + 3x = 32
Now, at t = 75 min, we have
⇒3x = 32 – 25
2.303 P
k= log 0 7
t Pp ⇒x=
3
⇒ Pt = P0 × 10–kt/2. 303 Now, since this is a first order reaction, rate law is
–5.2×10 –3 ×75 2.303 V 2.303 12.5
= 233. 8 × 10 2.303 k= log 0 = log
t V n+ 10 12.5 − x
B
Pt = 158. 22 m Hg
1 8 . 6 0 | Chemical Kinetics

2.303 12.5 2.303 3.956


= log ; k = 0. 0207 min–1 k= log
10 7 6 3.956 – 1.281
12.5 −
3 k = 0. 065
Sol 5: We have initially, volume strength = 20 2.481
Now, when, τ = inch, we have
According to reaction 1000
2.303 3.956
1 0. 065= log
H2O2 → H2O + O t 3.956 – 2.481
2 2
1 2.303
1 mole (34g) of H2O2 gives moles of O2 i. e. 11. 21 ⇒t= × 0.49
at STP 2 0.065
t = 15. 13 weeks
Now, volume strength is the volume of O2 given by unit
volume of H2O2 t = 15. 13 weeks
Let normality of H2O2 = N longer = 9. 13 weeks
weight
Then, N = Sol 7: We have,
Eq. weight
H +
⇒ Weight = 17 N (equivalent weight = 17) A →B + C

Now, 34 g of H2O2 gives 11. 21 of O2 Let initially x moles of A be present


H +
11.2 × 17N A →B + C
\ 17 N g of H2O2 gives of O2
34 At t = 0 x 0 0
11.2 × 17N At t = ∞ 0 x x
Volume strength = = 5. 6 N
34
We know optical rotation of B and C are 40º and –80º
Now, initially volume strength = 20 respectively at completion,
20
⇒ N0 = = 3. 75 N total optical rotation
5.6
⇒ 40x – 80x = -10
At time, t = 6 hours, let normality be N.
⇒ x = 0. 5
Since, 10 mL of solution be diluted to 100 mL,
Now, optical rotation at t = 0
N.10
Now normality = = 0. 1 N
100 ⇒ 60 × 0. 5 = 30º
Now, since this is first order reaction, according to rate Using first order rate law,
law, as N is proportional to number of moles of H2O2 2.303 θ − θ∞
k= log 0
2.303 N t θt − θ∞
k= log 0 = 2.303 log 3.57 ; k = 0. 022 hr–1
t N 6 3.125 q0 = initial optical rotation

Sol 6: We have for oxide film formation. 0.693 0.693 1


or t1/2 = = +
k 2.303 θ0 − θ∞
2.303 τ log
k= log max θt − θ∞
6 τmax − τ
Putting values
Where, tmax = maximum thickness of oxide film
(at t → ∞) 0.693 20
t1/2 = +
τ = thickness at time t 2.303 (30 − 1 − 20)
log
(5 − 1 − 20)
We are given
since θ = 5º
3.956
tmax = inch 0.3 × 20
1000 at t = 20 min =
log2
1.281 t1/2 = 20 min
τ= inch, at t = 6 weeks
1000
Chem i str y | 18.61

Sol 8: Since, volume and temperature is constant, we +(log3 × 2.303 × 8.314 × 293 × 276)
∴ EA =
take P ∝ n 17
CH3OCH3(g)→CH4(g)+CO(g)+H2(g) EA = 43. 46 kJ/mol
at (b) When T2 = (273 + 40) K = 313K,
t=0 0. 4 0 0 0 k2 43.460  1 1 
We have, log =  − 
t = 4.5hr. 0. 4–x x x x k1 303 × 8.314  293 313 
We are given k = 4. 78 × 10 , since unit is –3 ⇒ k2 = 3312 k1

min–1. It is a first order reaction and 1


Further, as k ∝
t
PA = P0e–kt
t2 k1 6.4
= 0.4 × e(–4. 78 × 10
–3 × 4. 5 × 60)
∴ = ⇒ t2 =
t1 k2 3.12
⇒ PA = 0.11 t2 = 20. 47 hours
0. 4 – x = 0. 11
⇒ x = 0. 29 Sol 10: We have, according to Arrhenius equation

Now, at t = 4. 5hr, mean molecular mass, M2 k2 EA 1 1


log =  − 
k1 2.303R  t1 t2 
(P0 − x)MCH + x.MCH + MCO + x + M0 + xMH
3OCH3 Here,
= 4 2
P+x+x+x+x
EA = 70 ks mol–1
0.11 × 46 × 0.29 × 16 + 0.29 × 28 + 0.29 × 2
= = 18. 77 t1 = (273 + 25) K = 298 K
0.11 + 0.29 + 0.29 + 0.29
t2 = (273 + 40) K = 313 K
at t = 0, molecular mass
Putting values
M1 = MCH = 46 k2
3OCH3 70000  1 1 
log =  − 
Pt = 0. 4 – x + 3x = 0. 4 × 2x = 0. 98 k1 2.303 × 8.314  298 313 
According to Graham’s law ⇒ k2 = 3. 87 k1
P Now, equation
Rate of diffusion ∝
M A→B
D0 P0 M2 18.77 0.4 According to rate law
= = ×
Dt Pt M1 46 0.98
[A] = [A0] e–kt
D0 At T = 298 K, k = k1, … t = 20 min,
= 0. 26
Dt 3[A0 ]
[A] =
4
Sol 9: (a) According to Arrhenius equation, we have
3 −k .20
∴ = e 1
k2 EA  1 1  4
log =  − 
k1 2.303  T1 T2  ⇒ k1 = 0. 014 min–1
Here, we have ∴ k2 = 3. 87 k1 = 0. 055 min–1
T1 = (273 + 20)K = 293 K Now, at T = 313 K, t = 20 min,
T2 = (273 + 3)K = 276 K k = 0. 055 min–1
k1 [A] = [A0] e–0. 055 × 20
k2 =
3
Putting values [A] = 0. 3279 [A0]
∴ 67. 21 % of A got decomposed.
1 EA  1 1 
log =  − 
3 2.303 × 8.314  293 276 
1 8 . 6 2 | Chemical Kinetics

Sol 11: We have, according to Arrhenius equation d[C]


We have, = k2[A]
k2 EA 1 1  dt
log =  − 
k1 2.303R  T1 T2  d[C] −(k +k )t
⇒ = k2[A0] e 1 2
dt
For, A → products
[C] t
If k at 310 K is taken to be k −(k1 +k 2 )t
⇒ ∫ d[C] = k 2 [A0 ]∫ e dt
k 0 0
Then, k at 300 K is
2 k 2 [A0 ] −(k1 +k 2 )t
[C] = (1 − e )
Putting this in equation, we get k1 + k 2
EA  1 1  k [A ](1 − e 1 2 )
−(k +k )t
log 2 =  −  [C]
2.303 × 8.314  300 310  = 2 0
[A] −(k +k )t
(k1 + k 2 ).[A0 ]e 1 2
log2 × 2.303 × 8.314 × 310 × 300
⇒ EA = k2 (k1 +k 2 )t
10 = (e − 1)
k1 + k 2
EA = 53. 67 kJ/mol
Now we are also given at T = 310 K, Now, we have k1 = 1. 3 × 10–5 s–1,

t1/2 = 30 min k2 = 9k1 = 1. 17 × 10–7 s–1

0.693 Time, t = 1 hour = 3600 s


∴ k at 310 K = = 0. 0231 min–1
t1/2 Putting values,
At 310 K, for (ii) B → products [C] 9 1.3×10−4 ×3600
= (e − 1)
k = 211 for (i) [A] 10

= 0. 0462 min–1 [C]


= 0. 537
[A]
Further, for (ii)
(EA ) f k
EA = = 26. 802 k J/mol Sol 13: As Cis-(en)2(OH)2+ 

k b
2
trans-Cr(en)2(OH)2+
Therefore, using Arrhenius equation, we get
We have,
k 268.02  1 1  kf
log =  − 
0.0769 2.303 × 8.314  310 300  Eq. constant = = 0. 16
kb
k = 0. 0327 min–1
and kf = k1 = 3. 3 × 10–1 s–1
kt
Sol 12: We are given, ⇒ kb = = 2. 0625 × 10–4 s–1
0.16
k1 B
Now using formula for eq. reactions.
A
 xeq 
k2 C ln   = (kf + kb) t
 xeq .x 
 
Here, xeq
We have to find t for which x =
k1 1 q
= , k = 1. 3 × 10–5 s–1  
k2 9  x 
eq
Now, both are first order reactions ln   = (3. 3 × 10–4 + 2. 0625 × 10–3)t
 xeq 
d[A]  xeq − 
∴ = –(k1 + k2)[A]  2 
dt
ln 2
⇒ [A] = [A0] e
−(k1 +k 2 )t ⇒t= s
2.3925 × 10−5
Now, for A → C,
t = 289. 71 s ⇒ t = 4. 83 min
Chem i str y | 18.63

1 k

Sol 14: We have, A  B
k 2

k1 [B]eq

Energy →
Also, we know, keq = = Ef Eb
k2 [A]eq
k1
⇒ = 4, k1 = 10–2 s–1
k2 A B ∆H

10−2 Reaction coordinate →


⇒ k2 = = 2. 5 × 10–3 s–1
4 We see that
Now at eq. , [A] = [A0] – xeq
Eb = Ef + |∆H|
[B] = xeq
20Eb
⇒ But Ef =
xeq 31
Then, =4
− xeq
[A]e 20Eb 11Eb
∴Eb = + 33 ⇒ = 33
We are given [A] 0 = 0. 01 mole L–1 31 31
⇒ Eb = 63 kJ/mol
xeq
=1 Ef = Eb – 33
0.01 xeq
5xeq = 0 + 60. 07 Ef = 30 kJ/mol
xeq = 0. 008 mole L–1
Now, using equilibrium first order formula, Sol 16: We have rate k′[complex] a, k′ = k[H+] b

 xeq  Let’s assume that this is Pseudo first order reaction, that is
ln   = (k1 + k2)t a=1
 xeq − x 
  0.693
Then, we have t1/2 = ,
At t = 30 s, k′
1.386
 0.008  t3/4 =
ln   = (12. 5 × 10 ) × 30 = – 0. 375
–3 k′
 0.008 − x 
We note that, here t3/4 = 2. t1/2
x = 0. 0025 mole L–1
which is true for given data also

Sol 15: We have, Now, when, [H+] = 0. 01

 B(g)
A(g) 

 0.693 0.693 0.693
t1/2 = 1 = = ⇒ (0. 01)b =
k′ + b
k[H ] k
For forward reaction, we have
∆H = ∆E = –33 kJ/mol When [H+] = 0. 02
0.693 1.386
We know, (0. 02)b = =
k.t1/2 k
−∆Hº
ln k = (since ∆S ≈ 0) These both will be satisfied for b = 1.
RT
with T = 300 K, ∆H = 33 kJ/mol ∴ Taking a = b = 1, all the given data can be verified
and there are no contradictions
we get, k = 5. 57 × 105
∴a=b=1
Now, we are given
Ef 20 k
= Sol 17: A 
1
→B
Eb 31
2k
Now, we have for this transformation A  →C
−d[A]
We have, k for disappearance of A, = (k1 + k2)t
dt
∴ k = k1 + k2
1 8 . 6 4 | Chemical Kinetics

Using Arrhenius equation, Sol 19 We have,


−E1 −E2
−E
Rate, R = k3[COCl] [Cl2]
Ae RT = A1e RT + A2e RT
(∵ (iii) is slowest step (RDS))
A = Pre exponential constant Also, from equilibrium of (ii),
1 k2 [COCl]
Differentiating with respect to , we get =
T k −2 [CO][Cl]
−E −E −E
−AE RT −A1E1 RT1 −A2E2 RT2
e = e + e And from equilibrium of (i),
R R R
k1 [Cl]2
⇒ Ek = E1k1 + E2k2 =
k −1 [Cl2 ]
E1k1 + E2k 2 k 
1/2
⇒E= [Cl] =  1  ([Cl2 ])1/2
k
 k −1 
E1k1 + E2k 2
⇒E= Putting these values back in rate formula,
k1 + k 2
we get
1
+
Sol 18: (a) We have, k2 k  2
Rate = k 3 [CO]  1  ([Cl2 ])1/2 [Cl]
k
k −2  k −1 
1
A + B 
 C
k 2
k1 d[COCl2 ] k 2 k1
C  
→ D = k3 [CO][Cl2 ]3/2 = k[CO] [Cl2] 3/2
dt k −2 k −1
Since second step is RDS,
1/2
Rate = k3[C] k 2  k1 
k = k3 .  
d[C] k −2  k 2 
Also, = –k3[C] + k2[A] [B] – k2[C]
dt
d[C] k [A][B] k1
Now, at steady state, = 0 ⇒ [C] = 1 2B(g)
dt k3 + k 2
Sol 20: A(g)
k1k 3 [A][B] k2
∴ Rate = C(g)
k3 + k 2
We have,
(b) If k2 >> k3, then k2 + k3 ~
_ k2
−d[A]
Rate = = –(k1 + k2)[A]
k1k 3 dt
Then, Rate = [A] [B]
k2 [A] = [A]0 e–kt ; k = k1 + k2
Using Arrhenius equation, 1 d[B]
Further, Rate = = k1[A]
−EA 2 dt
k = A e RT
Putting value of [A] and integrating
Ea Ea
1 3 −(Ea +Ea −Ea )
A1 e RT A3 e RT 1 3 2 2k1 [A1 ]
A1 A3
k= = e RT [B] = (1 − e−kt )
Ea
2 A2 k1 + k 2
A2 e RT k 2 [A]0
−Ea Similarly, [C] = (1 − e−kt )
Comparing with k = Ae RT k1 + k 2

A1 A3 Now, we are given [A]0 = 1 atm


A=
A2 At t → ∞, Pt = 1. 5 atm
Ea = Ea + Ea − Ea Putting values and taking t = ∞, we get
1 3 2
Chem i str y | 18.65

2k1 k2 Sol 23: 2A + B + C → D + 2E


+ = 1. 5
k1 + k 2 k1 + k 2 (i) Since, this is first order w. r. t. A, second order w. r. t.
B, and 0 order w. r. t. C.
⇒ 2k1 + k2 = 1. 5 k1 + 1. 5k2
Rate law = k[A] [B]2[C]0
k
⇒ k1 = k2 = Rate,R = k[A] [B]2
2
Now, taken at t = 10s, Pt = 1. 4 atm (ii) Now rate, R′ = k[2A] [2B]2 = 8k[A] [B]2 = 8k
k[A]0 ∴ Rate becomes 8 times
∴ [A]0e–k. 10 = (1 − e−k.10 )
k
k[A]0 Sol 24: We know, for first order reaction
(1 − e−k.10 ) = 1. 7
2k 2.303 [A]
k= log 0
[A]0 = 1, 30 [A]t
1 e−10k At T = 27ºC = 300 K, at t = 30 min, 50% of reaction gets
∴ e–10R + 1 – e–10R + – = 1. 4
2 2 completed, i. e. [A] t = 0. 5[A]0
⇒ e–10R = 0. 2 2.303
k= log2
⇒ k = 0. 16 30
k = 0. 0231 min–1 = 3.85 × 10–4 s–1
k
⇒ k 1 = k2 = = 0. 08
2 At T = 47ºC=320 K, time taken for 50% completion is
10 min.
Sol 21: For 50% completion, time taken 2.303
∴k= log2
0.693 10
t1/2 =
k k = 0. 0693 min–1 = 11.55 × 10–4 s–1
0.693 Now, by Arrhenius equation
⇒k= = 0. 01 min–1
69.3
k2 EA  1 1 
Now, for 80%, [A] = 0. 2[A0] ln =  − 
k1 2.303  T1 T2 
Using [A] = [A]0e–RT ⇒ 0. 2 = e–RT
ln5 At T = 300 K, k = 0. 0231 min–1
⇒t=
0.01 T = 320 K, k = 0. 0693 min–1
t = 161 min Putting values

0.0693 EA  1 1 
Sol 22: We have, from Arrhenius equation, log =  − 
0.0231 2.303 × 8.314  300 320 
k2 Ea 1 1 
log =  −  EA = 43. 78 kJ/mol
k1 2.303R  T1 T2 
k2
Now, = 4, T1 = 27ºC = 300 K Sol 25: Firstly, we assume that reaction is first order and
k1
see if the data is consistent.
T2 = 47ºC = 320 K
For first order reaction, we have
Putting values, we find 2.303 θ − θ∞
k= log 0
EA  1 1  t θt − θ∞
log 4 =  − 
2.303 × 8.314  300 320  At time, t = 10 min,

2log2 × 320 × 300 × 2.303 × 8.314 2.303 32.4 − ( −11.1)


⇒ EA = k= log
20 t 28.8 − ( −11.1)
EA = 55. 33 kJ mol–1 k = 8. 14 × 10–3 min–1
At time, t = 20 min
1 8 . 6 6 | Chemical Kinetics

2.303 (32.4 + 11.1) Sol 28: Rate = k[A]


k= log
t 25.5 − ( −11) (i) Initial rate = k[A] 0
k = 8. 64 × 10–3 min–1 = 1. 8 × 10–2 × 0. 1
At time, t = 30 min = 1 × 10–3 mol sec–1 L–1
2.303 32.4 − (11.1) (ii) After 60 sec (1 min),
k= log = 8. 70 × 10–3 min–1
t 22.4 − ( −11) Rate = k[A] 1
At t = 40 min, = k[A]0 e–k×60
2.303 32.4 − (11.1) = 5. 495 × 10–3 mol sec–1 L–1
k= log = 8. 71 × 10–3 min–1
40 19.6 − ( −11.1)
We see that all values of k are pretty close to each other, Sol 29: Since, unit of rate constant is min–1, it is first
order reaction.
∴ The reaction is first order.
Initial rate = k [A]0 = 10–3 × 0. 2 = 2×10–4 mol min–1 dm–3
1 After 200 minutes,
Sol 26: We know, for nth order reaction t1/2 ∝
[A]n0−1 −3 ×200
[A] = [A] 0 e−10 = 0. 8187[A] 0
Here as [A]0 is doubled, t1/2 gets halved,
∴ 18. 12 % of reactant converted into product.
1
∴ t1/2 ∝
[A]0
Sol 30: (i) At time, t = 10 min, [A] = 0. 8 [A]0
Or n – 1 = 1
∴ 0. 8[A]0 = [A]0 e–10k
⇒n=2
⇒ k = 0. 022 min–1
Hence, second order reaction.
(ii) When 75% reaction is completed,
Sol 27: We have, by Arrhenius equation 1
[A] = [A]0,
4
k2 Ea 1 1
log =  −  1
k1 2.303k  T1 T2  ∴ [A]0 = [A]0 e–0. 022t
4
Now, given data, ⇒ t = 63. 01 min.
at t = 50ºC = 323 K,
k = 1. 5 × 10+7 sec–1.
Exercise 2
at T = 100ºC = 373 K,
k = 4. 5 × 107 sec–1 Sol 1: (B) From the table, we see that when (A) is
doubled, rate get becomes 4 times, keeping (B) constant
Filling the data,
∴ Rate ∝ (A) 2
Ea
 1 1 
log 3 =  −  Also, when (B) is doubled, keeping (A) doubled.
2.303 × 8.314  323 373 
−Ea Rate becomes 2 times
Ea = A e RT ∴ Rate ∝ (B)
∴ Rate = k(A)2 (B)
Ea = 2. 2 × 107 J mol–1
−Ea
Now,k = A e RT Sol 2: (A) Rate, ri = k(A) n[B] m
m
+Ea B  k 2n
⇒ A = ke RT rf = k[2A] n     = [A] n [B] m
2.2×107
2
  2 m

7e 8.214 ×323 rf
= 1. 5 × 10 = 2(n – m)
ri
A = 5. 42 × 1010 s–1
Chem i str y | 18.67

Sol 3: (A) We have t1/2 = 15 min (0. 8 M → 0. 4M) Rate = k[A]


Now, for 0. 1 M to 0. 025 M, = 0. 01 × 0. 1 M min–1
t = 2 × t1/2 = 30 min = 10–3 M min–1
t t
(0. 1 
1/2
→ 0. 5 
1/2
→ 0. 025)
Sol 9: (C) For zero order reaction, rate is always
constant.
Sol 4: (D) Only statement (D) is correct as k is constant
at a given temperature. i. e. rate = 10–2 M min–1

(A) and (B) are correct for first order reaction. (C) is A(g) → 2B(g)
wrong as t=0 0. 1
d[C] 1 d[A]  d[A]  t=1 0. 1–x   2x
= −  not 2 
dt 2 dt  dt 
1 d[B]
= 10–2
2 dt
Sol 5: (D) For a first order reaction,
[B] = 0. 02 t
[A] = [A]0e–kt
At t = 60 sec = 1 minute
3
When, [A] = [A]0 , t = t3/4
4 [B] = 0.02 M
3 −k.t
⇒ = e 3/ 4
4 Sol 10: (D) Let time be t
0.29 Then, for X →A + B
1 k
⇒ t3/4 =
k
50% reaction gets completed at time t
Sol 6: (D) rate ∝ [O] 2 1 −k t
⇒ [X]0 = [X]0 e 1
2
∴ When [(O)] is doubled, rate becomes 4 times.
ln2
k1 =
t
Sol 7: (C) A + 3B → P
k
For Y 
2→C + D
∆H = -2x kJ/mole of A  …(i)
96 % of reaction gets completed at time t.
M → 2Q + R
∴ 0. 04[Y] 0 = [Y]
−k 2 t
e
∆H = -x kJ/mole of M  …(ii) 0
ln25
We see that, if these reactions are carried simultaneously k2 =
t
energy released from (i) and energy absorbed is (ii)
counter each other further, ∆H = 2OH, rate of second k2 ln25
= = 4. 65
reaction will be double of that of (i) k1 ln2
−1 d[B] y
Now, rate of first reaction= = Sol 11: (D) We know, for nth order reaction
3 dt 3
1
2y 1 d[Q] d[Q] 4 ∝
Rate of second reaction= = ⇒ = y P0n−1
3 2 dt dt 3 n−1
(t1/2 )2  P0 
⇒ = 1 
Sol 8: (B) We have t = 138. 6 min for (t1/2 )1  P0 
 2 
1M → 0. 25 M Putting values,
2 × 0.693
i.e., 2t1/2 = 138. 6 = 950  500 
n−1
k =  
t t 235  250 
(1 
1/2
→ 0. 5 
1/2
→ 0. 25)
log 4.04
⇒ k = 0. 01 ⇒n–1= = 2; ⇒ n = 3
log2
When [A] = 0. 1,
1 8 . 6 8 | Chemical Kinetics

Sol 12: (C) We have first order reaction Sol 16: (A) We have for first order,

2.303 [A] (A) = (A) 0e–kt


k= log 0
t [A]t 0.1
(A)0 = mol L–1 = 0. 05 mol L–1
at t = 20 min, (A) t = 0.8(A)0 2
k = 3. 465 × 10–6 s–1, t = 200 s
(Since 20% reaction completed)
−6 ×200
(A) = 0. 05 e−3.465×10
2.303 5
⇒k= log ≈ 0. 05 M
20 4
k = 1. 11 × 10–2 min–1
Sol 17: (D) R is universal gas constant
0.693
t1/2 = = 62. 13 minutes k is rate constant
k
A is pre exponential factor
Sol 13: (C) Rate = k(A) = k(A) 0e–kt
Ea is activation energy
It follows an exponential decay.
Sol 18: (C) This is the correct definition.
Sol 14: (D) A(g) → 2B(g)
−E0 /RT
  100 2  Sol 19 (B) k = A e ;As T → ∞,
2    −E0 /RT
B   V   10 4 1 k = A = 6 × 1014 s–1(∵ e → 1)
We have, keq = =   = . = 108
[A]  10
−5
 10 −5 10
 V  Sol 20: (B) We have, from Arrhenius equation
 
k 1.5 × 10 −3 k2 EA 1 1
108 = f = log =  − 
kb kb k1 2.303R  T1 T2 
⇒ kb = 1. 5 × 10–11 L mol–1 s–1 Here, at T1 = 27ºC = 300 K

Sol 15: (B) A + B → C + D 0.693


k1 = min–1
20
t=0 1 1 0 0
t=1 1-x 1–x x x At T2 = 47ºC = 320 K

We have, 0.693
k2 = min–1
−d[A] 5
Rate = = k(A) 1/2(B) 1/2
dt Putting these values,
−d[A] EA  1 1 
⇒ = k(1 – x)1/2 (1 – x)1/2 log 4 =  − 
dt 2.303 × 8.314  300 320 
−d[A] ⇒EA = 55. 14 kJ/mol
⇒ = k(1 – x)
dt
This can be written as, Sol 21: (C) We have, 27ºC = 300 K, 3. 8 × 10–16 of
−d[A] reactant molecules exist in the activated region.
= k(A)
dt i. e, N = 3. 8 × 10–16 N0

⇒ (A) = (A) 0e–kt Now, N = N0 e−Ea /RT

when (A) = 0. 25(A)0 Ea = RT loge N0 = 8. 314 × 300 loge


N
2 n2 2 × 2.303log2 N0
t= =
k 2.303 × 10−3 3.8 × 10−16 N0
t = 600 s
Ea = 100 kJ/mol
Chem i str y | 18.69

Sol 22: (D) Since, at 400 K, 0. 0001% (10–4%) of collisions 0.693 2.303  100 
are effective only 10–4% of molecules have their energy = log  
t1/2 t  100 – 99 
above activation energy.
N0 0.693 2.303 × 2
Ea = 2. 303 RT log =
N 6.93 t
N0
= 2. 303 × 8. 314 × 400 log So, t = 46.06 min.
10−6 N0
= 45. 944 k J/mol = 11. 05 k cal/mol Sol 7: (B) Because two molecules are taking part in
elementary reaction.

Previous Years’ Questions Sol 8: (C) Since –


dx
∝ [CO]2 so on doubling the
dt
1 d[A] 1 d[B] d[A] 1 d[B] concentration of CO, the rate of reaction will increase
Sol 1: (A) A → 2B ; – 2 = ;– = by 4 times.
2 dt 2 dt dt 4 dt

∆T 50 Sol 9: (A) R = k(A)(B)2 order of reaction =2+1= 3


Rate at 50°C T
Sol 2: (C) = (2) 1 = (2)10 = 25 = 32 times
Rate atT1 °C
Sol 10: (D) The differential rate law for,
NO + Br2 → NOBr2 would be
2.303 a
Sol 3: (C) k = log10 ;
t a−x dc
– =k[NOBr2][NO]
dt
t = 2 × 102, a = 800, a – x = 50 [NOBr2 ]
We have, Kc =
2.303 800 2.303 [NO][Br2 ]
k= log10 = log10 16
2 × 10 2 50 2 × 102 Provided the first reaction attains equilibrium rapidly.
dc
2.303 4 2.303 ∴– = k × kc × [NO]2[Br2] = k[NO]2[Br2]
= log10 2 = × 4 × 0.301 = 1.38 × 10 s
–2 –1
dt
2 × 102 2 × 102
∴The order of the reaction with respect to NO(g) is 2.

Sol 4: (A) 2A + B → Product Sol 11: (A) For A


When conc. of B is doubled, the half-life did not Rate = k[Cl2][H2S] (By slow step)
change, hence reaction is of first order w.r.t. B. When
concentration of A is doubled, reaction rate is doubled, For B
hence reaction is of first order w.r.t. A, Rate = k[Cl2][HS–]
Hence, over all order of reaction is 1 +1 = 2
[H+ ][HS − ]
keq =
So, unit of rate constant mol lit s . –1 –1
[H2S]
(According to equilibrium)
Sol 5: (D) Rate= k(N2O5)
k eq [H2S]
hence 2.4 × 10–5 Rate = k[Cl2]
[H+ ]
= 3.0 × 10 (N2O5) or (N2O5)
–5

= 0.8 mol l–1 [H2S]


Rate = k.keq[Cl2]
[H+ ]
Sol 6 (C) In first order reaction for x% completion
a
Sol 12: (D) t1/2 = (for zero order reaction)
2.303  100  2k 0
k= log  
t  100 – x%  a 2
k0 = = =1
2 × t1/2 2 × 1
1 8 . 7 0 | Chemical Kinetics

A0 – [A]t 0.50 – 0.25 Sol 19: (D) Rate equation is to be derived w.r.t slow
k0 = ⇒ k0 = =1
t t Step ∴ from mechanism (A)
t = 0.25 hr. Rate = k[Cl2] [H2S]

Sol 13: (D) So, ∆HReaction = Ef – Eb = 80 – 100 = –20. Sol 20: (B)
Temperature coefficient µ =2;
Sol 14: (A) For endothermic reaction ∆H = +ve ∆T
k
Then from equation ∆H = EaF.R – EaB.R ; EB.R < EF.R . µ 10 =2 ;
k1
50
k2
Sol 15: (B) In photochemical reaction, the rate of µ 10 = 25 = 32 =
k1
formation of product is directly proportional to the
intensity of absorbed light. Therefore 32k1 = k2

Sol 16: (B) 2.303 0.1


Sol 21: (B) k = log ;
1 40 0.025
A → 2B 0.693
2 k=
20
d[A] d[B]
− =
+ 0.693
dt 2dt For a F.O.R., rate = × 10−2 = 3.47 × 10−4 M / min.
20
d[A] 1 d[B]
− =
dt 4 dt
K −Ea  1 1 
Sol 22: (A)
= log 2  − 
Sol 17: (C) K1 2.030R  T2 T1 
K2
0.6932 0.6932 = 2;=
T2 310K T1 300K
=
=
 λ = min−1 K1
t1/2 6.93
−E  1 1 
[A ] ⇒ log2
=  − 
2.303 2.303 × 8.134  310 300 
Also t= log 
λ [A]
=⇒ Ea 53598.6
= J / mol 53.6 KJ / mol
[A ] = initial concentration (amount)
[A] = final concentration (amount)
Sol 23: (D)
2.303 × 6.93 100
∴ t= log = 46.06 minutes
0.6932 1 −1 d[A] d[B] d[C] d[D]
Rate of Reaction = =
− = =
2 dt dt dt dt
Sol 18: (C) Let rate of Reaction = k(A)x(B)y
x d[C]
For a zero order reaction k = …. (i) Or, = k[A]x [B]y
t dt
Where x = amount decomposed Now from table,
k = zero order rate constant 1.2 × 10–3 = k [0.1]x[0.1]y  .....(i)
for a zero order reaction 1.2 × 10–3 = k [0.1]x[0.2]y  .....(ii)
[A]0 2.4 × 10–3 = k [0.2]x[0.1]y  .....(iii)
k=  …. (ii)
2t1/2
Dividing equation (i) by (ii)
Since [A0]=2M, t1/2 = 1hr; k=1 1.2 × 10−3 k[0.1]x [0.1]y
⇒ =
∴ from equation (i) 1.2 × 10−3 k[0.1]x [0.2]y
0.25 y
=t = 0.25 hr 1 
1 ⇒ 1=
 
2
Chem i str y | 18.71

⇒ y=0 +1.08
= × 10 −2 = 3. 6 × 10–3 mol L–1
3
Now dividing equation (i) by (iii)
d[H2O] 6 d[NO]
−3 x y (iii) =
1.2 × 10 k[0.1] [0.1] dt 4 dt
⇒ =
−3
1.2 × 10 k[0.2]x [0.1]y 3 1.08 × 10 −2
= × = 5. 4 × 10–3 mol L–1
1 y 2 3
1  1 
⇒   = 
2 2 Sol 2: (a) 2H2O2 → 2H2O + O2
⇒ xx==
1 −1 d[H2O2 ] −1 d[H2O] d[O2 ]
We know, = =
2 dt 2 dt dt
d[C]
Hence = k[A]1 [B]0
dt d[H2O] d[O2 ]
=2 = 2 × 3. 6 M min–1
dt dt
Sol 24: (A) In 50 minutes, concentration of H2O2 d[H2O]
= 7. 2 M min–1
1 dt
becomes of initial.
4
−d[H2O2 ] 2 d[H2O] −d[H2O2 ]
⇒ 2 × t1/2 = 50 minutes (b) = = = 7. 2 M min–1
dt 2 dt dt
⇒ t1/2 =
25 minutes
Sol 3: N2 + 3H2 → 2NH3
0.693
⇒ K= per minutes
25 d[N2 ] −1 d[H2 ] 1 d[NH3 ]
(a) = =
0.693 dt 3 dt 2 dt
rH = × 0.05 = 1.386 × 10−3
2O2 25 −d[N2 ] 1 d[NH3 ]
=
dt 2 dt
2H2O2 → 2H2O + O2
1
= × 2 × 10–4 mol L–1s–1 = 10–4 mol L–1 s–1
1 2
rO = ×r
2 2 H2O2 −d[H2 ] 3 d[NH3 ]
(b) = ×
dt 2 dt
rO
= 0.693 × 10−3
2 3
= ×2 × 10–4 mol L–1 s–1 = 3 × 10–4 mol L–1 s–1
6.93 × 10−4 mol / minute × litre
rO = 2
2

Sol 4: (i) Reaction of first order in A, second order in B


JEE Advanced/Boards and 0 order w. r. t. C.
dx
= k [A] 1[B] 2[C] 0, k = [D]t
Exercise 1 dt
dx
⇒ = k[A] [B] 2
Sol 1: 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g) dt
−1 d[NH3 ] −1 d[O2 ] (ii) If [A], [B], [C] are all doubled.
Rate of reaction = = =
4 dt 5 dt rf = k[2A] [2B] 2 = 8k[A] [B] 2 = 8r
1 d[NO] 1 d[H2O] Rate becomes 8 times
=
4 dt 6 dt
1 d[NO] 1 1.08 × 10−2 Sol 5: We have, by ideal gas equation
(i) Rate of reaction = =
4 dt 4 3 n
PV = nRT ⇒ P = RT
= 9 × 10–4 mol L–1 V
P = CRT
−d[NH3 ]
(ii) = +4 d[NO] P
dt 4 dt C=
RT
1 8 . 7 2 | Chemical Kinetics

∆C 1 ∆P k2
Rate of reaction = = ⇒ k1 = = 2k3 ⇒ 2k1 = k2 = 4k3
∆t RT ∆T 2
We have, R = 0. 0921 L atm/mol. k
1 4
T = 27ºC = 300 K Sol 9: 4 1 H → 2 He ; ∆H = 2. 6 MeV

ΔP = (2 – 1. 1) atm = 0. 9 atm It means 4 atoms of H, eject 26 MeV energy.

ΔT = 75 × 605 = 4500 s Energy released by 1 mole of


1 0.9 NA
Rate of reaction = × Ms–1 H= = 26 × 106 × 1. 6 × 10–14 J = 6. 26 × 1011 J
0.0921 × 300 75 × 60 4
= 7. 23 × 10–6 Ms–1 Power output of sun = 3. 9×1026 W = 3. 9 × 1026 J/s
Rate of reaction in terms of pressure i.e. it radiates 3. 9 × 1026 J in one second.
∆P 0.9 Number of moles of H required per second
= = atm min–1 = 0.012 atm min–1
∆t 75
3.9 × 1026
= = 6. 23 × 1014
6.26 × 1011
Sol 6: 2A + B2 → 2AB
1.7 × 1030
Since, this is an elementary reaction, Total moles of H on sun = = 1. 7 × 1033
10 −3
rate, ri = k[A] 2[B2] 1.7 × 1033
Time taken = = 2. 72 × 1018 s
If volume of vessel reduced to one-third, [A] and [B2] 6.23 × 1014
becomes 3 times each.
∴ rf = k[3A] 2[3B2] = 27k (A) 2[B2] = 27ri Sol 10: A(g) + 2B(g) → C(g) + D(g)

Hence, rate becomes 27 times. t = 0 0. 6 0. 8 0 0


t 0. 6–x 0. 8–2x x x
Sol 7: 3BrO → BrO3 + 2Br
– -
Since this is elementary reaction
We have, Rate, r = k(B) 2(A)
−1 ∆[BrO] ∆[BrO3− ] Now,ri = k(0. 6)(0. 8)2 = 0. 381 k
Rate = =
3 ∆t ∆t
WhenPi = x – 0. 2 atm
1 ∆[Br] −∆[BrO − ]
= = k[BrO–] +2= = 3k[BrO–] 2 PA = 0. 6 – x = 0. 4 atm
2 ∆t ∆t
We have, 3k = 0.056 PB = 0. 8 – 2x = 0. 8 – 0. 4 = 0. 4 atm

k = 0.0186 mol–1 s–1 rf = k(0. 4)(0. 4)2 = 0.064 k


rf 0.064 1
∆[BrO3− ] = =
(a) = k[BrO–] 2 = 0. 0186[BrO–] 2
∆t ri 0.384 6
Hence rate constant = 0. 0186 L mol–1s–1
Sol 11: A → B
∆[Br − ]
(b) = 2k[BrO–] 2 = 0. 037[BrO–] 2 k = 1. 2 × 10–2 Ms–1
∆t
Rate constant = 0. 037 Lmol–1s–1 Since unit of rate constant is Ms–1, it is zero order
reaction
1
Sol 8: We have, N2O5(g) → 2NO2(g) + O2(g) Rate law [B] = kt
2
−d[N2O5 ] 1 d[NO ] At t = 10 min
⇒ = 2
dt 2 dt [B] = 1. 2 × 10–2 × 10 × 60 M
1 d[O2 ] [B] = 7. 2 M
= = +k[N2O5]
1 dt
At t = 20 min
2
k
Hence, k1 = k, k2 = 2k, k3 = [B] = 1. 2 × 10–2 × 20 × 60 M = 14. 4 M
2
Chem i str y | 18.73

But, [A] 0 = 10 M and [B] cannot be greater than [A0] [A]0. When A is 10% unreacted,
∴ [B] = 14.4 M implies that reaction has reached 1
[A] = [A ]
completion, i. e. 10 0
1
[B] max = 10 M ∴ [A]0 = [A]0 – kt
10
[B] = 10 M
9 3
⇒ [A] 0 = [A]0t
Sol 12: For zero order reaction, 10 4

[A] = [A]0 – kt ⇒ t = 1. 2 hr
At t = 0, [A] = [A]0 = 0. 1 M
At t = 1 min, [A] = 0. 09 M Sol 16: (i) We know, for first order reaction
0. 09 = 0.1 – k [A] = [A]0e–kt
⇒ k = 0. 01 M min–1 k=
1 [A]0
ln
t [A]
At t = 2 min, [A] = 0. 1 – 0. 01 × 2
1
At t = 72 min, 75% reaction completed, i. e. [A] = [A]0
= 0. 08 M, which is the value given. 4
1
∴ k = 0.01 M min–1 ∴k = ln 4 = 0. 019 min–1
72
When reaction is 50% complete,
Sol 13: For zero order reaction
ln2
[A] = [A]0 – kt t = t1/2 = = 36 min
k
We are given,
(ii) When reaction is 87. 5% complete, [A] = 0. 125[A]0,
k = 2 × 10–2 mol L–1sec–1
1 1
∴t= ln
and at t = 25 sec, (A) = 0. 25 M k 0.125
[A]0 = [A] + kt t = 108 min
= 0. 25 + 2 × 10–2 × 25 = 0. 75 M
Sol 17: We have, for first order reaction
Sol 14: It is a zero order reaction (∵ unit of rate constant 1 [A]0
k= ln
is M sec–1) t [A]t
6 × 10−6 (i) At t = 10 min, reaction is 20% complete, i. e. [A] = 0.
[H+]0 = = 6 × 10–2 M
0.1 × 10−3 8[A]0
k = 107 mol L–1 sec–1 1 [A]0
k= ln
[H+ ]
10 0.8[A]0
Time taken to disappear =
k k = 0. 0223 min–1
6 × 10 −2
= sec = 6 × 10 sec
–9

107 (ii) When reaction is 75% complete,


1
Sol 15: Since it is a zero order reaction [A] = [A]0
4
[A] = [A]0 – kt
1 [A]0 1 [A]0
1 t= ln = ln
When t = 1 hour, [A] = [A]0 k [A]t 0.0223 1
4 .[A]0
4
(∵ 75% reacted) t = 62. 17 min.
1
∴ [A]0 = [A]0 – k Sol 18: Order will be equal to 1.
4
3 1 [A]0
⇒ k = [A]0 M hr–1 t= ln
4 k [A]t
1 8 . 7 4 | Chemical Kinetics

When reaction is 99. 9 % complete, k = 0. 02 min–1


[A]t = 10–3 [A] 0 k = 3. 3 × 10–4 sec–1.
1 [A]0 3 6.909
t1 = ln = ln10 =
k 10−3 [A] k k Sol 22: If we assume the reaction to be of first order,
0
[A]0 then, let [A]t = α and [A]0 = C0.
When reaction is 50% completed, [A]t =
2 a = C0e–kt
1 [A]0 ln2 0.693
∴t2 = ln = = At time
k 0.5[A]0 k k
t = 0, α = C0
We see that t2 ≈ 10t1
t = t, α = C0e–k = aC0, a = e–k
t = 2t, α = C0e–2k = a2C0, a = e–k
Sol 19: We have, first order reaction
t = 3t, α = C0e–3k = a3C0, a = e–k
N = N0e–kt
Therefore, taking the reaction to be of first order, we
here, k = 1. 5 × 10–3 sec–1
found the concentration of A to be of the form given in
N ∝ 1. 25 (wt. ∝ molar) question. Therefore, the reaction is of first order.
N∝5
−1.5×10−3 t Sol 23: For first order reaction,
∴1. 25 = 5e
1 5 [SO2Cl2] = [SO2Cl2]0 e–kt
⇒t= ln
1.5 × 10−3 1.25 k = 2. 2 × 10–5 sec–1,
t = 924. 3625 t = 90 min = 5400 sec
[SO2Cl2 ] −5400×2.2×10−5
∴ = e = 0. 888
Sol 20: We have, [SO2Cl2 ]0
[N]0 = 500 11. 2 % of [SO2Cl2] decomposed.
At t = 20 months, [N]t = 420,
ln2
Using first order to rate law, Sol 24: For A, k1 = ln2 =
t1/2 5
1 [N]0 Initial concentration = a0
k= ln
t [N]t Let [A]t = a

k = 8. 717 × 10–3 month–1 Then, a = e0 e−k1t


ln2
The drug will be ineffective (will expire) when it has For B, k2 = ln2 =
t1/2 1.5
decomposed 30%, i. e. [N] = 0. 7 [N] 0.
Initial concentration
1 [N]0 1 [N]0
∴ t = log = log [A]0 a0
t [N]t 8.717 × 10−3 0.7[N]0 [B]0 = =
4 4
t ≈ 41 months [B]4 = b
a0 −k 2 t
Sol 21: For first order reaction Then, b = e
4
1 [A]0
k = log When a = b,
t [A]t
a0 −k 2 t
We are given, 2% of virus gets inactivated every minute a0 e−k1t = e
4
at the beginning, i. e. , at t = 1 min, [A]t = 0. 98[A]0
4= e 1 2
(k −k )t

1 [A]0
k = log ln 4
1 0.98[A]0 ⇒t=
k1 − k 2
Chem i str y | 18.75

ln 4 2ln2 2 × 5 × 15 ln2 0.693


= = = ∴k= = = 0. 013 min–1
ln2 ln2  1 1  10 t 53
− ln2  − 
5 15  5 15  (i) We see that both values of k are same, this is first
order reaction.
t = 15 min.
[N2O] −2 ×100
(ii) = e–kt = e−1.3×10 = 0. 27
Sol 25: From the data, we observe that, when [H2] [N2O]0
is halved, keeping [NO] constant, reaction rate gets
Thus 73% of N2O will decompose.
halved. So, order w. r. t H2 is 1.
When [NO] is doubled, keeping [H2] constant, reaction Sol 28: As in previous question, we assume order = 0
rate becomes 4 times so, order w. r. t. NO is 2. and calculate k at different time.
Rate = k[NO]2 [H2] At t = 0 sec, P = P0 = 4 × 103 Pa
(a) Order = 2 + 1 = 3 At t = 100 sec, P = 3. 5 × 103 Pa
(b) When, [NO] = 1. 5 × 10 M, –4
P0 − P (4 − 3.5) × 103
We have, k1 = = Pa/s
[H2] = 4 × 10–3 M, t 100
k1 = 5 Pa/s
Rate = 4. 4 × 10–4 M sec–1
At t = 200 sec, P = 2 × 103 Pa
4.4 × 10−4
∴k = (4 − 3) × 103
(1.5 × 10−4 )2 × (4 × 10−3 )2 k = k2 = = 5 Pa/s
200
When [NO] = 1. 1 × 10–3 M, At t = 300 sec, P = 2. 5 × 103 Pa
[H2] = 1. 5 × 10 M –3
(4.2.5) × 103
k3 = = 5 Pa
(c) Rate = 4. 88 × 106 × (1. 1 × 10–3)2 × (1. 5 × 10–3) 300
Rate = 8. 85 × 10–3 M sec–1 We see that k1 = k2 = k3 = 5 Pa/s is same for all. Hence
this is zero order reaction, rate constant = 5 Pa/s
Sol 26: From given data, we observe that, when [Cl2] is
tripled, rate becomes 3 times, so, order w. r. t. Cl2 is 1. Sol 29: We know, for nth order reaction
1
When [NO] is tripled, rate becomes 9 times, so, order t1/2 ∝
w. r. t [NO] is 2. [A]n0−1

(a) Order w. r. t. NO = 2 We have, at [A]0, (t1/2)1 = t = 50 min


Cl = 1 [A]0
at , ( t1/2 )2 = 25 min
(b) Rate = k[NO] [Cl2]
2
2
n−1
(c) When [Cl2] = 0. 05 M, [NO] = 0. 05 M,   [A]0  
   
Rate = 10–3 50  2   1
∴ =   =
25 [A]0 2 −1
n
rate 10−3  
k= = = 8 M–2 sec–1  
2 2
[NO] [Cl2 ] (0.05) (0.05)
1
(d) If [Cl2] = 0. 2 M, [NO] = 0. 4 M, 2= ⇒ 2n–1 = 2–1
n−1
2
Rate = k[NO] 2 [Cl2] = 8 × (0. 4)2 (0. 2) n – 1 = –1
Rate = 0. 256 mol sec L –1 –1
⇒n=0

Sol 27: Let us assume that this is first order reaction.


i. e. [A] = [A]0e–kt. Using this, we will calculate k at both
times. If they are same, then our assumption is correct.
At t = 53 min, 50% reaction completed, i. e. [A] = 0.
5[A]0
1 8 . 7 6 | Chemical Kinetics

Sol 30: (n0 − x)a + xa + xa (n0 + x)a


Vn = V2 = =
A → B+ C N N
t=0 P0 0 0 NV2
⇒ n0 + x =
t P0 − x x x a
t→∞ 0 P0 P0 NV0 N
x= − n0 =
(V − V1 )
a a 2
We have, at time t = t1
1 n 1 n
k = ln 0 = ln 0
P1 = Pt = P0 – x + x + x t nt t n0 − x
P2 = P0 + x ⇒ x = P2 – P0 1 NV1
= ln
At time, t → ∞, t  NV N 
a  1 −  (V2 − V1 )
Pt = P3 = 2P0  a a
P3 1 V1
⇒ P0 = k= ln
2 t 2V1 − V2
Taking first order reaction,
1 (PA )0 1 P 1 P0 Sol 33: A → 2B + 3C
k= ln = ln 0 = ln
t (PA )t t P0 − x t P0 − P2 + P0 Time, t = 0 a
1 P0 1 P3 Time, t a – x 2x   3x
k= ln = ln
t 2P0 − P2 3 2(P3 − P2 ) Time, t → ∞ 0   2a   3a
Let n-factor of A, B and C be n and normality of reagent
Sol 31: Here, we have, at time t = N then at time, t
P2 N. V2 = (a – x)n + 2xn + 3xn
PB + PC = P2 = 2x ⇒ x =
2
NV2 = n(a + 4x)
at time t → ∞, PB + P0 = P3 = 2P0
NV2
P3 a + 4x =
⇒ P0 = n
2
at time, t → ∞
1 (P ) 1 P3 1 P
k = ln A 0 = ln = ln 3 NV3 = 2a. n + 3a. n
t (PA )t t  P3 P2  t P3 − P2
 −  ⇒ a = NV3 = 5an
2 2
NV3
a=
5n
Sol 32: A → B + C
NV2 NV3
Then 4x = –
time n 5n
t=0 n0 0 0 V3 
N
x=  V2 − 
t n0 – x x x 4n  5 
t→∞ 0 n0 n0
1 a 1 NV3
n0 − a k= ln = ln
At time, t = 0, Vr = V1 = t a−x t  NV NV2 NV3 
N 5n  3 − + 
 5n 4n 20n 
NV1
⇒ n0 = V3 4V3
a 1 1
= ln = ln
(n-factor of A, B, C = a) t 5 t 5(V3 − V2 )
V3 − V + 4V3
4 2
(using NV1 = n0a)
1 4 V3
Normality of reagent = N k= ln
t 5 ( V3 − V2 )
At time, t = t,
Chem i str y | 18.77

Sol 34: S→G+F x


⇒ = 856 – 758
Time t = 0 a 0 0 2
Time, t a–x x x x = 196 mm

Time t → ∞ 0 a a 1 758
k= ln
7.5 758 − 196
Let specific rotation of Glucose and Fructose be q1 and
q2 respectively k = 0. 039 hr–1
Then, at time t x
t = 10 hr, Pt = 889 = P0 +
2
xq1 + xq2 = rt
x = 2(883 – 758)
rt
x= x = 248 mm
θ1 + θ2
1 758
At time, t → ∞ k= ln
10 758 − 248
aq1 + aq2 = r∞
k = 0. 039 hr–1
r∞
a=
θ1 + θ2 Thus, all 3 values of k are approximately the same,
hence first order reaction.
2.303 a 1 a
k= log = log
t a−x t a−x Sol 36 : (CH3)2O(g)→CH4(g)+H2(g)+CO(g)
1 r∞ Time t = 0 P0 0 0 0
k= log
t  r rt 
(θ1 + θ2 )  ∞ −  Time, t P0 – x x x x
 θ1 + θ2 θ1 + θ2  t→∞ 0 P0 P0 P0
1 r∞
k= log
t r∞ − r1 Total pressure, at time t,
Pt = P0 – x + x + x + x = P0 + 2x
3
Sol 35: As H3(g) → As(s) + H2(g) Increase in pressure = (P0 + 2x) – P0 = 2x
2
t = 0P0 We will assume that this is a first order reaction and
3 check the consistency of given data.
t = 1P0 – x x
2
At t = 0, P0 = 312 mm Hg
Since, as a solid, it won’t contribute to pressure.
At t = 390 s, pressure increases;
3 x
∴ At time t, Pt = P0 – x + x = P0 + DP = 96 mm Hg = 2x
2 2
Let’s assume reaction is first order and calculate k at x = 48 mm Hg
1 P
different times, using k = ln 0 1 P 1 312
4 P0 − x ∴k= ln 0 = ln
t P0 − x 390 312 − 48
t = 0 P0 = 758 = Pt
k = 4. 28 × 10–4 s
x
t = 5 hrs , Pt = 827 = P0 +
2 At t = 1195 s, DP = 250 = 2x
x
827 = 758 + x = 125 mm Hg
2
1 312
⇒ x = 138 mm k= ln = 4. 28 × 10–4 s
1195 312 − 125
1 758
k= ln
5 758 − 138 At t = 3155 s, DP = 467 = 2x
x = 233. 5 mm Hg
k = 0. 04 hr–1
1 312
x k= ln = 4. 30 × 10–4 sec–1
t = 7. 5 hr, Pt = 856 = P0 + 3155 312 − 233.5
2
1 8 . 7 8 | Chemical Kinetics

At t → ∞,DP = 2P0 = 624 mm Hg Now, since, this is first order reaction.

≈ 619 mm Hg 2.303 (P ) 2.303 90


k= log A 0 = log
Thus, we see that all 3 values of k are approximately the t (PA )+ 10 47
same. Therefore, this is a first order reaction.
k = 6. 49 × 10–2 min–1
So, rate = k[(CH3)2O], k
1 13.1 − ( −3.8)
= 4. 28 × 10–4 sec–1 k1 = 2.303log .
60 11.6 − ( −3.8)
1 = 1. 55 × 10–3 min–1
Sol 37: H2O2(g) → H2O() + O (g)
2 2
At time, t = 120 min, qt = + 10. 2º
Here, Vr ∝ [H2O2]
Assuming this is a first order reaction 2.303 (13.1) − ( −3.8)
k2 = log = 1. 57 × 10–3 min–1
120 (10.2) − ( −3.8)
2.303 [H O ] 1 V
k= log 2 2 0 = log 0
t [H2O2 ]t t Vt At time, t = 180 min, qt = +9. 0º
At time, t = 0, Vr 22. 8 cc = V0
2.303 (13.1) − ( −3.8)
k3 = log = 1. 54 × 10–3 min–1
t = 10,Vr = 13. 3 cc = Vt 180 (9.0) − ( −3.8)
2.303 22.8 At time, t = 360 min, qt = +5. 87º
k1 = log = 5. 4 × 10–2 min–1
10 13.3
2.303 (13.1) − ( −3.8)
t = 20,Vr = 8. 25 cc = Vt k4 = log = 1. 55 × 10–3 min–1
360 (5.87) − ( −3.8)
2.303 22.8
k2 = log = 5. 1 × 10–2 min–1 We see that, k1, k2, k3 and k4 are all same within
20 8.25
experiment value.
k1 and k2 are equal within experimental error.
Therefore, this is a first order reaction
Therefore, first order reaction.
0.693 0.693
Half-life = = = 10. 677 min
k 6.49 × 10−2
Sol 38: For inversion of cane sugar, assuming first order,
(i) (PA)I = 90 mm Hg
1 θ − θ∞
k= log 0 (ii) (PA)f = 47 mm Hg
t θf − θ∞
(iii) k = 6. 49 × 10–2 min–1
At time, t = 0, θ = q0 = + 13. 1
(iv) t1/2 = 10. 67 min
At time, t → ∞,θ = θ∞ = –3. 8
At time, t = 60, θ+ = 11. 6º Sol 40: 2N2O5(g)→4NO2(g)+O2(g)
time, t = 0 P0 0 0
Sol 39: A(g) → 2B(g) + C(g)
time, t = t P0 – 2x 4x x
Time, t = 0 P0 0 0
t→∞ 0 2 P0 P0
Time, t P0 – x 2x x
2
Time, t→∞ 0 2P0 P0 P0
At t → ∞, Pt = 584. 5 = 2P0 +
At, t → ∞,Pt = 3P0 = 270 mm Hg 2
5P0
P0 = 90 mm Hg = (PA) ⇒ = 584. 5
2
At, t = 10 min, Pt = P0 – x + 2x + x = P0 + 2x = 176
⇒ P0 = 233. 8 mm Hg
2x = 176 – 90
At t = 30 min,
x = 43 mm Hg
Pt = 284. 5 = P0 – 2x + 4x + x
(PA)+ = P0 – x = 90 – 43 = 47 mm Hg
⇒ P0 + 3x = 284. 5
Chem i str y | 18.79

3x = 284. 5 – 233. 8 Fraction decomposed


x = 16. 9 mm Hg Vt −25 × 5.05 × 10−2
= 1. 10 = 1 – 0. 284
PN = P0 – 2x V0 2.303
2O5

= 233. 8 – 2 × 16. 9 = 200 mm Hg Fraction decomposed = 0. 716


We have,
1
Sol 42: H2O2 → H2O + O
−1 d[N2O5 ] 2 2
= k[N2O5]
2 dt We are given complete dissociation gives 46. 34 mL O2.
[N2O5 ]t t Also VO ∝ [H2O2]
d[N2O5 ] 2
∫ = −2k ∫ dt
[N2O5 ]0 ( VO is volume of O2 a given sample of H2O2 can give)
[N2O5 ]0 0 2
∴ [H2O2] 0 ∝ 46. 34
[N2O5 ]t
ln = –2kt Also, at t = 5.1 days, VO = 10. 31 mL
[N2O5 ]0 2

Then [H2O2] t ∝ (46. 34 –10. 31)


2.303 [N O ]
k= log 2 5 0
2t [N2O5 ]t 2.303 [H O ]
So, k = log 2 2 0
t [H2O2 ]t
2.303 (PN O )0
k= log 2 5 (∵ PN O ∝ [N2O5]) 2.303 46.34
2t (PN O )t 2 5
k= log
2 5
5.1 46.34 − 10.31
2.303 233.8
= log k = 4. 93 × 10–2 days–1.
2 × 30 200
When 20 mL, O2 lost,
k = 2. 605 × 10–3 min–1.
[H2O2] t ∝ (46. 34 –20. 00)

Sol 41: (a) Assuming first order reaction 2.303 [H2O2 ]0


t= log
V k [H2O2 ]0 − [H2O2 ]t
2.303
k= log 0
t Vt
2.303 46.34
= log
We have,V0 = 22. 8 cc 4.93 × 10 −2 46.34 − 20
At t = 10 min, Vt = 13. 8 cc t = 11. 45 days

2.303 22.8
k1 = log = 5. 02 × 10–2 min–1 Sol 43: A(aq) → B(aq) + C(aq)
10 13.8
t = 0   n0
At t = 20 min, Vt = 8. 25 cc
t = t   n0 – x   x    x
2.303 22.8 t →∞ 0   n0     n0
k2 = log = 2 × 10–2 min–1
20 8.25
At t → ∞,θ∞ = –5º = n0. θB + n0θC
Since, k1 ≈ k2. This is first order reaction.
We have, θA = 20º, θB = 30º,
0.693 0.693
(b) t1/2 = = = 13. 75 min θC = –40º
k 5.05 × 10−2
∴ 30n0 – 40n0 = –5
(c) At t = 25 min,
n0 = 0. 5
2.303 V At time, t = 6. 43 min.
k= log 0
25 Vt
qt = (n0 – x)θA + x(θB + θC) = 2. 5
1 8 . 8 0 | Chemical Kinetics

20n0 + x(30. 40 – 20) = 2. 5 k1 [x]0 k 2 [x]0


= (1 − e−kt ) + (1 − e−kt )
30x = 20 × 0. 5 – 2. 5 k k

30x = 7. 5  k + k2  (1 −e−kt )
 [x]0 (1 − e ) = [x] 0 e
−kt
=  1
x = 0. 25  k 
For first order conversion, [x]t e−kt 1
∴ = =
2.303 n [y] + [2] 1−e −kt
e
+ (k1 +k 2 )t
−1
k= log 0
t n0 − x
Sol 45: Using results of previous question
2.303 0.5
= log
6.93 0.5 − 0.25 k 2 [A]0
[C]t = (1 − e−kt ) , k = k1 + k2
k = 0. 1 min–1
k

[A]t = [A]0e–kt
Sol 44:
[C]t k2 (1 − e−kt ) 1
= = (e−kt − 1)
k1 B [A]t k1 + k 2 e −kt k1
1+
x k2
k2 C We have, k1 = x hr–1, k2 = 10 k1
= 10 × hr–1, t = 1 hr
(B = y, C = z)
[C]t 1
We have, ∴ = (e(x +10x) − 1)
[A]t 1
1+
d[x] 10
= –(k1 + k2)[x] [C]t
dt 10 11x
= (e – 1)
[A]t 11
[x]t t
d[x]
∫ = −(k1 + k 2 )∫ dt
[x]0
[x] 0 Sol 46: We have,
k k
⇒[x] t = [x]0e–kt, k = k1 + k2 A → B 
1 2→ C,

d[B] ln2 ln2


Now, = k1[x] t k1 = ,k =
dt ln1 2 2
d[B] For [A]
= k1[x]0e–kt
dt d[A]
[B]t t
= –k1[A]
−kt
dt
∫ d[B] = k1[x] 0 ∫e
0 0 ⇒ [A] = [A] 0 e−k1t

−k1 [x]0 t
d[B]
[B]t = e−kt = k1[A] – k2[B]
k 0 dt
d[B]
−k1 [x]0 = k1[A] 0 e−k1t – k2[B]
[B] t = (1 − e −kt
) dt
k1 + k 2
d[B]
+ k2[B] – k1[A]0 e−k1t = 0…(i)
dt
k 2 [x]0
Similarly [C] t = (1 − e−kt ) This is a linear differential equation.
k1 + k 2

[B]t + [C]t = [y] + [x] Solving this, we get


Chem i str y | 18.81

k1 [A]0 −k1t −k 2t  (Ea )2  1 1 


[B] t = [e −e ] k2 = 2 antilog   − 
k 2 − k1
 2.303R  300 T  
d[B]t k1
Now, at [B] max, =0 =2
dt k2
d[B]t
In (i), putting = 0, we get  ((Ea )1 − (Ea )2 )   1 1
dt 4antilog   −  =2
 2.303R   300 T 
k1[A]0 e−k1t = k2[B]
(Ea )1 .(Ea )2  1 1 1
 −  = log
k 2k1 [A]0 −k1t −k 2t 2.303R  300 T  2
k1[A]0 e−k1t = [e −e ]
k 2 − k1 (Ea )1 = 20 kJ/mol,

−k1t −k1t −k1t −k 2t


k 2e .k1e = k 2e .k 2e (Ea )2 = 2. 8314 kJ/mol
3
k1 ⇒ (28.314 − 20) × 10  1 − 1  =0. 7
= (k −k )t
e 1 2 8.314  300 T
k2
1 1
 logk1 − logk 2  − = 7 × 10–4
t =  300 T
 .2.303
 k1 − k 2  1
= 2. 63 × 10–3
1 ln2 −4 1 T
t= ln = ln = 4
k1 − k 2 4.ln2 ln2 2 T = 379. 75 K

∴ t = 4 min.
Sol 48: H2O + O → 2OH–, Ea
1

k1 2OH– → H2O + O, Ea
B 2
Sol 47: A
Potential energy →

k2 C
E a2
[B] k1
= Ea1
[C] k2 2OH

[B] k1
We need, =2= H2O+O
[C] k2
Reaction coordinate →
Let temperature be T.
By Arrhenius equation.
Ea = Ea – ∆H = (77. 72) kJ mol–1
2 1
Ea = 5 kJ mol–1
k2 Ea 1 1 2
log =  − 
k1 2.303R  T1 T2 
Sol 49: For t1/2 = 1 min, k = 0.693
t1/2
For A 
k1
→ B, k2 = k1, k1 = 8,
 = 0. 693 min = 1. 155 × 10 s –1 –2

−1
Ea = 20 kJ/mol (E1), T1 = 300, T2 = T Ea  A 
−Ea

Now, k = A e RT
⇒T=  ln 
R k
k1 (Ea )1  1 1
log =  −  A = 5 × 1013 sec–1
8 2.303R  300 T 
Ea = 104. 5 kJmol–1
 (Ea )1  1 1  −1
k1 = 8 antilog   −  3 
T = 104.5 × 10  ln 5 × 1013 
 2.303R  300 T  

8.134  1.155 × 10 −2 
 
For A 
k2
→ C, similarly,
 T = 349. 1 K
1 8 . 8 2 | Chemical Kinetics

Sol 50: From Arrhenius equation k 308 k


Sol 53: Temperature coefficient = = 1. 75
k2 Ea
1 1 k 298 k
log =  − 
k1 2.303R  T1 T2  By Arrhenius equation

For T1 = 27ºC = 300 K and k 308 k Ea


 1 1 
log =  − 
k2 k 298 k 2.303k  298 308 
T2 = 47ºC = 320 K, =4
k1
log1.75 × 2.303 × 8.314 × 298 × 308
Ea  1 1  Ea =
∴ log 4 =  −  10
2.303 × 8.314  300 320 
= 42. 711 kJ mol–1
log 4 × 2.303 × 8.314 × 300 × 320
Ea = Ea = 10. 757 kJ mol–1
20
Ea = 55. 33 kJ/mol
Sol 54: At T1 = 380ºC = 653 K,

0.693 –1 0.693
Sol 51: For t1/2 = 2 hr, k = 0.693 = hr k1 = 0.693 = = 1. 925 × 10–3 min–1
t1/2 2 t1/2 360
= 9. 625 × 10–5 sec–1
T2 = 450º C = 723 K, k2 = k
So, we have, k1 = 3. 46 × 10–5 sec–1
Ea = 200 k J mol–1
k2 = 9. 625 × 10 sec –5 –1
By Arrhenius equation
Ea = 100 kJ mol–1
k2 Ea 1 1
T1 = 25ºC = 298 K log =  − 
k1 2.303R  T1 T2 
T2 = T
k 200 × 103  1 1 
By Arrhenius equation. log =  − 
−3 2.303 × 8.314  653 723 
1.925 × 10
k2 Ea
1 1
log =  −  k
k1 2.303R  T1 T2  log = 1. 548
1.925 × 10 −3
9.625 × 10 −5 100 × 103  1 1 k = 6. 81 × 10–2 min–1
log =  − 
−5 2.303 × 8.314  298 T 
3.46 × 10 2 × 0.693
Time required for 75 % reaction = 2t1/2 =
1 1 6.8 × 10−2
⇒ − = 8. 5 × 10–5 Time = 20. 4 minutes
298 T
T = 306 K Sol 55: We have,

Sol 52: By Arrhenius equation k1


(i) NO + Br2 NOBr2
k = A e−Ea /RT k2
k3
k2 (Ea −Ea )/RT (ii) NOBr2 + NO  
→ 2NOBr
= e 1 2
k1
This is RDS
We have,
Here, we use equilibrium approach, as equilibrium is
Ea = 75 kJ mol–1 achieved fast
1
Ea = 25 kJ mol–1 Rate = k3[NOBr2] [NO]
2
T = 25ºC = 298 K For equilibrium of (i),
k2
∴ = 5. 8 × 108 k1 [NOBr2 ]
k1 =
k2 [NO][Br2 ]
Therefore, rate of reaction increases by 5. 8 × 108 times.
Chem i str y | 18.83

k1 equilibrium constant = k1, fast


[NOBr2] = [NO] [Br]
k2 (ii) 2I + H2 
k2
→ 2HI, RDS

k1k 3 [I]2
Hence, rate = [NO] [Br] = k[NO] [Br2]
2 2 from (i) equilibrium, k1 =
k2 [I2 ]
k1k 3 [I] 2 = k1[I2]
k=
k2 from (ii)Rate = k2[I] 2[H2]
= k2k1[I2] [H2]
Sol 56: (i) 2NO → N2O2
= k[H2] [I2] , k=k2k1
equilibrium constant = k1 (fast)
(c) (i) I2 → 2I
(ii) N2O2 + H2 
k2
→ N2O + H2O

equilibrium constant = k1, fast
RDS
k3 (ii) I + H2 → HI2
(iii) N2O + H2  → N2 + H2O
 k
3
→ 2HI, RDS
(iii) IH2 + I
As equilibrium step is fast, we use equilibrium approach
equilibrium constant = k2, fast
[N2O2 ]
from (i), k1 = [I]2
[NO] 2 from equilibrium (i), k1 =
[I2 ]
[N2O2] = k1[NO] 2 [I] 2 = k1[I2]
Also, from (ii), Rate = k2[N2O2] [H2] from equilibrium (ii),
= k1k2[NO] [H2] 2
[IH2 ]
k2 = [HI] 2
= k[NO] [H2] 2
[I][H2 ]
k = k 2k 3 [IH2] = k2[I] [H2]

1  k since (iii) is RDS,



Sol 57 (i) NO + NO  N2O2 [fast] k −1
Rate = k3[IH2] [I]
(ii) N2O2 + O2 
→ 2NO2 (RDS)
k2
= k3k2[I] 2[H2]
from equilibrium of (i),
= k1k2k3[I2] [H2]
k1 [N2O2 ]
= Rate = k[H2] [I2]
k −1 [NO]2
(d) No, it cannot distinguish between the three mechanisms
k1 as all the 3 molecules gives the same rate law.
[N2O2] = [NO] 2
k −1
(e) Mechanism (a) becomes most improbable as it just
from (ii) involves one step and it is highly unlikely that I2 and H2 will
combine directly at 200ºC without breaking into radicals.
1 d[NO2 ] k 2k1
Rate = = k2[O2] [N2O2] = [NO] 2[O2]
2 dt k −1

1 d[NO2 ]
Exercise 2
Rate = = k[NO]2[O2] ,
2 dt Single Correct Choice Type
k 2k1
k= Sol 1: (B) We know,
k −1 1
Coefficient in rate law =
stiochiometric coefficient
Sol 58: (a) H2 + I2 → 2HI Given rate law
since, this is one step, rate = k[H2] [I2] 1 d[C] −1 d[D] +1 d[A] d[B]
+ = = = −
2 dt 3 dt 3 dt dt
(b) (i) I2 → 2I
Reaction is 3D + B → 2C + 4A
1 8 . 8 4 | Chemical Kinetics

Sol 2: (D) If volume is reduced to half, pressure will get −kt


doubled. log(a0–x) = + log a0
2.303
Now, reaction is first order w. r. t O2 and second order −kt
Slope of log (a0 – x) vs. t graph is
w. r. t N2 2.303
−k
\ Rate = k[O2] [N2] 2 Slope of given graph = –3. 3 × 10–3=
2.303
rf = k[2O2] [2N2] 2 ⇒ k = 7. 7 × 10–3
rf = k[2O2] [2N2] 2 = 8ri
Sol 8: (C) Volume strength = 5. 6 N0 = 16. 8º
Sol 3: (C) We have Now, after 2. 303 hours, let normality be N.
When 20 mL of this solution is diluted, Normality
becomes
Ef N.20 N
Energy →

Eb =
∆Η 100 5
It is diluted against 0. 02 M KMnO4.
Reaction coordinate→ Under acidic conditions, normality of KMnO4 = M × 5
∴ |∆H| = Eb – Ef = (200 – 180) kJ mol–1 = 0. 02 × 5 = 0. 1 N

|∆H| = 20 kJ/mol Now, using N1V1 = N2V2


N
. 25 = 0. 1 × 37. 5
5
Sol 4: (D) For zero order reaction
N = 0. 75 N
d[B]
rate, =k Now volume strength
dt
[B] = kt V = N × 5. 6 = 0. 75 × 5. 6 = 4. 2 V
Now,
[A] = [A]0 – kt
2.303 V
1 k= log 0
At time t = t3/4, [A] = [A0] t Vt
4
t = 2. 303 hours, V0 = 16. 8 V,
3[A]0
⇒t =
4k Vf = 4. 2 V

⇒t3/4 ∝ [A0] 2.303 16.8


k= log
2.303 4.2
Similarly, t1/2 ∝ [A0]
k = 0. 60 hr–1

Sol 5: (C) Here, t1/2 ∝ (A)0, therefore, it is a zero order


Sol 9: (A) For experiment 1,
reaction.
 d[A]  1.5M
So, rate of reaction   will be independent of time.
Conc.(M)→

 dt 

Sol 6: (B) The given option is correct as there is very 0.95M


little probability for more than 3 atoms to collide
simultaneously. 10min
Time(min)→
2.303 a
Sol 7: (C) We have k = log 0
t a0 − x −∆[A] 0.55
Average rate = = = 0. 055 min–1
∆t 10
kt = 2. 303 log a0 – 2. 30 log(a0–x)
For experiment 2,
Chem i str y | 18.85

Conc.(M)→ Sol 12: (B)

EP
1.5M
P

Energy →
0.8M
S+E
ES
5
Time(min)→
Reaction coordinate→
∆A
Average rate, r2 =
∆t This is the plot for enzyme catalysed reaction.
0.2 1 Correct option is (B).
= M min–1 = M min–1
5 25 Multiple correct choice type
r 0.55 [A]0
⇒ 1 = = 1. 375 ≈ 1. 5 = 1
r2 1 / 25 [A]0 Sol 13: (A, D) We have, emission rate of SO3
2
Hence the reaction is first order
= 6. 93 × 10–6 gm/L/day
When (A) = 1. 8 M
6.93 × 10−6
Rate, r = 1. 8 × [x]2 = mol/L/day
80
1.8
= M min–1 = 0. 072 M min–1 = 8. 6625 × 10–8 mol/L/day
25
≈ 0. 08 M min–1 For decomposition of SO3,

0.693 0.693
k= = = 6. 93 × 10–3 day–1
Sol 10: (A) Since k1 << k2 second reaction will have the t1/2 100
most activation energy
d[SO3 ]
Further, since the overall reaction is exothermic, = 8. 6625 × 10–8 – 693×10–3[SO3]
dt
therefore the final energy of products should be less
d[SO3 ]
than the reactants plot which satisfies above 2 is (A). At steady state, =0
dt
k1 8.6625 × 10−8
Sol 11: (A) NO(g) + Br2(g) NOBr2(g) ⇒ [SO3] =
k2 6.93 × 10−3
NOBr2(g) + NO(g) → 2NOBr(g)
3 k [SO3] = 1. 25 × 10–5 M

We use equilibrium approach In 10–3 of air, moles of SO3 = 1. 25 × 10–5×103

Since second step is RDS, = 1. 25×10–2 mol


When dissolved in water (1 L),
Rate, R = –k3[NOBr2] [NO]
[SO3] = 1. 25 × 10–2 M
From equilibrium of (i),
Normality of SO3 = 2M = 2. 5 × 10–2 N
k1 [NOBr2 ]
= N1V1 = N2V2
k2 [NO][Br2 ]
2. 5 × 10–2 × 1000 = 1 × V2
k1
⇒ [NOBr2] = [NO] [Br2] V2 = 25 mL
k2
k 3k1 SO3 + H2O → H2SO2
Therefore, rate = [NO]2 [Br2 ]
k2 Rate of H2SO4 production
Order w. r. t. NO = 2 980 × 103
= 980 kg/day = mol/day = 104 mol/day
98
SO3 required = H2SO4 manufactured = 104 mol/day
1 8 . 8 6 | Chemical Kinetics

number of moles  [A]1/2 


Now V = 2  [A]1/2 − 0 
M  0
2 
 
10 4 k
= = 8 × 108 L/day
1.25 × 10−5
[A]0
If SO3 emission stopped, t3/4 =
k
d[SO]3
= –6. 93 × 10–3[SO3]
dt Sol 15: (A, D) Solution will be optically active and
−6.93×10−3 t dextro after very long time
⇒ [SO3] = [SO3]0 e

[SO3] 0 = [SO3]0 e−6.93×10


−3 t After 75% conversion of A in to B and C angle of rotation
of solution will be 36°
[SO3] 0 = 1. 25 × 10–5 M

t = 1000 days Sol 16: (C, D)


(A) is correct
\[SO3]0 ≈ 1. 2 × 10–8 M
Rate, R = k[A] m[B] n[C]0
−d[A] log R = log k + m log[A] + n log[B]
Sol 14: (A, B, D) = k(A) 1/2
dt If all concentration other than (A) are constant,
[A] t
−d[A] d(logk)
∫ = ∫ k dt Then =m
1/2
[A]0 [A] 0 d(log[A])
[A] t (C) Order of reaction can be fractional
2[A]1/2 = kt
[A]0 0
(D) Order of a reaction can only be determined
kt experimentally
(A) 1/2 = [A]1/2
0 =
2
−1 1/2 1/2) Sol 17: (A, C, D)
k= (A .A
2 0 (A) Unit of A = Unit of k ≠ mol L–1s–1
kt
A = + A0 (B) Order of an elementary must atleast be 1 (atleast 1
2 molecule should be present)
Straight line (C) Molecularity can be defined for any elementary
[A]0 reaction.
At t = t1/2, (A) =
2 (D) Decay constant (λ) of radioactive substance is
independent of temperature.
2 2k
t1/2 =
[A0 ]1/2 Sol 18: (A, C) With increase in [A]0, rate will increase,
[A0 ]1/2 − 0
2 leading to increase in yield of B. A → B has higher Ea,
1/2 which means it has lower k and thus with increase in
 [A]  temperature k1 will increase more than k2, resulting in
2  [A0 ]1/2 1/2
0 2([2A]0 − 
 2 increase in yield of B.
k

2 2k 2[A]1/2 Sol 19: (A, B, C)


= = 0
( 2 − 1)
( 2 − 1)[A]0 k (D) A zero order reaction is always complex, rest all are
correct.
[A]0
At t = t3/4, (A) =
4
2k
\t3/4 =
[A]1/2
[A]1/2
0 −
0
2
Chem i str y | 18.87

Assertion Reasoning Type Sol 22: (A)

Sol 20: (C) Order of an elementary reaction cannot be k1 B


fractional, through the overall order of a reaction can x
be fractional.
k2 C
k1 2B
A (B = y, C = z)

k2 2C We have,
[B] k 1 d[x]
We have, = 1 = = –(k1 + k2)[x]
[C] k2 2 dt
1 [x]t t
For every mole of A consumed, mole used for forming d[x]
3 ∫ = −(k1 + k 2 )∫ dt
B and rest for forming C. [x]
[x]0 0
[A]0 = 2 moles
⇒[x]t = [x]0e–kt, k = k1 + k2
At end of 50% reaction, A0 = 1 mole
1 2 d[B]
Bn = ×2×1 = moles Now, = k1[x]t
3 3 dt
2 4 d[B]
Cn = ×2×1 = moles = k1[x]0e–kt
3 3 dt
[B]t
[Since, for every mole A, 2 moles of B (or C) is produced] t
−kt
∫ d[B] = k1[x]0 ∫e
0 0
Sol 21: (D) A(aq) → B(aq) + C(aq)
−k1 [x]0 t
t=0 n0 [B]t = e−kt
k 0
t = t n0 – x x x
−k1 [x]0
t →∞ 0 n0 n0 [B]t = (1 − e−kt )
k1 + k 2
At t → ∞,θ∞ = –5º = n0.θB + n0θC
k 2 [x]0
Similarly [C]t = (1 − e−kt )
We have, θA = 20º, θB = 30º, k1 + k 2

θC = –40º [B]t + [C]t = [y] + [x]

\ 30n0 – 40n0 = –5 k1 [x]0 k 2 [x]0


= (1 − e−kt ) + (1 − e−kt )
n0 = 0.5 k k
 k + k2  (1 −e−kt )
At time, t = 6.43 min. =  1 −kt
 [x]0 (1 − e ) = [x]0 e
 k 
θt = (n0 – x)θA + x(θB + θC) = 2.5
[x]t e−kt 1
20n0 + x(30.40 – 20) = 2.5 ∴ = =
[y] + [2] 1−e −kt
e
+ (k1 +k 2 )t
−1
30x = 20 × 0.5 – 2.5
Sol 23: (C) Using results of previous question
30x = 7.5

x = 0.25 k 2 [A]0
[C]t = (1 − e−kt ) , k = k1 + k2
k
For first order conversion,
[A]t = [A]0e–kt
2.303 n 2.303 0.5
k= log 0 = log
t n0 − x 6.93 0.5 − 0.25 [C]t k2 (1 − e−kt ) 1
= = (e−kt − 1)
[A]t k1 + k 2 e −kt k1
k = 0.1 min–1 1+
k2
1 8 . 8 8 | Chemical Kinetics

We have, k1 = x hr–1, k2 = 10 k1 Paragraph 2

= 10 × hr–1, t = 1 hr Sol 28: (B) We have,


[C]t 1 n1A(g) → n2B(g)
∴ (e(x +10x) − 1)
=
[A]t 1
1+ time 0 a 0
10
[C]t 10 11x time t a – n1x n2x
= (e – 1)
[A]t 11
−1 d[A]
\Rate = k[A] = = k[A]
n1 dt
Sol 24: (C) For reactions with order ≤ 1, time of at t
completion can be determined as those reactions gets d[A]
⇒ ∫ = −n1k ∫ dt
fully completed in specific amount of time. a
dt 0

For reactions with order > 1, reaction never goes to 100 at


n = –n1kt
% completion and hence time of completion cannot be a
determined. −n1kt
at = a e

Sol 25: (A)


Sol 29: (D) n1A(g) → n2B(g)
Without catalyst t = 0 a 0
−n1kt n2 −n1kt
t=1 ae a(1 − e )
n1
Ea Total moles present
Energy

R
 −n kt n n −n kt 
= a e 1 + 2 − 2 e 1 
P
 n1 n1 

Reaction coordinate n n  −n kt 
= a  2 −  2 − 1  e 1 
n 
 1  n1  
With catalyst
Concentration is to remain same at time t,

total moles present(n) a


∴ = 0
V V0
Ea
n  n  −n kt 
Energy

R V0 n
⇒V = = V0  2 −  2 − 1  e 1 
a0  n1  n1
P
 

Reaction coordinate Sol 30: (B) If n1 = 1, n2 = 2


at time t,

Comprehension Type nA = ae–kt

Paragraph 1 V = V0(2 – (2 – 1)e–kt)

= V0(2 – e–kt)
2 4
Sol 26: (B) Total number of moles = 1+ + = 3 moles  e−kt 
3 3 nA ae−kt
(A) = = = (A)  
2 V V0 (2 − e−kt )
0  2 − e−kt 
Sol 27: (C) Moles of B = = 0. 666 moles.  
3
Chem i str y | 18.89

Paragraph 3 Sol 33: (B) Slope of ln(1 – f) vs f graph


k1 [A]0 −3 –1
Sol 31: (C) (B) = [e
−k1t
−e
−k 2t
] = –k = hr
k 2 − k1 200
3
d[B] k [A] −k t −k t ⇒k = hr–1
= 1 0 ( −k1e 1 + k 2e 2 ) 200
dt k 2 − k1
1
d[B] When f =
When (B) is maximum, =0 2
dt 1
d[B] = 1 – e–kt
=0 2
dt n2 0.693 × 200
−k1t −k 2t
t= = = 46. 2 hrs.
⇒ −k1e + k 2e =0 k 3

−k1t −k 2t
k1 e = k 2e Sol 34: (A) f = 1 – e–kt

k1 f = [1 – e–3t/200]
=
k2
k1 1 k Paragraph 5
(k1 – k2)t = ln ; ⇒t = ln 1
k2 k1 − k 2 k 2 3
Sol 35: (C) For t = 100 min, x = a
4
Sol 32: (C) For k1 = 1000 s–1, k2 = 20 s–1, 1 a n2
\k = ln = min–1
100 3 50
[A]t = [A]0 e–1000t a− a
4
1000 When x = 0. 9 a,
[B]t = [A] [e−1000t − e−20t ]
20 − 1000 0 1 a
k= ln
1 1000 t a − 0.9a
≈ [A]0e–20t, tmax = n
1000 − 20 20
1 50ln10 50 50
t= ln10 = = = ; = 166. 66 min
[B]t will increase till tmax and then decay exponentially k ln2 ln2 0.3

[C]t = [A]0 – ([A]t + [B]t) 2


Sol 36: (B) [A]0 = = 0. 16
= [A]0 – [A0] e–1000t – [A]0e–20t 12.5
We have,
= [A]0(1 – e –1000t
–e –20t
) 1 d[B]
= k[A]
≈ [A]0(1 – e )
–20t 3 dt
A(g) → 3B(g) + 2C(g)
[C]t will approach [A]0 asymptotically.
At time 0 0. 16
At time t 0. 16–x 3x 2x
Paragraph 4
d[A]
df Also, = –k[A]
We have = k(1 – f) dt
dt
[A] = [A]0 e–kt
f f
df −2 ×100
∫1−f = ∫ k dt = 0. 16 e1.386×10
0 0
= 0. 04
f
−ln(1 − f)0f = k f
0 i. e. , 0. 16 – x = 0. 04
–ln(1 – f) = kt x = 0. 12
f = 1 – e–kt (B) = 3x = 0. 36.
1 8 . 9 0 | Chemical Kinetics

Match the Columns We know,

Sol 37: (A) → s 1


t1/2 ∝
[A0 ]n−1
We have,
decreasing graph
1 d[B] −d[A]
=
2 dt dt Matches (C).

Straight line with slope equal to 2. 1


(U) vs t(order = 2)
[A]
(B) → r
we have,
[A] = [A]0e–kt
−d[A] −k
exponential decay =
dt [A]2
(C) → p
[A] t
d[A]
(B) = 2([A]0 – [A]); = 2[A]0 (1 – e–kt) ⇒ ∫ = −k ∫ dt
[A]0 [A]2 0
Exponential graph will approach 2(A)0 asymptotically.
[A]
(D) → q −1 t
⇒ = −k t
[A]0 0
For zero order, [A0 ]

[A] = [A]0 – kt 1 1
⇒ − = –kt
Straight line with slope –k. [A]0 [A]

1 1
Sol 38: We will draw all graphs given in Column-II and ⇒ = kt +
[A] [A]0
then match them with Column-I.
Straight line with positive slope and positive intercept.
(p) ln (A) vs t (order 1)
Matches no option in Column-I.
We have, [A] = [A]0e–kt
(V)r vs [A] (order = 1)
ln[A] = ln[A]0 – kt
r = k[A]
Straight line with negative slope matches (A). Straight line with positive slope.
(q) t1/2 vs (A)0 (order = 1) Matches (D)
0.693 (A) → p
t1/2 =
k (B) → q, s
It is independent of [A]0, straight line parallel to x-axis. (C) → r, t
Matches (B)
(D) → v
(r) r vs t (order > 0)

r = k[A]n, n > 0
Previous Years’ Questions
for order > D, rate decreases with increasing t as (A)
decreases with t Sol 1: (A) The rate constant (k) of all chemical reactions
\decreasing graph (not straight line) matches (C). depends on temperature.

(s) r vs t (order = 0) k = Ae–Ea /RT


where, A = Pre-exponential factor,
For order, r is constant of time, graph is straight line
parallel to x-axis. Ea = Activation energy.

(t) t1/2 vs [A]0 (order > 1)


Sol 2: (C) A catalyst increases the rate of reaction but
by the same factor to both forward and backward
Chem i str y | 18.91

directions. Hence, a catalyst shorten the time required Sol 11: k = 1.5 × 10–6 s–1
to reach the equilibrium.
100
kt = ln
100 – x
Sol 3: (D) Rate will be directly proportional to both
concentration and intensity, i.e, rate of formation of AB 100
⇒ ln
* ∝ C. I. 100 – x
= 1.5 × 10–6 s–1 ×10 × 60 × 60s; = 0.0054
Sol 4: (D) Order of a reaction can take any real value, 100
⇒ = 1.055
i.e, negative, integer, fraction, etc. 100 – x
⇒ x =5.25% reactant is converted into product
Sol 5: (A) According to Arrhenius equation, rate
ln2 0.693
constant increases exponentially with temperature : Half-life = = = 462000 s; = 128.33 h
k = Ae–Ea /RT k 1.5 × 10 −6

Sol 12: The minimum rate of decay required after 6.909


Sol 6: (A) Living plants maintain an equilibrium
h is 346 particles min–1.
between the absorption of C14 (produced due to cosmic
radiation) and the rate of decay of C14 present inside ⇒ Rate = kN
the plant. This gives a constant amount of C14 per gram Rate 346 × 66.6 × 60
of carbon in a living plant. ⇒N= =
k 0.693
= 1.995 × 106 atoms
Sol 7: (B) Fossil whose age is closest to half-life of C–14
(5770 yr) will yield the most accurate age by C–14 dating. N0
⇒ kt = ln
N
N0 ln2 N
Sol 8: (A) λT =ln ⇒ × 6.909 = ln 0 = 0.0715
N 66.6 N
where N0 = Number of C14 in the living matter and
N = Number of C14 in fossil. Due to nuclear explosion, N0
⇒ = 1.074
amount of C14 in the near