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CHEMISTRY
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Exhaustive Theory
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Electrochemistry
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17. ELECTROCHEMISTRY
1. INTRODUCTION
Electrochemistry is a branch of chemistry which deals with interconversion 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 conductorsElectronic/Metallic and Electrolytic/Solution.
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 deelectronation (oxidation) of ions is known as electrolysis.
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 gion 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 gion = 6.02 × 1023 ions
Thus, charge on one gion 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, oxidationreduction occurs simultaneously. Oxidation occurs at anode whereas
reduction occurs at cathode.
Nikhil Khandelwal (JEE 2009 AIR 94)
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 halfreaction 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 halfreactions. According to the equations, three moles of electrons
produce one mole of iron and 2 moles of electrons produce 1 mole of chlorine gas.
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 halfreaction 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
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 halfreaction that takes place.
Hydrogen is produced during the reduction of water at the cathode. The equation for this halfreaction is:
(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
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)
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
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
(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 ’
(d) Ions present in solution constantly reunite to form neutral molecules and, thus, there is a state of dynamic
equilibrium between the ionized and nonionized 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.
(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.
Where, V is the volume in mL containing 1 gmole of the electrolyte. If c is the concentration of the solution in
1000
gmole 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)
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
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).
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)
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
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 )
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 ;
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−
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
Salt Bridge: A Salt bridge is usually an inverted Utube 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 halfcells.
Significance of salt bridge: The following are the functions of the salt bridge:
(i) It connects the solutions of two halfcells and completes the cell circuit.
(ii) It prevents transference or diffusion of the solutions from one halfcell to the other.
(iii) It keeps the solutions in two halfcells electrically neutral.
(iv) It prevents liquidliquid junctionpotential, 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.
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
H2(g)
(at 1 atm)
H3 O+(aq.) Pt black
(1 M) electrode
The hydrogen electrode thus obtained forms one of two halfcells of a voltaic cell. A voltaic cell is created when this
halfcell is connected with any other halfcell. 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)
To salt
bridge
Saturated
KCl solution
Hg2Cl2 and
Hg paste
Mercury
1
→ Hg + Cl
Reaction when electrode act as cathode: Hg2Cl2 + e− ←
2
(ii) Silversilver 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 halfcell potential. Similarly
for reductant, all ions present with reductant should be considered.
Aman Gour (JEE 2012 AIR 230)
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:
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

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
→ 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
K + + e− → K(s) 2.93
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
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 halfreactions, 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
Example: Calculate the free energy change for the following electrochemical cell.
º
Cu2+ (aq) + 2e− → Cu(s) Ereduction = +0.339 volts
º
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) Ecell = +1.101 volts
[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
Ammonia produced at cathode combines with zinc ions to form complex ion.
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
These type of cells are used in spacecrafts. 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
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 ).
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 halfreactions for each process. Zn(s) → Zn2+ (aq) + 2e− ; Cu2+ (aq) + 2e− → Cu(s)
º
(ii) Look up the standard potentials for the reduction halfreaction. 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
(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 nonstandard cell potential, Ecell .
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 halfcell. 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.
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]
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
PROBLEMSOLVING 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
(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 halfreactions 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 halfreactions for the cell.
º
(iii) Look up the reduction potential, Ereduction, for the reduction halfreaction in a table of reduction potentials.
(iv) Look up the reduction potential for the reverse of the oxidation halfreaction and reverse the sign to
º º
obtain the oxidation potential. For the oxidation halfreaction, Eoxidation = −Ereduction .
(v) Add the potentials of the halfcells to get the overall standard cell potential.
º º º
Ecell −Ereduction
= + Eoxidation
(e) For determining nonstandard 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
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
nonelectrolytes.
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
nonspontaneous 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. Halfcell: A single electrode immersed in a solution of its ions.
f. Salt bridge: A device (porous disk or bridge i.e. Utube 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 nonspontaneous 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 Nonspontaneous
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]
Solved Examples
2H+ + 2e⁻ → H2; ERP =0
= 0.799 – 0.948 = – 0.149 V
∴ ECell = 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 = Ecell + 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?
= (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
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
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.
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 Cl2Cl– and O3O2 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?
(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+
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
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 halfcell 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 nbutyric 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
halfcells
(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
(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+ – +
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.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 halfcell 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)
Q.23 Given below are the halfcell 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+
JEE Advanced/Boards
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. PtH2 (1 atm)  H+ (1M) M/32 C6H5NH3ClH2 (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, PtH2(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 halfcell 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–PbCl2Pb 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 byproducts. 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).
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
Q.8 Which of the following arrangement will produce Q.12 StatementI: The voltage of mercury cell remains
oxygen at anode during electrolysis? constant for long period of time.
(A) Dilute H2SO4 solution with Cu electrodes. StatementII: It because net cell reaction does not
(B) Dilute H2SO4 solution with inert electrodes. involve active species.
Paragraph 2: Copper reduces NO3– into NO and NO2 Q.3 The halfcell 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.20
(D) AgNO3 solution (s) Ag deposition at cathode (A) (P) (B) (Q) (C) (R) (D) (S)
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
(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
Exercise 2 Exercise 2
Q.3 Q.5 Q.9 Q.4 Q.7 Q.16
Q.20
Answer Key
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
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
Exercise 2
Comprehension Type
Solutions
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
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))
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
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
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, E1 = 0. 8, n = 1 Sol 21: CH3COOH CH3COO– + H+
∆G1 = – nF E1 Cα 2
ka = = Ca2
∆G1 = –0. 8 F 1−α
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
(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
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 m3m2 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, Ecell = 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
Ecell =Ecathode − Eanode =−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 saltbridge.
Chem i str y  17.59
−394.4 kJ mol−1
∆Gf CO2 ( ) = Sol 22: (C)
∆G = Σ∆Gf products − Σ∆Gf reac tants According to Debye Huckle onsager equation,
⇒ E =
−2.69 V E +E = 0. 982
H2 /H+ Ag+ /Ag
As E° value is negative reaction is nonspontaneous.
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+]
E = 0. 344 Cα 2
ka =
1−α
0.0591 1
E = E – log = 0. 226
2 [Cu2+ ] ka = 6. 74 × 10–4
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
[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
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+ +
0.0591 [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
Ag+ + e– → Ag E = 0. 799 V
Sol 20: Cu + 4NH3 → [Cu(NH3)4]
2+ 2+
We have, A – 4x = 2 Adding,
∆G1 = –RT ln kf = – 43. 757 RT ∆G'1 = –nF E° = –2F × 0. 136 = –0. 272 F
∆G = –RT ln kf = –1. 82F – 43. 757RT – 0. 83 F ∆G'3 = –nFE° = –6F(1. 33) = –7. 98 F
[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
Charge needed = 10–2 F = 965 C Sol 38: At anode, for quinhydrone electrode,
= 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
At cathode
[H+ ].[HS – ]
= k1
O2 + 2H2O + 4e → 4OH– [H2S]
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 = 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–
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
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
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.
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 mol1 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
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
201718 100 &
op kers
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By E ran culty
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o titut
Ins
CHEMISTRY
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SECOND
EDITION
Exhaustive Theory
(Now Revised)
Formula Sheet
9000+ Problems
based on latest JEE pattern
Plancess Concepts
Topic Covered Tips & Tricks, Facts, Notes, Misconceptions,
Key Take Aways, Problem Solving Tactics
Chemical Kinetics
PlancEssential
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
Product
Reactant
Time
Concentration vs Time
Figure 18.1: Concentration vs Time
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)
∆[O2 ] 1 ∆[H2O2 ]
The rate of reaction = =–
∆t 2 ∆t
=
∆t →0 ∆t dt
B
Note: For the reaction n1A + n2B → m1C + m2D
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)
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)
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
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)
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 M1sec1, then order = 1(1)=2.
Aman Gour (JEE 2012, AIR 230)
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.
(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)
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 zeroorder 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
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)
Sol: Order is the number to which the concentration of the reactants/products are raised corresponding mostly to
the coefficients.
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.
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)
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
Zeroorder 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 zeroorder reactions. Another example
of zeroorder 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 zeroorder 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) Halflife 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
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 firstorder reaction.
C2H4(g) + H2(g) → C2 H6(g)
Rate = k [C2H4]
All natural and artificial radioactive decay of unstable nuclei takes place by firstorder 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 firstorder reaction for a firstorder reaction
Examples:
226
(a) 88 Ra →24 He + 86
222
Rn ; Rate = k[Ra]
(b) Decomposition of N2O5 and N2O are few more examples of firstorder reactions.
2.303 [R]
(i) Unit of rate constant: K = log 0 = sec–1
t [R]
(ii) Halflife period (t1/2):
2.303 pi
k= log ...(xi)
t pA
2.303 pi
= log
t 2pi – pt
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
Time
−
k(a − x) ka
1
The slope of the line is , where ‘k’ can be evaluated.
k
1/(ax)
1 0.5a 1
(b) Halflife period (t1/2) = ⋅ = Figure 18.5 Second order plot
k a × 0.5a ka
Thus, halflife period is inversely proportional to initial concentration.
(c) Secondorder 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 firstorder kinetics with
respect to the reactant taken relatively in small amount.
Examples
For a zeroorder 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 zeroorder 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 firstorder 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 firstorder 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.
For a secondorder 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 secondorder reaction.
0.00 5.0 0
100 200 300 0 100 200 300 100 200 300
Time sec. Time sec Time sec.
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
Conc.
[C]
[B]
[A]
Time
k
CH3CHO
2→ CO + CH4
Illustration 9: If the time required to decompose SO2Cl2 to half of its initial amount is 60 minutes and the
decomposition is a firstorder reaction, then calculate the rate constant of the reaction. (JEE MAIN)
0.693
Sol: For a firstorder 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 firstorder 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 firstorder 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
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
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.
Illustration 12: In a secondorder 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
(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.
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
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.
Illustration 13: The reaction 2NO + Br2 → 2NOBr obeys the following mechanism:
fast
Step I:
NO + Br2 ← → NOBr
2
Slow
Step II: NOBr2 → 2NOBr
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
Fraction of molecules
capable of bringing
effective collisions
Energy E
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.
A A
A A A A
B B
B B
B B
Reactants Products
Figure 18.13: Collision theory
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
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
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.
Reaction path
without catalyst Energy of
activation
Energy of
Potential Energy
without
activation
Reaction catalyst
with
Reactants path with catalyst
catalyst
Products
Reaction coordinate
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 nonspontaneous 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.
Note: In the following reaction formation of methanol from bromoethane 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
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 firstorder 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
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
20
Chem i str y  18.25
1 1 1
k= − , for secondorder reactions;
t (a − x) a
1 1 1
k= − , for thirdorder reactions;
2t (a − x)2
a2
t1/2
t1/2
t1/2
2
Conc. Conc. 1/a 1/a
1 −n
Figure 18.17: Plots of halflives versus concentration (t1/2 ∝ a )
PROBLEMSOLVING 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
∆[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) Problemsolving 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.
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 zeroorder 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:
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
dt dt
where k is rate constant or velocity constant.
dx
When [A] = [B] = 1 mol/L, then =k
dt
Various types of Type of Integrated rate equation Unite of rate t1/2 Halflife t3/4 period
reactions reaction constant period
Zeroorder Concentration
d[A] A0
reaction – = k0[A]0 time–1
dt 2k
dx
Differential form =k
dt
Chem i str y  18.29
Firstorder 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)
0 1 2 3
(conc) (conc) (conc) (conc)
1/(a  x)
2
(conc)
log[A]
1/(a x)
t t t t
0 1
(conc) (conc) 1/a 1/a
HalfLife
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
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:
Example 2: The specific reaction rate of a firstorder
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 firstorder 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
(a) Comparing equations (i) and (ii), [A] > 1, R1< R2 < R3.
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 firstorder 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 firstorder 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
(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
JEE Main/Boards
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 halflife 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 halflife 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 firstorder 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 preexponential 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?
(a) Derive the rate law using the steadystate 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 preexponential 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 − 2k −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
Q.4 The rate equation for the reaction (C) 0.02 M (D) 0.002 M
(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 halflife 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
(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 halflife 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)
(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 halflife 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 JK1 mol1 and log
dt dt dt dt
2 = 0.301) (2013)
Q.17 The halflife period of a first order chemical (A) 53.6 kJ mol1 (B) 48.6 kJ mol1
reaction is 6.93 minutes. The time required for the (C) 58.5 kJ mol1 (D) 60.5 kJ mol1
completion of 99% of the chemical reaction will be
(log 2 = 0.301) (2009)
Q.23 . For the nonstoichiometry 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 L1s1) 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 × 103
reaches 0.05 M, the rate of formation of O2 will be:
0.1 M 0.2 M 1.2 × 103 (2016)
0.2 M 0.1 M 2.4 × 103
(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
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 nfactor of A B & C are same]
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 ∞
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.
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.
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 halflife of 1 minute?
(a) H2 + I2 → 2HI (one step)
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
1.5
t
1.2
1
(C) (D)
0.8 Experiment1
d[A] d[A] 0.6 Experiment2
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)
(1) (2) (3) (4)
(A) ∆E for Ea for ∆Eoverall Ea for
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
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 min1
(B) For a zeroorder 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 zeroorder 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 zeroorder 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
tatementI is true, statementII is true and
statementII is correct explanation for statementI
(C) Half life of reaction is 15 min
(B) StatementI is true, statementII is true and
(D) After 75% conversion of A in to B and C angle of statementII is NOT the correct explanation for
rotation of solution will be 36° statementI
(C) StatementI is true, statementII is false.
Q.16 Which of the following statement is incorrect?
(D) StatementI is false, statementII is true.
(A) The order of reaction is the sum of powers of all the
concentration terms in the rate equation.
Q.20 StatementI: 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 StatementII: 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 StatementI: 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
StatementII: 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 preexponential factor (A) for second order Q.22 StatementI: The overall rate of a reversible
reaction is mol L–1 s–1 reaction may decrease with the increase in temperature.
(B) A zeroorder reaction must be a complex reaction StatementII: 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 StatementI: 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 StatementII: 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 StatementI: 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
StatementII: 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 StatementI: 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 ]
StatementII: 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 ⋅ ekt (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
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 ax 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.
(C) 166.66 min (D) 156.66 min ColumnI (Graphs ColumnII (Coordinates)
reaction A → Products)
(A) (p) ln [A] (yaxis), t(xaxis)
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
1 T T
(u) (yaxis), t(xaxis)
[A] (C) (D)
(order = 2)
K K
(v) r (yaxis), [A](xaxis)(order = 1)
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 halflife 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 halflife 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 halflife 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 halflife 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
(A) 0.5 mol1 dm3 (B) 1.0 mol dm3 (A) 2 (B) 3 (C) 0 (D) 1
(C) 1.5 mol dm3 (D) 2.0 mol1 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 firstorder
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 preexponential 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
Exercise 2 Exercise 2
Q.2 Q.10 Q.16 Q.8 Q.12 Q.28 Q.29
Q.33 Q.34 Q.37
Answer Key
Q.5 k = 0.022 hr–1 Q.23 Rate = K(A][13]2 rate will became 8 times
Q.9 (a) 43.46 kJ mol–1 (b) 20.47 hour Q.25 It is first order kinetics with
Q.15 Er=6 × 104 J; Eb = 9.3 × 104 J (b) = 5.495 × 10–3 mol–1 l–1 s–1
Exercise 2
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
1 Q.51 306 K
Q.44
e
(K1 +K2 )
t −1 Q.52 Rate of reaction increases 5.81 × 108 times
Exercise 2
Q.19 A, B, C
Comprehension Type
Q.37 A → s; B → r; C → p; D → q Q.38 A → p; B → q, s; C → r, t; D → v
Q.15 (a) 1 (b) 693x103 min1 (c) 200 min (d) 950 mm Q.16 D
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
⇒ 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 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
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
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
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
2k
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
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,
7e 8.214 ×323 rf
= 1. 5 × 10 = 2(n – m)
ri
A = 5. 42 × 1010 s–1
Chem i str y  18.67
(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,
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
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.
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
⇒ 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
∆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
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
1 [A]0
k = log ln 4
1 0.98[A]0 ⇒t=
k1 − k 2
Chem i str y  18.75
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
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
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,
−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
∴ 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
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,
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 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
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
dt
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
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
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
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,
R V0 n
⇒V = = V0 2 − 2 − 1 e 1
a0 n1 n1
P
= 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
−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
[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 ColumnII and ⇒ = kt +
[A] [A]0
then match them with ColumnI.
Straight line with positive slope and positive intercept.
(p) ln (A) vs t (order 1)
Matches no option in ColumnI.
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 xaxis. (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.
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 : Halflife = = = 462000 s; = 128.33 h
k = Ae–Ea /RT k 1.5 × 10 −6
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