Chemistry Formula Booklet

1
C H E M I S T RY
FORMULA SHEET
IDEAL 21ST CENTURY COMPETITIONS

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APPLICATION OF MOLE CONCEPT
1. LAWS OF CHEMICAL COMBINATION

1.1 Law of conservation of mass [Lavoisier]
1.2 Law of constant composition [Proust]
1.3 Law of multiple proportions [Dalton]
1.4 Law of reciprocal proportions [Richter]
1.5 Gay Lussac law of combining volumes [Guess Who??]
"Wonder these laws are useful?"
"These are no longer useful in chemical calculations now but gives an idea of earlier
methods of analysing and relating compounds by mass."
2. MOLE CONCEPT
2.1 Definition of mole : One mole is a collection of that many entities as there are number of atoms
exactly in 12 gm of C-12 isotope.
or 1 mole = collection of 6.02 1023 species
6.02 1023 = NA = Avogadro's No.
` 1 mole of atoms is also termed as 1 gm-atom, 1 mole of ions is termed as 1 gm-ion and
1 mole of molecule termed as 1 gm-molecule.
2.2 Methods of Calculations of mole :

Given no.
(a) If no. of some species is given, then no. of moles =
NA
Given wt.
(b) If weight of a given species is given, t hen no of moles = (for atoms),
Atomic wt.
Given wt.
or = (for molecules)
Molecular wt.
(c) If volume of a gas is given along with its temperature (T) and pressure (P)
PV
use n =
RT
where R = 0.0821 lit-atm/mol-K (when P is in atmosphere and V is in litre.)
1 mole of any gas at STP occupies 22.7 litre.
Gases do not have volume. What is meant by "Volume of gas"?
Do not use this expression (PV = nRT) for solids/liquids.
How would I calculate moles if volume of a solid is given?

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2.3 Atomic weight:It is the weight of an atom relative to one twelvth of weight of 1 atom of C-12
Be clear in the difference between 1 amu and 1 gm.

(a) Average atomic weight = % of isotope X molar mass of isotope.
The % obtained by above expression (used in above expression) is by number (i.e. its a mole%)
2.4 Molecular weight : It is the sum of the atomic weight of all the constituent atom.
ni Mi
(a) Average molecular weight =
ni
where ni = no. of moles of any compound and mi = molecular mass of any compound.
Make yourselves clear in the difference between mole% and mass% in question related to above.
Shortcut for % determination if average atomic weight is given for X having isotopes XA & XB.
Average atomic weight wt of X B

% of XA = 100
difference in weight of X A & X B
Try working out of such a shortcut for XA, XB, XC
3. EMPIRICAL FORMULA, MOLECULAR FORMULA :

3.1 Empirical formula : Formula depicting constituent atom in their simplest ratio.
Molecular formula : Formula depicting actual number of atoms in one molecule of the compound
3.2 Relation between the two : Molecular formula = Empirical formula n

Molecular mass
n = Empirical Formula mass
Check out the importance of each step involved in calculations of empirical formula.
3.3 Vapour density :

Vapour density : Ratio of density of vapour to the density of hydrogen at similar pressure and
temperature.
Molecular mass
Vapour density =
2
Can you prove the above expression?
Is the above parameter temperature dependent?
4. STOICHIOMETRY : Stoichiometry pronounced (stoy key om e tree) is the calculations of the

quantities of reactants and products involved in a chemical reaction. Following methods can be used for
solving problems.

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(a) Mole Method Balance reaction required

(b) Factor Label Method
(c) POAC method } Balancing not required but common sense use it with slight caree.
(d) Equivalent concept } to be discussed later
5. CONCEPT OF LIMITING REAGENT.

5.1 Limiting Reagent : It is very important concept in chemical calculation. It refers to reactant which
is present in minimum stoichiometry quantity for a chemical reaction. It is reactant consumed fully in a
chemical reaction. So all calculations related to various products or in sequence of reactions are made on
the basis of limiting reagent.
It comes into picture when reaction involves two or more reactants. For solving any such reactions,
first step is to calculate L.R.
5.2 Calculation of Limiting Reagent :

(a) By calculating the required amount by the equation and comparing it with given amount.
[Useful when only two reactant are there]
(b) By calculating amount of any one product obtained taking each reactant one by one irrespective of
other reactants. The one giving least product is limiting reagent.
(c) Divide given moles of each reactant by their stoichiometric coefficient, the one with least ratio is
limiting reagent. [Useful when number of reactants are more than two.]
actual yield
6. PERCENTAGE YIELD : The percentage yield of product = the theoretical maximum yield 100
The actual amount of any limiting reagent consumed in such incomplete reactions is given by
[% yield given moles of limiting reagent] [For reversible reactions]
For irreversible reaction with % yield less than 100, the reactants is converted to product (desired)
and waste.
7. SOME EXPERIMENTAL METHODS :

7.1 For determination of atomic mass :
Dulong's and Petit's Law :
Atomic weight specific heat (cal/gmC) 6.4
Gives approximate atomic weight and is applicable for metals only. Take care of units of
specific heat.
7.2 For molecular mass determination :
(a) Victor Maeyer's process : (for volatile substance)
Procedure : Some known weight of a volatile substance (w) is taken, converted to vapour and
collected over water. The volume of air displaced over water is given (V) and the following expressions
are used.
w w
M= RT or M= RT
PV (P P' )V
If aq. tension is not given If aq. tension is P'

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Aqueous tension : Pressure exerted due to water vapours at any given temperature.
This comes in picture when any gas is collected over water. Can you guess why?
(b) Silver salt method : (for organic acids)

Basicity of an acid : No. of replacable H+ atoms in an acid (H contained to more electronegative
atom is acidic)
Procedure : Some known amount of silver salt (w1 gm) is heated to obtain w2 gm of while shining
residue of silver. Then if the basicity of acid is n, molecular weight of acid would be
w2 1
M salt w1 and molecular weight of acid = M n(107)
salt
108 n
This is one good practical application of POAC.
(c) Chloroplatinate salt method : (for organic bases)
Lewis acid : electron pair acceptor
Lewis base :electron pair donor
Procedure : Some amount of organic base is reacted with H2PtCl6 and forms salt known as chloroplatinate.
If base is denoted by B then salt formed
(i) with monoacidic base = B2H2PtCl6
(ii) with diacidic base = B2(H2PtCl6)2
(iii) with triacidic base = B2(H2PtCl6)3
The known amount (w1 gm) of salt is heated and Pt residue is measured. (w2 gm). If acidity of base is 'n'
w2 1 M salt n (410)
then M salt w1 and M
base =
195 n 2
CONCENTRATION TERMS
CONCENTRATION TERMS :
1.1 General concentraction term :
Mass
(a) Density = , Unit : gm/cc
Volume
Density of any substance
(b) Relative density =
Density of refrence substance
Density of any substance
(c) Specific gravity =
Density of water at 4C
Density of vapour at some temperature and pressure
(d) Vapour density = Density of H gas at same temperature and pressure
2
(1) Which of these are temperature dependent.

(2) Classify them as w/w, w/v, v/v ratio.
1.2 For solutions (homogeneous mixture) :
What is solute and solvent in a solution.

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If the mixture is not homogeneous, then none of them is applicable.
Classify each given ratio as w/w, w/v, v/v and comment on their temperature dependence.
w wt .of solute
(a) % by mass : = wt .of solution 100
W
[X % by mass means 100 gm solution contains X gm solute ; (100 X) gm solvent ]
w wt.of solute
(b) % := 100 [for liq. solution]
V volume of solution
w
[X % means 100 ml solution contains X gm solute ]
V
for gases % by volume is same as mole %
v volume of solute
(c) % : = volume of solution 100
V
Moles of solute
(d) Mole % : = 100
Total moles
Moles of solute
(e) Mole fraction (Xa) : = Total moles
Mole of solute
(f) Molarity (M) : =
volume of solution in litre
Moles of solute
(g) Molality (m) : = Mass of solvent (in kg )
Mass of solute 6 Mass of solute

(h) Parts per million (ppm) : = Mass of solution 10 Mass of solvent 106
Get yourselves very much confortable in their interconversion. It is very handy.
1.3 Some typical concentration terms :

(a) Oleum : Labelled as '% oleum' (for e.g. 102% oleum), it means maximum amount of H2SO4 that
can be obtained from 100 gm of such oleum (mix of H2SO4 and SO3) by adding sufficient water.
Work out what are the maximum and minimum value of the %
(b) H2O2 : Labelled as 'volume H2O2 (for e.g. 20V H2O2), it means volume of O2 (in litre) at 1 atm &
273 K that can be obtained from 1 litre of such a sample when it decomposes according to
1
H2O2 H2O + O
2 2
Work out a relationship between M and volume H2O2 and remember it

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EUDIOMETRY
EUDIOMETRY :
Eudiometry or gas analysis involves the calculations based on gaseous reactions or the reactions in which at
least two components are gaseous, in which the amounts of gases are represented by their volumes, measured
at the same pressure and temperature. Some basic assumptions related with calculations are:
1. Gay-Lussac's law of volume combination holds good. According to this law, the volumes of gaseous reactants
reacted and the volumes of gaseous products formed, all measured at the same temperature and pressure,
bear a simple ratio.
N2 (g) + 3H2 (g) 2NH3 (g)
1 vol. 3 vol. 2 vol.
Problem may be solved directly is terms of volume, in place of mole.
2. The volumes of solids or liquids is considered to be negligible in comparison to the volume of gas. It is due
to the fact that the volume occupied by any substance in gaseous state is even more than thousand times the
volume occupied by the same substance in solid or liquid states.
2H2 (g) + O2 (g) 2H2O (l)
2 mole 1 mole 2 mole
2 vol. 1 vol. 0 vol.
3. Air is considered as a mixture of oxygen and nitrogen gases only. It is due to the fact that about 99% volume
of air is composed of oxygen and nitrogen gases only.
4. Nitrogen gas is considered as an non- reactive gas. It is due to the fact that nitrogen gas reacts only at very
high temperature due to its very high thermal stability. Eudiometry is performed in an eudiometer tube and
the tube can not withstand very high temperature. This is why, nitrogen gas can not participate in the
reactions occurring in the eudiometer tube.
EUDIOMETRY : [For reactions involving gaseous reactants and products]

The stoichiometric coefficient of a balanced chemical reactions also gives the ratio of volumes in
which gaseous reactants are reacting and products are formed at same temperature and pressure.
The volume of gases produced is often given by mentioning certain solvent which absorb contain
gases.
Solvent gas (es) absorb
KOH CO2, SO2, Cl2
Ammonical Cu2Cl2 CO
Turpentine oil O3
Alkaline pyrogallol O2
water NH3, HCl
CuSO4 /CaCl2 H2O
Check out for certain assumption which are to be used for solving problem related to this.

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ATOMIC STRUCTURE
STRUCTURE OF ATOM
1. Rutherford's Model
(a) Electrons, protons & neutrons are the most important fundamental particles of atoms of all elements
(Except hydrogen)
(b) Z
XA , Mass number (A) = Atomic number (Z) + number of neutrons (n)
(c) Rn = R1 (A)1/3 , R1 = 1.33 1013 cm A = mass number

1 Z . 2e
(d) m v 2 K ; r = distance of closest approach , v = initial velocity of a -particle
2 r
2. Light
(a) Photon is considered massless bundle of energy.
(b) E = mc2
(c) Ephoton = h = hc/ = hc
hc 1240 eV . nm
(d) E=

no. of molecules reacting
(e) Quantum efficiency or Quantum Yield =
no. of quanta absorbed
3. Bohrs Model
Kq1q 2 1
9 2 2
(a) Electrostatic force = where K = 40 = 9 10 N-m / C
r2
Kq1q 2
(b) Potential energy due to electrostatic force =
r
KQ
(c) Potential due to a charge particle (Q) at a distance r =
r
h
(d) Bohr quantization rule mvr = n = n .
2
(e) According to newtons second law in a uniform circular motion resultant of all the forces towards
mv 2
centre must be equal to .
r
Kq1q 2 mv 2
(f)
r2 r

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E1 2 2 2 me 4 K 2 2 22 me 4K 2 Z2
(g) En = Z = Z ; E1 =
n
2 n 2h 2 h2
2 2
h n
(h) rn = 2 2
4 e m K Z
2
2e K Z
(i) vn =
h n
(j) Revolutions per sec = v/2r
(k) Time for one revolution = 2r/v
(l) Ionisation energy = E n Eelectron = Eelectron
4. Spectral lines
1 1 1 2
(a) Rydbergs Equation RH
2

2
Z ; RH 109700 cm1
n1 n 2
(b) For First line of a series n2 = n1 + 1
(c) Limiting spectral line (series limit) means n2 =
(d) H line means n2 = n1+1 ; also known as line of longest , shortest , least E
(e) Similarly H line means n2 = n1+ 2

n ( n 1)
(f) Number of spectral line observed in the spectrum =
2

when e de-excites to ground state , n = number of higher orbit
(g)
n=5
n=4
Bracket
series
n=3
Paschen
series
n=2
Balmer
series
n=1
H H H

Lyman
series

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5. Photoelectric effect
(a) Kinetic energy = = h w = h h 0
where w = work function
0 = Threshhold frequency
1 2
(b) Accelerating potential = eV = KE = mv
2
(c) 1/2 = a(zb) b = screening constant
6. De-broglie, Heisenberg & Schrodinger equations

(a) Number of waves = n = principal quantum number
(b) = h/mv = h/p
150
(c) wavelength of electron ()
Vin volts
(d) x.p h/4
h
(e) Orbital angular momentum = l (l 1)
2
h
(f) Spin angular momentum = S = S(S 1)
2
(g) Magnetic momentum () = n ( n 2) B.M. ; n = number of unpaired electron
(h) Radial Nodes = (n l 1)
(i) Angular nodes =l
(j) Total nodes = (n1)
7. Terms associated with elements

(a) Isotopes
(b) Isobars
(c) Isotones (A Z)
(d) Isoelectronic
(e) Isosters
(f) Isodiaphers (A 2Z)
(g) paramagnetic
(h) Diamagnetic
8. Eleectromegnetic Spectrum
increases
Cosmic -rays X-rays Vaccum UV Visible Near Far Micro Radio

Rays UV IR IR Waves Waves
7 6 5 3 1 0
= 10
14
10
13
10
11
10
10
9
8
10 10 10
4
10 10
2
10
10 10 10 10
12
10

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IDEAL GAS
Parameters:
(i) Forces of attraction

(ii) Thermal energy small moderate very large
(iii) Shape fixed not fixed not fixed
(iv) Volume fixed fixed not fixed
(v) Density very high moderate very low
GASEOUS STATE : The state is characterized by sensitivity of volume change with change of pressure and
temperature. It is due to large distance between molecules as compared to their own
dimensions. There exists weak Vander Waal's forces, molecules move independent of
each other with speed about 400 m s1 .
Are volume of solids & liquid totally independent of pressure??
IDEAL GAS : A gas with no intermolecular attractions & having very negligible volume occupied by molecules
when compared with volume of gas is termed as ideal gas. A theoretical concept which for gases
present can be obtained only under certain condition.
REAL GAS : Considerable forces of attraction & appreciable size of molecules. These under " certain
conditions" behave like ideal. [Refer : sheet of real gas behaviour]
Parameter associated with the gas : P ,V ,T , n

where
P represents pressure exerted by the gas molecules on the walls of the container assuming negilible
intermolecular attractions,
V represents free volume available for motion (equal to the volume of the container),
T represents absolute temperature, n represents no of moles.
Conversion factors : Pressure 1 atm =1.013 105 Pa = 760 mm of Hg = 760 torr = 1.013 bar
Volume 1 l = 1dm3 = 103 m3 = 1000 ml = 1000 cm3
5
Temperature TK = TC +273.15 = T +255.37
9 F
INSTRUMENTS FOR PRESSURE CALCULATIONS :

A hdg
Barometer : P = where d = density of fluid
A
h = vertical height
g = acceleration due to

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Manometer : Pgas = Patm + hdg
EQUATION & GRAPHS OF EXTENSIVE UTILITY IN GASEOUS STATE :
Two Parameters 'y' & 'x' if are related as

(a) y = m x + C (where m & C are constants) [then there will be a direct relationship
between them & graph will be a straight line as shown ]
y = mx + C (straight line)
m
(b) xy = constant (rect hyperbola) / y = +C (where m & C are constant)
x
(c) y2 = Kx ( K is a constant)
(d) x2 = Ky ( K is a constant)
Experimental Gas laws Relationship between various parameter of the gas. Gaseous state is the only state
that allows a quantitative descriptive between the four parameters, P, V, T & n. The relationship which
connects the four variables is known as equation of state, which can be obtained experimentally from the
following gas laws.
# All are based on experimental data.
# All are applicable for ideal gases only.
# Get yourselves comfortable with all the various types of graphs to get a 'feel' of them.
1
I. Boyle's law V T , cons tan t P1 V1 = P2 V2
P n cons tan t
graphs are Isotherms
Plot the different curves for difference values of n & V to compare.

V1 V
II. Charle's law V T P , cons tan t T1
= T2
n cons tan t 2
graphs are Isobars
Plot graphs of V vs Tc & V vs TF

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P1 P2
III. Gay Lussac's law P T V , cons tan t T1
= T2
n cons tan t
graphs are Isochor
V1 V2
IV. Avogadro's law V n ( T , P constant ) n1 = n2
log V 45
log RT/ P
log n
P1 V1 P2 V2
Combined Gas Law : T1 = T2
Equation Of State : PV = nRT
d = density of gas
PV = Mw R T R = Universal Gas constant = 0.0821 atm litres kelvin1 mol1
PM = dRT = 8.314 joule / kelvin = 2cal kelvin1 mol1
Dalton's law of partial pressure :

Ptotal = PA + PB + ....... ; Pwet gas = Pdry gas + PH O vapour ( i.e. aq. tension.)
2
PA , PB are partial pressures . ; PA = mole fractionA Total pressure

Partial pressure
and % of gas in mixture = 100 .
Total pressure
Amagat's Law :
The total volume of a mixture of gases is equal to the sum of the partial volumes of the constituent gases, at
same Temperature & Pressure.
Graham's law of Diffusion or Effusion :
1 1 P
r or r r [For gases effusing at different pressures]
d M M
r is rate of diffusion of any gas.
r1 d2 M2 volume / time M2
= = ; = d is density at some temperature.
r2 d1 M1 volume / time M1
moles diffused dis tan ce travelled in a narrow tube Pr essure drop I
r = = =
time taken time taken Pr essure drop II
It should be noted that the rate of diffusion or effusion actually depends on pressure difference of the gas
and not simply on its pressure. Moreover the pressure difference is to be measured for this gas only i.e. if a
container holds [He] at a pressure of 0.1 atm and if a small pin-hole is made in the container and if the
container is placed in a room, then the rate of effusion of He gas from the container to outside depends only
on its pressure difference , which is 0.1- 0 (as there is no He in the atmosphere). This implies that the
diffusion of a gas is not dependent on the diffusion of any other gas.
Whenever we consider the diffusion of a gas under experimental conditions, we always assume that the gas
diffuses in vaccum and during the time period for which the diffusion is studied the rate of diffusion (or the
composition of diffusing or effusing mixture of gases) remains constant.

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Isotropic Separation Factor :

n11 n12
f = = f.
n1 n 2
n1 , n2 and n11 , n12 are the concentration of two isotopes before and after processing .
M2
Theoretical separation factor f =
M1
If required enrichment of species (1) is attained after 'x' times, then :
n11 n12
(f )x = = f.
n1 n 2
2 log f
Solving using Graham's law , x = .
M
log 2
M1
Miscellaneous concepts used in Gaseous State:

(a) Bursting of containers : two concepts used depending upon type of container.
(i) Bubble type (very thin skin) cannot tolerate difference in pressure on the skin
outside pressure = inside pressure
Any change in these cause change in volume & the container burst due to maximum stretching.
(ii) Cylinder type (thick skin) can withstand pressure difference till a limit but cannot have volume change.
Any change cause a change in pressure & when it exceeds the limits the container burst.
(b) Connecting containers having gases
On removal of nozzel the gas from higher pressure will travel so as to have equal pressure at both the
containers.... from idea of total moles & final temperature each parameter can be calculated.
(c) Changes in Open vessel : Pressure of gas remains constant & so is the volume.
n1 T1 = n2 T2
P1 P2
(e) Changes in closed vessel : n n
1 2
(f) Analysis of a reaction involving gaseous

A(g) + B(g) C(g)
What happens to pressure as reaction proceeds (in a closed container)
Dd
(g) Vapour density and degree of dissociation = ( n 1) d

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Kinetic theory of gases :

1 1
PV = m N u2 = M u2 (For 1 mole)
3 3
Types of velocities :
u12 u 22 ...... u 2N
u2 = ; u = root mean square speed .
N
Finds applications in K.E.
3R T 3PV 3P
u = = = ;
M M d
u1 u 2 ...... u N 8RT
Average speed = =
N M
Finds application in Collision theroy

2RT
most probable speed =
M
most probable : average : r. m. s. = 1 : 1.13 : 1.22
8
Relationship between three
= 2 : : 3 types of speeds

urms > uav > ump
3 R 3
Average kinetic energy of a single molecule = . .T = kT
2 N 2
k = Boltzman constant = 1.3806 10 16 erg deg 1 .
3
Total kinetic energy for one mole of a gas = RT .
2
3
kinetic energy of n moles of a gas = n RT
2
3/2
M
Maxwell distribution Laws: dNu = 4N exp(Mu2 / 2RT) u2 du
2RT
3/ 2
m
= 4N exp( mu2 / 2kT) u2 du
2kT
Collision frequency & Mean Free Path :

d1 d 2 ...... d n
Mean free path =
n
Average velocity / R M S velocity kT
= =
collision number or frequency 2 2 P
k = Boltzman constant ; = collision diameter .
Z1 = 2 2 u N * [collisions made by one molecule
1
Z11 = 2 *2
2 u N

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REAL GAS
THE REAL PATH

Vander Waals equation of state :
a 2
P 2 .n (V n b) = n R T .
V
a , b are Vander Waals constants ; different for each gas
unit of a atm L mol 2 2 ; S.I. unit Pa m6 mol 2
unit of b L mol 1 ; S.I. unit m3 mol 1
greater the value of 'a' more easily the gas is liquefiable ;
greater the value of 'b' greater the molecular size ,
Real gases : Deviation from ideal behaviour

The curve for the real gas has a tendency to coincide with that of an ideal gas
at low pressures when the volume is large. At higher pressures,
however deviations are observed.
Compressibility factor :
PV volume observed
z = =
nRT volume ideal
Boyle Temperature :
a
TB =
bR
Inversion Temperature :
2a
Ti =
bR
Interpretation Of Deviation From Vander Waals Equation :
PV a
(i) At low pressure z = = 1
RT VRT
PV Pb
(ii) At high pressure z = = 1+
RT RT
PV a
(iii) At extremely low pressure z = = 1 ; Pb =
RT V

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S\OME OTHER EQUATION OF STATE
Dieterici Equation :
Pena/VRT (V n b) = n R T
Berthelot Equation :
n2 a
P (V n b) = n R T (a & b are Berthlot's constant different from Vander Waal's constant)
T V2
Virial Equation Of State For 1 Mole Of Gas :

PV 1 1 1
z = = 1+B + C 2 + D 3 + ...... (B, C, D... are temp. dependent constant)
RT V V V
a
B = second virial coefficient = b
R T gas dependent
C = third virial coefficient = b2 .
Critical Phenomenon : Critical Temp , Critical pressure , Critical volume

8a a
Tc = ; Pc = ; Vc = 3 b
27 R b 27 b 2
The law of corresponding states :

p T Vm
pr = p , Tr = T and Vr = V
c c c
p = prpc, T = TrT c and Vm = VrVc
Substituting these expression in the van der Waals equation

p a
(V b) = RT
T
Vm m
2

p p a
We obtain r c (V V b) =RT
T rT c
Vr2 Vc2 r c
Replacing pc, Vc and Tc in terms of a, b and R, we get
a a 8a
p
r 2
2 2 {Vr (3b)b} = RT
Tr
27b Vr (3b) 27 Rb
i.e. (pr + 3/ Vr2 ) (3Vr 1) = 8Tr
(p r p c )(Vr Vc ) p c Vc
pVm p r Vr 3 p r Vr
Z= = R (T T ) = T =
T 8 T
RT r c c r r

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THERMODYNAMICS
The subject of Thermodynamics deals basically with the interaction of one body with another in terms of
quantities of heat & work. It may be defined as the branch of science which deals with energy changes
associated with various physical & chemical processes. The entire formulation of thermodynamics is based
on a few (Three) fundamental laws which have been established on the basis of human experience of the
experimental behaviour of macroscopic aggregates of matter collected over a long period of time.
SOME BASIC DEFINITATIONS

System : the macroscopic part of the universe under study is called a system.
Surroundings : the rest of the universe outside the system is called surroundings.
Boundary : The actual or imaginary surface that separates the system from the surroundings is called the
boundary.
TYPES OF SYSTEMS
Isolated system : A system is said to be isolated if it cannot exchange matter and energy with the surroundings.
Example : coffee in a thermos flask.
Closed system : A system is said to be closed if it can exchange energy but not matter. Example : Coffee in
a closed stainless steel flask.
Open system : A system is said to be open if it can exchange matter. Example : A thermos flask or a steel
flask if not closed.
PROPERTIES OF SYSTEM
The state of a system is defined by a particular set of its measurable quantities called properties. They can be
categorised into extensive and intensive properties.
Intensive property is one whose value is independent of the size (or mass) of the system. An extensive
property is one whose value depends on the size (or mass) of the system.
* Extensive properties are additive but intensive propreties are non additive.
* Ratio of two extensive property gives an intensive property.
Extensive Properties Intensive Properties

Volume Molar volume
Number of moles Density
Mass Refractive index
Free Energy (G) Surface tension
Entropy (S) Viscosity
Enthalpy (H) Free energy per mole
Internal energy (E & U) Specific heat
Heat capacity Pressure
Temperature
Boiling point, freezing point etc
STATE FUNCTON OR STATE VARIABLE
Variables like P, V , T are State Functions or State Variables because their values depend only on the present
state of a system and not on how the state was reached.

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Condition for a function to be a state function :

(i) If is a state function
B
d = B A
A
(ii) If is a state function
d =0
(iii) If = f(x, y) is a state function, Euler's reciprocity theorem must be satisfied.

=
y x y x y x
x y
PATH FUNCTION
Functions which depend on the path means how the process is carried out e.g. work & heat.
THERMODYNAMIC PROCESS
A thermodynamic process involves change of a system from one state to another state.
A process is called Isothermal, if the temperature of the system remains constant during the change.
It is carried out in a thermostat and in such a process the exchange of energy between the system and
surroundings takes place. In such a process dT = 0
A process is called Adiabatic, if the system does not exchange heat with surroundings. Such a process is
carried out in perfectly insulated containers. During it the temperature of the system may change. In such a
process dq = 0.
A process carried out at a constant pressure is called an isobaric process. In such a process
dP = 0.
A process in which the volume of the system remains constant is called an isochoric process, whereby
dV = 0.
In a cyclic process a system undergoes a number of different processes and finally returns to its
initial state. T = 0 & V = 0.
REVERSIBLE AND IRREVERSIBLE PROCESS

A process which is carried out so slowly that the system and the surroundings are always in equilibrium is
known as a Reversible Process (quasi-static). If this condition does not hold good, the process is said to be,
Irreversible.
In a reversible process the driving force is infinitesimally larger than the opposing force.
A reversible process in very slow and takes infinite time. Where as an irreversible process completes in finite
time.

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Reversible process irreversible process
TYPE OF EQUILIBRIUM :
1. Thermal equilibrium : Equality of temperature
2. Mechanical equilibrium : No pressure difference
3. Material equilibrium : No net change in amount
WORK
Two types of work normally come across in chemistry. These are Electrical Work and
PV-work (pressure volume work)
In thermodynamics we mainly discuss PV-work
V2
WPV = Pext dV
V1
But later on we will discuss electrical work also Welectric = VIt

IUPAC convention for work :
* Work done by system is expressed with ive sign
* Work done on system is expressed with +ive sign
HEAT
Heat is defined as the energy that flow into or out of a system because of a difference in temperature
between the thermodynamic system and its surrounding.
According to IUPAC convention heat given by system is expressed with -ive sign heat given to system is
expressed with +ive sign.
* qV = nCvdT
* qp = nCpdT
* Cp,m Cv,m = R
* Cv & Cp depend on tempeture
INTERNAL ENERGY (E & U)

Every system having some quantity of matter is associated with a definite amount of energy, called internal
energy.
U = UKinetics + UPotential + UElectronic + Unuclear + .....
U is a state function & is an extensive property.

U = Ufinal Uinitial
* For a given system
U = f (T, V)
U U
dU = T . dT + dV
v V T
* For isochoric process : dV = 0

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U
dU = T dT
v
dU = Cv . dT
U C v .dT
* For an ideal gas
U
0
V T
dU = Cv . dT
U C v .dT
ZEROTH LAW OF THERMODYNAMICS

Two systems in thermal equilibrium with a third system are also in thermal equilibrium with each other.
FIRST LAW OF THERMODYNAMICS

"Total energy of universe remain constant." It is law of conservation of energy.
Let us consider a system whose internal energy is U1. If the system is supplied with heat q, the internal
energy of the system increases to U1 + q. If work (w) is now done on the system, the internal energy in the
final state of the system, U2 is given by
U2 = U1 + q + w
or U2 U1 = q + w
U = q + w,
According to IUPAC , heat, added to the system and work done on the system are assigned positive values
as both these Modes increase the internal energy of the system.
ENTHALPY
Chemical reactions are generally carried out at constant pressure (atmospheric pressure) so it has been
found useful to define a new state function Enthalpy (H) as :
H = U + PV
H = U + (PV)
at constant pressure
H = U + P V
combining with first law.
H = qp
Hence transfer of heat at constant volume brings about a change in the internal energy of the system
whereas that at constant pressure brings about a change in the enthalpy of the system.
* For a given system

H = f (T, P)
H H
dH = T . dT + dP
P P T

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* For isobaric process : dP = 0
H
dH = T dT
P
dH = CP . dT
H C P .dT
* For an ideal gas
H
0
P T
dH = CP . dT
H C P .dT
RELATIONSHIP BETWEEN H & U

The difference between H & U becomes significant only when gases are involved (insignificant in solids
and liquids)
H = U + (PV)
If substance is not undergoing chemical reaction or phase change.
H = U + nRT
In case of chemical reaction
H = U + ng)RT
CALCULATION OF WORK DONE IN VARIOUS PROCESS

1. Isothermal process
Since dT = 0 dU = 0 for an ideal gas
from Ist law q = w
If process is reversible
V2
W = nRT ln V
1
If process is irreversible
nRT nRT
W = Pext P P
2 1
In case of free expansion pext = 0

W=0
2. Isobaric process
W = Pext (V2 V1)
& H = qp
3. Isochoric process
Since dV = 0 W=0
from 1st law U = q

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4. Adiabatic process :
q=0
P2 V2 P1V1
W = nCv (T2 T1) =
1
for reversible adiabatic process PV = constant.
5. Cyclic process
work done = Area enclose in PV-diagram P W
For clockwise it is ive
For anti-clockwise it is +ive V
SECOND LAW OF THERMODYNAMICS

The essence of first law is that all physical and chemical processes take place in such a manner that the total
energy of the universe remain constant.
However, it is observed that all processes have a natural direction ,i.e. a direction in which they take place
spontaneously. First law fails to answer this. Another feature of the spontaneous processes is that they
proceed only until an equilibrium is achieved.
The direction of a spontaneous process and that it eventually reaches equilibrium, can be understood on the
basis of entropy concept introduced through the second law of thermodynamics.
CARNOT CYCLE
P (P1,V1)A
T2
B (P2,V 2)
q2
(P4,V4)D
T1
C (P3,V3)
q1
V
V2
AB Isothemal reversible expansion q2 = wAB = nRT2 ln V
1
BC adiabatic reversible expansion wBC = CV (T1 T2)
V4
CD Isothemal reversible compression q1 = wCD = nRT1 ln V
3
DA adiabatic reversible compression wDA = CV (T2 T1)
w Total q1 q 2 T2 T1
Carnot efficiency = q q T
2 2 2
q1 q 2

T1 T2 = 0 for rev. cycle

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q rev
T
= dS = 0
Entropy (denoted by S) is a state function.
q rev
S = T
Statements of second law of thermodynamics

(i) No cyclic engine is possible which take heat from one single source and in a cycle completely convert it into
work without producing any change in surrounding.
(ii) In an irreversible process entropy of universe increases but it remains constant in a reversible process.
Ssyt + Ssurr = 0 for rev. process
Ssyt + Ssurr > 0 for irrev. process
Ssyt + Ssurr 0 ( In general )
PHYSICAL SIGNIFICANCE OF ENTROPY

One can think entropy as a measure of the degree of randomness or disorder in a system. The greater the
disorder, in a system, the higher is the entropy.
CALCULATION OF ENTROPY CHANGE

General Expression
T2 V2 T2 P1
S = nCV ln T + nR ln V or nCp ln T + nR ln P
1 1 1 2
Reversible & irreversible isothermal expansion and contraction of an ideal gas

U = 0; H = 0
V2
S = nR ln V
1
Isobaric heating or cooling :

U = CV T
H = CP T = qP
T2
S = nCP ln T
1
Isochoric heating or cooling :
U = CV T = qV
H = CP T
T2
S = nCV ln T
1
Adiabatic process :

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U = CV T
H = CP T
T2 V2
S = nCV ln T + nR ln V for irreversible process
1 1
S = 0 for reversible adiabatic compression and expansion.
THIRD LAW OF THERMODYNAMICS

At absolute zero, the entropy of a perfectly crystalline substance is taken as zero, which means that at
absolute zero every crystalline solid is in a state of perfect order and its entropy should be zero.
By virtue of the third law, the absolute value of entropy (unlike absolute value of enthalpy) for any pure
substance can be calculated at room temperature.
T
q rev
ST S0K =
0 T
since S0K = 0
T
q rev
ST =
0 T
Absolute entropies of various substances have been tabulated and these value are used to calculate entropy
changes for the reactions by the formula;
Sr = PS (products) RS (reactants)
Variation of Sr with temperature & pressure :
T2
Sr T2 Sr T1 = (Cp)r ln T
1
p1
Sr p2 Sr p1 = ngR ln p
2
Similarly
H r T2 H r T1 = (Cp)r (T2 T1) {Krichoff's equation}
U r T2 U r T1 = (Cp)r (T2 T1)
GIBBS FREE ENERGY (G) AND SPONTANEITY:

A new thermodynamic state function G , the Gibbs free energy is defined as :
G = H TS
at constant temperature and pressure
G = H T S
If G)T,P < 0 process is irreversible (spontaneous)
G)T,P = 0 process is reversible
G)T,P > 0 process is impossible (non spontaneous)

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The use of Gibbs free energy has the advantage that it refers to the system only (and not surroundings).
To summaries, the spontaneity of a chemical reaction is decided by two factors taken together:
(i) the enthalpy factor and (ii) the entropy factor.
The equation G = H T S takes both the factors into consideration.
(Hr( (S r ( (
(Gr
T,P T,P T,P Remarks
ve + ve Always ve Reaction is spontaneous
+ ve ve Always + ve Reaction non spontaneous
At low temperature, G = + ve Non spontaneous

+ ve + ve
At high temperature, G = ve Spontaneous
At low temperature, ve Spontaneous

ve ve
At high temperature, +ve Non spontaneous
Variation of Gibb's function (G) with temperature and pressure :

G = H TS
= U + PV TS
dG = dU + PdV TdS + VdP SdT
dG = VdP SdT
* At constant temperature
dG = VdP
G
or P V
T
* At constant pressure
dG = SdT
G
S
T P
Relationship between G & WnonPV
dU = q + WPV + WnonPV
for reversible process at constant T & P
dU + pdV TdS = WnonPV
dH - TdS = WnonPV
(dGsystem)T,P = WnonPV
(dGsystem)T,P = (WnonPV) system
NonPV work done by the system = decrease in gibbs free energy

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Some facts to be remembered :
(a) Standard condition

* For gases / solid / liquid
P = 1 bar
* For ion / substance in solution
concentration =1 M
(b) Gr = (Gf)product (Gf)reactant
Hr = (Hf)product (Hf)reactant
Sr = (Sf)product (Sf)reactant
(All about equation will be derived in thermochemistry)
THERMOCHEMISTRY
Thermochemistry is the branch of physical chemistry which deals with the thermal or heat changes caused
by chemical reactions. It is based on first law of thermodynamics.
ENTHALPY
Chemical reactions are generally carried out at constant pressure (atmospheric pressure) so it has been
found useful to define a new state function Enthalpy (H) as :
H = U + PV
and hence, H = U + (PV)
At constant pressure
H = U + P V
Combining with first law,
H = qp
Hence, transfer of heat at constant pressure brings about a change in the enthalpy of the system.
Enthalpy change, rH of a reaction-Reaction enthalpy-Heat of reaction
The enthalpy change accompanying a reaction is called the reaction enthalpy. It may also be defined as the
amount of heat lost or gained in the chemical reaction, when all the reactants and products are maintained
at the same temperature and pressure. The enthalpy change of a chemical reaction may be given as
rH = (sum of enthalpies of products)-(sum of enthalpy of reactants)
= ( H)products S( H)reactants
where is the stoichiometric coefficients of reactants and products, respectively.
Types of Reactions :
(i) Exothermic Reactions : Heat is evolved during the reaction. For such reactions rH is negative, which
implies that
P H (products) < R H (reactants)

(ii) Endothermic Reactions : Heat is absorved during the reaction. For such reactions rH is positive, which

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implies that
P H (products) > R H (reactants)

Factors affecting DH of the reactions are :
(i) Physical states of reactants & products
(ii) Allotropic forms of elements
(iii) Reaction condition
H = U + ng RT
where H = Heat change of reaction at constant pressure or enthalpy change.
U = Heat change of reaction at constant volume or internal energy change.
ng = Total moles of gaseous products total moles of gaseous reactants.
(iv) Temperature :
H 2 H1
T2 T1 = CP)r (Kirchoff's Equation)
Where C P C P ( products ) C P (reac tan ts)
U 2 U1
T2 T1 = CV)r
Thermochemical Equations : An equation which indicates the amount of heat change in the reaction.
These can be added, subtracted or multiplied whenever required. It indicates the amount of heat change in
the reaction, which is written on the extreme right of the reaction.
for example aA(g) + bB(g) cC(g) + dD(g) DH = x kJ mol1
Hess's law of constant heat summation:

According to Hesss law (a consequence of first law), if a set of reactants is converted into a set of product
by more than one sequence of reactions, the total enthalpy change will be the same for every sequence.
As such, the chemical equations can be treated ordinary algebraic expressions and can be added or subtracted
to yield the required equation. The corresponding enthalpy changes are also manipulated in the same way to
obtain the enthalpy change for the desired equation.
Standard enthalpy of Reaction, rH :

As enthalpy of a reaction depends on the conditions under which a reaction is carried out, it is necessary to
specify some standard conditions. The standard enthalpy of reaction is the enthalpy change for a reaction,
when all the participating substance (reactants and products) are in their standard condition.
The standard condition are :

* Solid / liquid / gas should be at 1 bar
* for substance dissolved in solution concentration should be 1M.
Enthalpy changes in chemical reactions :
(1) Enthalpy of Formation, fH :

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It is the enthalpy change when one mole of a substance is formed from its elements in their most abundant
naturally occuring form (also called reference states). For example, the reference state of oxygen, carbon
and sulphur are O2 gas, Cgraphite and Srhombic , respectively. Some reactions with standard molar enthalpies of
formation are :
1
H2(g) + O (g) H2O(l) ; fH = 285.8 kJ mol1
2 2
By convention, enthalpy of formation fH, of an element in reference state is taken as zero.
The enthalpy of formation can be used to determine the enthalpy change of any reaction as
rH = a i f H(Products) b i f H(reactants)
i i
where ai and bi represent the coefficients of the products and reactants in the balanced chemical equation.
(2) Enthalpy of Combustion, CH :

It is the enthalpy change (always negative) when one mole of the substance undergo complete combustion.
For example
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) ; cH = 890.8 kJ mol1 at 298 K.
(3) Enthalpy changes during phase transformations :

(i) Enthalpy of Fusion, fus.H : It is the enthalpy change that accompanies melting of one mole of a solid
substance at constant temperature (melting point of solid) and pressure.
for example,
H2O(s) H2O(l) ; fusH = + 6.00 kJ mol1
(ii) Enthalpy of Vaporisation, vapH :

It is the amount of heat required to vapourise one mole of a liquid substance at constant temperature
(boiling point of liquid) and pressure for example :
H2O(l) H2O(g) ; vapH = + 40.79 kJ mol1
(iii) Enthalpy of Sublimation, subH :

It is the amount of heat required to sublime one mole of a solid substance at constant temperature (sublimation
temperature of solid) and pressure. For example
CO2(s) CO2(g) ; DsubH = +25.2 kJ mol1
(4) Bond Enthalpies (Bond energies), DbondH :

The bond enthalpy of diatomic molecules like H2, Cl2, O2 etc. may be defined as the enthalpy change
(always positive) when one mole of covalent bonds of a gaseous covalent substance is broken to form
products in the gas phase, under conditions of constant pressure and temperature. For example
Cl2(g) 2Cl(g) ; ClClH = +242 kJ mol1
O2(g) 2O(g) ; O=OH = +428 kJ mol1
In case of polyatomic molecules, bond dissociation enthalpy is different for different bonds within the same
molecule. In such cases, mean bond enthalpy is used. Mean bond enthalpy may be defined as the average
enthalpy change to dissociate a particular type of bond in the compounds.
In gas phase reactions, the standard enthalpy of reaction, rH, is related with the bond enthalpies of
reactants and products as

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rH = bond enthalpies (reactants) bond enthalpies (products)
(5) Ionisation Enthalpy (DiH)

It is the enthalpy change (always positive) when an electron is remove from an isolated gaseous atom in its
ground state under conditions of constant temperature and pressure.
X(g) X+(g) + e
(6) Electron Gain Enthalpy (DegH)

It is the enthalpy change when an electron is added to a natural gaseous atom to convert it into a negative
ion under conditions of constant temperature and pressure.
X(g) + e X(g)
(7) Lattice Enthalpy (DlatticeH)

The lattice enthalpy of an ionic compound is the enthalpy change which occurs when one mole of an ionic
compound dissociates into its ions in gaseous state under conditions of constant temperature and pressure.
Na+Cl(s) Na+(g) + Cl(g) ;
Dlattice H = + 788 kJ mol1
(8) Enthalpy of Atomisation, aH :

It is the enthalpy change (always positive) when one mole of a substance is completely dissociated into
atoms in the gaseous state, under constant pressure and temperature condition.
For example
H2(g) 2H(g) ; aH = 435.0 kJ mol1
CH4(g) C(g) + 4H(g) ; aH = 1665 kJ mol1
(9) Enthalpy of Transition

It is the enthalpy change when one mole of one allotropic form changes to another under conditions of
constant temperature and pressure. For example
C(graphite) C(diamond) DtrsH = 1.90 kJ mol1
(10) Enthalpy of Hydration, hydH :

It is the enthalpy change (always negative) when one mole of an anhydrous (or partly hydrated) compound
combines with the required number of moles of water to form a specific hydrate at the specified temperature
and pressure. For example :
CuSO4(s) + 5H2O(l) CuSO4 5H2O(s) ; (hyd)H = 78.20 kJ mol1
(11) Enthalpy of Solution, solH :

It is the enthalpy change when one mole of a substance is dissolved in a specified amount of solvent under
conditions of constant temperature and pressure. When large volume of solvent is taken, the enthalpy
change is called enthalpy of solution at infinite dilution. For example
NaCl(s) NaCl(aq) ; solH = + 4kJ mol1
or, NaCl(s) Na+ (aq) + Cl(aq) ; solH = + 4kJ mol1
(12) Enthalpy of Neutralisation neutH :
It is the enthalpy change (always negative) when one g-equivalent of an acid and one g-equivalent of a base

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undergo complete neutralisation in aqueous solution and all the reactants & products are at the same
specified temperature and pressure.
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l) ; neutH = 57.7 kJ eq1
The enthalpy of neutralisation of strong acid and strong base is always constant ( 57.7 kJ eq1), independent
from the acid and base taken. However, the magnitude of enthalpy change of neutralisation decreases when
any one of the acid or base taken is weak.
(13) Resonance energy :

It shows the difference in energy of most stable resonating structure and actual resonance hybrid.
Measurement of U and H : calorimetry

The process of measurement of energy changes in the physical or chemical processes is carried out in a
vessel called Calorimeter, which is immersed in a known volume of a liquid, knowing the heat capacity of
the Calorimeter and the liquid in which Calorimeter is immersed, it is possible to determine the heat absorbed
or evolved in the process by measuring temperature changes. Measurements are made under two different
conditions :
(i) At constant volume, qv or U or E
(ii) At constant pressure, qp or H
(i) U measurement : For chemical reactions, heat absorbed at constant volume, is measured in a bomb
Calorimeter. In this Calorimeter, a steel vessel (the bomb) is immersed in a water bath. A combustible
substance is burnt in pure oxygen supplied in the bomb. Heat evolved during the reaction is transferred to
the water around the bomb and its temperature is monitored. Since the bomb Calorimeter is sealed, its
volume does not change, i.e., the energy changes associated with reactions are measured at constant volume.
(ii) H measurement : Measurement of heat change at constant pressure (generally at atmospheric pressure)
can be done in a Calorimeter shown in the figure. In this case, the Calorimeter is left open to atmosphere. As
the reaction occurs in the Calorimeter, the temperature change is noticed and then heat of reaction is

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measured with the knowledge of heat capacity of Calorimeter system.
CHEMICAL EQUILIBRIUM
TYPES OF REACTION:
(i) Reversible :
(ii) Irreversible
STATE OF EQUILIBRIUM
Most of the chemical reaction do not go to completion in a closed system and attain a state of equilibrium.
There are two approaches to understand nature of equilibrium. The One stems from thermodynaics.
Equilibrium criteria is explained on the basis of thermodynamic function like H (change in enthalpy), S
(change in entropy) and G (change in Gibb's function). At equilibrium macroscopic properties of the
system like concentration, pressure ect. become constant at constant temperature.
Other approach comes from kinetics as developed by Guldberg and Waage (1863). Equilibrium is said to
have reached in a physical or chemical system when rate of forward and reverse processes are equal.
At equilibrium
Rate of forward reaction = Rate of backward reaction.
rf
rate
State of
equilibrium
rb
time
Example:
N2(g) + 3H2(g) 2NH3(g)
Starting with pure H2 and N2 as reaction proceeds in forward direction. Ammonia is formed. At initially
conc. of H2 and N2 drops and attain a steady value at equilibrium. On the others hand conc. of NH3
increases and at equilibrium attains a constant value.
Concentration time graphs for

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concentration.
[H2]
[N2]
[NH3]
t
fig (1)
IMPORTANT CHARACTERISTIC OF EQUILIBRIUM

(i) Equilibrium is possible only in closed system.
(ii) The rate of forward process at equilibrium is equal to rate of backward process.
(iii) All measurable properties of system remain constant over time.State of chemical equilibrium is
characterised by equilibrium constant. Equilibrium constant have constant value at a given
temperature.
(iv) At equilibrium entropy of universe is maxmized.
(v) Both, Kinetic and Thermodynamics theories can be invoked to understand the extent to which
a reaction proceed to forward direction. e.g. If extent of reaction is too large for forward direction
(equilibrium is tilted heavily to forward direction) than
(a) Specific rate of forward reaction >>> specific rate of backward reaction
(b) Gibb's function of product is vary small as compared to Gibb's function of reactant.
LAW OF CHEMICAL EQUILIBRIUM OR MASS ACTION (By Guldberg and Waage)

A general equation for a reversible reaction may be written
mA + nB l xC + yD
rate of reaction in inforward direction(rf) [A]m [B]m ; rf = kf [A]m [B]m
rate of reaction in inforward direction(rb) [C]x [D]y ; rb = kb [C]x [D]y
At equilibrium, rf = rb
[ C ] x [ D] y
Keq or Kc = where Kc = kf / kb
[A]m [B]m
where we use [ ] to indicate "molar concentration."
Note : We should calculate the value of K from the activities of the reactants and products rather than from their
concentrations. However, the activity of a dilute solute is usefully approximated by its molar concentration, so
we will use molar concentrations. However, for gases we can use molar concentrations of gases and partial
pressure in our equilibrium calculations, The activity of a pure solid or pure liquid is constant , and the activity
of a solvent in a dilute solution is also constant.Thus these species (solids, liquids, and solvents) are omitted
from reactions quotients and equilibrium calculations.
o o
UNIT OF EQUILIBRIUM CONSTANT (K C , K C , K P & K P )
We have already noted that the value of an equilibrium constant has meaning only when we give the
corresponding balanced chemical equation. Its value changes for the new equation obtained by multiplying
or dividing the original equation by a number. The value for equilibrium constant, KC is calculate substituting
the concentration in mol/L and for KP by substituting partial pressure in Pa, kPa, etc. in atm. Thus, units of
equilibrium constant will turn out to be units based on molarity or pressure, unless the sum of the exponents
in the numerator is equal to the sum of the exponents in the denominator. Thus for the reaction:
H2(g) + I2(g) l 2HI, KC and KP do not have any unit

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N2(g) + 3H2(g) l 2 NH3 , KC has unit (mol/L)2 and KP has unit bar2 or
N2O4 (g) l 2NO2, KC has unit mol / L and KP has unit bar
However, these days we express equilibrium constants in dimensionless quantities by deviding concentration
by 1 M and partial pressure by 1 bar.
* Relationship between KP & KC

KP = KC (RT) ng
TYPE OF EQUILIBRIUM
(a) Homogeneous chemical equilibria
A homogeneous equilibrium is equilibrium with in a single phase i.e. when physical state of all the
reactants and product are same.
(ii) Liquid phase homogeneous equilibrium
Example : (i) I2 (aq) + I (aq) l I3 (aq)
[ I 3 (aq )]
Eq. constants is K=
[ I 2 (aq)][I (aq )]
(iii) Homogeneous equilibria in gases

Example : (i) C2H6(g) l C2H4(g) + H2(g)
Eq. constants is
[C 2 H 4 O)][H 2 ] [PC2H 4 ][PH 2 ]
KC = [C 2 H 6 (g )] KP = [PC2H6 ]
[ ] represents concentration PC2H 4 & other are partial pressure at equilibrium

in mol/ litre at equilibrium
(ii) 3O2(g) l 2O3(g)

Eq. constants is
[O 3 ]2 PO23
KC = KP =
[O 2 ]3 PO3 2
(b) Hetrogeneous equilibria

If reactants and product are found in two or more phases, the equilibria describing them is called
hetrogeneous equilibrium.
Example: CaO(s) + CO2(g) l CaCO3(s)
1 1
Eq. constants is KP = KC =
PCO [CO 2 (g)]
2
CHARACTERSTICS OF EQUILIBRIUM CONSTANT

(i) The expression for equilibrium constant, K is applicable only when concentrations of the reactants and
products have attained their equilibrium values and do not change with time.
(ii) The value of equilibrium constant is independent of initial concentration of the reactants and product.
(iii) Equilibrium constant has one unique value for a particular reaction represented by a balanced equation at a
given temperature.
(iv) The equilibrium constant for the reverse reaction is equal to the inverse of the equilibrium constant for the
forward reaction.
H2(g) + I2(g) 2HI(g)

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PHI 2
Kp = P .P ; 2HI(g) H2(g) + I2(g)
H2 I2
1
KP' = K
P
(v) The equilibrium constant K, for a reaction is related to the equilibrium constant of the corresponding
reaction whose equation is obtained by multiplying or dividing the equation.
1 1
H2(g) + I2(g) 2HI(g) ; H2(g) + I2(g) HI(g)
2 2
PHI
KP" = P1 / 2 .P1/ 2 = Kp
H2 I2
(vi) If reaction is performed is steps

A B ; overall reaction
Step-1 : A(g) C(g) + D(g) K p1
Step-2 : C(g) E(g) K p2
Step-3 : D(g) + E(g) B(g) K p3
A(g) B(g) Kp then Kp = K p1 . K p2 . K p3

APPLICATION OF EQULIBRIUM CONSTANT.
Now we will consider some applications of equilibrium constant and use it to answer question like:
(i) predicting the extent of a reaction on the basis of its magnitude.
(ii) predicting the direction of the reaction, and
(iii) calculating equilibrium concentration.
(i) Predicting the extent of a reaction
The magnitude of equilibrium constant is very useful especially in reactions of industrial importance. An
equilibrium constant tells us whether we can expect a reaction mixture to contain a high or low concentration
of product(s) at equilibrium. (It is important to note that an equilibrium constant tells us nothing about the
rate at which equilibrium is reached). In the expression of KC or KP, product of the concentrations of
products is written in numerator and the product of the concentrations of reactants is written in denominator.
High value of equilibrium constant indicates that product(s) concentration is high and its low value indicates
that concentration of the product(s) in equilibrium mixture is low.
For reaction, H2 (g) + Br2(g) l 2HBr(g), the value of
( PHBr ) 2
KP = 18
( PH )( PBr ) = 5.4 10
2 2
The large value of equilibrium constant indicates that concentration of the product, HBr is very high and
reaction goes nearly to completion.
Similarly, equilibrium constant for the reaction H2(g) + Cl2(g) l 2HCl(g) aty 300 K is very high and reaction
goes virtually to completion.
[ HCl ]2
KC = = 4.0 1031
[ H 2 ][Cl 2 ]
Thus, large value of KP or KC (larger than about 103), favour the products strongly. For intermedicate
values of K (approximately in the range of 103 to 103), the concentrations of reactants and products are
comparable. Small values of equilibrium constant (smaller than 103), favour the reactants strongly.
At 298 K for reaction, N2(g) + O2(g) l 2NO(g)

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[ NO ]2
KC = = 4.8 1031
[ N 2 ][ O 2 ]
The very small value of KC implies that reactants N2 and O2 will be the predominant species in the reaction
mixture at equilibrium.
(ii) Predicting the direction of the reaction.

The equilibrium constant is also used to find in which direction an rabidity reaction mixture of reactants and
products will proceed. For this purpose, we calculate the reaction quotient, Q. The reaction quotient is
defined in the same way as the equilibrium constant ( with molar concentrations to give QC, or with partial
pressure to give QP) at any stage of reaction. For a general reaction:
aA + bB l cC + dD
[C]c [D]d
QC =
[A]a [B]b
Then, if QC > Kc , the reaction will proceed in the direction of reactants (reverse reaction).
if QC < Kc, the reaction will move in the direction of the products
if QC = Kc, the reaction mixture is already at equilibrium.
In the reaction, H2(g) + I2(g) l 2Hl(g), if the molar concentrations of H2 , I2 and HI are 0.1 mol L1
respectively at 783 K, then reaction quotient at this stage of the reaction is
[ HI ]2 (0.4) 2
QC = = =8
[ H 2 ][ I 2 ] (0.1)(0.2)
KC for this reaction at 783 K is 46 and we find that QC < KC. The reaction, therefore, will move to right i.e.
more H 2 (g) and I 2 (g) will react to form more HI (g) and their concentration will decrease till
QC = KC.
(iii) Calculating equilibrium concentration.

(a) A + B C
at time t = 0 a b
at equlb. ax bx x
x
PT
(x / V ) a bx
Kc = ; Kp =
a x b x ax b x
PT PT
V V a b x a b x
(b) Equilibrium constant expressions in term of ''

PCl5(g) PCl3(g) + Cl2(g)
Initial partial pr. 1
At. Eq. 1
[p PCl3 (g ) ][p Cl 2 ( g ) ] 2 1
KP = ; KC =
p [ PCl 5 ( g )] 1 V
. PT
KP =
1 (1 )
2
KP = P
1 2 T
(IV) Degree of dissociation in terms of molar mass and vapour density

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(a) A(g) l nB(g)

M T MO DT DO
or
M O (n 1) D O (n 1)
MT = Theoretical molar mass of reactant
MO = Observed molar mass of mixture
MT MO
DT = and DO =
2 2
(b) nA (g) l An (g)
Initial conn a 0
a
at eqm 1(1)
n
MT MO

1
M O 1
n
FACTOR'S AFFECTING EQUILIBRIA (Le-chatelier's principle)

(i) Effect of change in concentration on equilibrium
A chemical system at equilibrium can be shifted out of equilibrium by adding or removing one more of
reactants or products. Shifting out of equilibrium doesn't mean that value of equilibrium constant change.
Any alteration of concentration of reactant or product will disturb the equilibrium and concentration of
reactant and product one readjust to one again attain equilibrium concentration.
In other word, as we add or remove reactant (or product) the ratio of equilibrium concentration become 'Q'
(reaction quotient) and depending upon.
Q<K : equilibrium will shift in forward direction.
Q >K : equilibrium will shift in backward direction.
Example : Fe3+ (a) + SCN (aq) l Fe (SCN)2+(aq)
[Fe(SCN ) 2 ]
(i) adding Fe3 or SCN will more = Q less then KC and equilibria will shift in forward direction.
[Fe3 ][SCN ]
(ii) Removing Fe(SCN)2+will have same effect
(iii) Adding Fe(SCN)2+from outside source in equilibrium mixture will have effect of increasing 'Q' hence reaction
shift in backward direction.
(ii) Effect of change in pressure

Sometimes we can change the position of equilibrium by changing the pressure on a system. However,
changes in pressure have a measurable effect only in system where gases are involved and then only when
the chemical reaction produces a change in the total number of gas molecules in the system.
As we increase the pressure of a gaseous system at equilibrium, either by decreasing the volume of the
system or by adding more of the equilibrium mixture, we introduce a stress by increasing the number of
molecules per unit of volume. In accordance with Le Chatelier's principle, a chemical reaction that reduces
the total number of molecules per unit of volume will be favored because this relieves the stress. The
reverse reaction would be favoured by a decrease in pressure.
Consider what happens when we increase the pressure on a system in which NO, O2 and NO2 are in
equilibrium.
Example : 2NO(g) + O2 (g) l 2NO2(g)

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The formation of additional amounts of NO2 decreases the total number of molecules in the system, because
each time two molecules of NO2 form, a total of three molecules of NO and O2 react. This reduces the total
pressure exerted by the system and reduces, but does not completely relieve, the stress of the increased
pressure. On the other hand, a decrease in the pressure on the system favors decomposition of NO2 into NO
and O2 which tends to restore the pressure.
Let us now consider the reaction
N2(g) + O2 (g) l 2NO(g)
Because there is no change in the total number of molecules in the system during reaction, a change in
pressure does not favor either formation or decomposition of gaseous nitric oxide.
(iii) Effect of change in temperature on equilibrium
Changing concentration or pressure upsets an equilibrium because the reaction quotient is shifted away
from the equilibrium value. Changing the temperature of a system at equilibrium has a different effect: A
change in temperature changes the value of the equilibrium constant. However, we can predict the effect of
the temperature change by treating it as a stress on the system and applying Le Chatelier's principle. When
hydrogen reacts with gaseous iodine, energy is released as heat is evolved.
H2(g) + I2(g) l 2I(g) H = 9.4 kJ (exothermic)

Because this reaction is exothermic, we can write it with heat as a product.
H2(g) + I2(g) l 2HI(g) + 9.4 kJ

Increasing the temperature of the reaction increases the amount of energy present. Thus, increasing the
temperature has the effect of increasing the amount of one of the products of this reaction. The reaction
shifts to the left to relieve the stress, and there is an increase in the concentration of H2 and I2 and a
reduction in the concentration of HI. When we change the temperature of a system at equilibrium, the
equilibrium constant for the reaction changes. Lowering the temperature in the HI system increases the
equilibrium constant from 50.0 at 400C to 67.5 at 357C. At equilibrium at the lower temperature, the
concentration of HI has increased and the concentrations of H2 and I2 have decreased. Raising the temperature
decreases the value of the equilibrium constant from 67.5 at 357C to 50.0 at 400C.
van't Hoff equation
d(nK) H K2

1
= H
1
(a) = ln
dT RT 2 K1 R T2 T1
(iv) Effect of catalyst on equilibrium
A catalyst has no effect on the value of an equilibrium constant or on equilibrium concentrations. The
catalyst merely increase the rates of both the forward and the reverse reactions to the same extent so that
equilibrium is reached more rapidly.
All of these effects change in concentration or pressure, change in temperature, and the effect of a catalyst
on a chemical equilibrium play a role in the industrial synthesis of ammonia from nitrogen and hydrogen
according to the equation.
N2 + 3H2 l 2NH3
One way to increase the yield of ammonia is to increase the pressure on the system in which N2, H2 and NH3
are in equilibrium or are coming to equilibrium.
N2 (g) 3H2(g) l 2NH3(g)
The formation of additional amounts of ammonia reduces the total pressure exerted by the system and
somewhat reduces the stress of the increased pressure.
Although increasing the pressure of a mixture of N2 , H2 and NH3 increase the yield ammonia, at low
temperatures the rate of formation of ammonia is slow. At room temperature, for example, the reaction is so
slow that if we prepared a mixture of N2 and H2, no detectable amount of ammonia would form during our
lifetime. Attempts to increase the rate of the reaction by increasing the temperature are counterproductive.

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The formation of ammonia from hydrogen and nitrogen is an exothermic process:

N2(g) + 3H2(g) 2NH3(g) H = 92.2 kJ
Thus increasing the temperature to increase the rate lowers the yield. If we lower the temperature to shift
the equilibrium to the right to favour the formation of more ammonia, equilibrium is reached more slowly
because of the large decrease of reaction rate with decreasing temperature.
Part of the rate of formation lost by operating at lower temperatures can be recovered by using a catalyst to
increase the reaction rate. Iron powder is one catalyst used. However, as we have seen, a catalyst serves
equally well to increase the rate of a reverse reaction in this case, the decomposition of ammonia into its
constituent elements. Thus the net effect of the iron catalyst on the reaction is to cause equilibrium to be
reached more rapidly.
A THERMODYNAMIC RELATIONSHIP :
G = G + RT lnQ [Q = Reaction quotient]

G = RT ln Keq (At eqm. (G)T,P = 0)
G = H TS
For Exothermic reaction
r H S
ln Keq = + r
RT R
r S r H
ln K1 = RT ln K
R 1
r S r H
ln K2 = KT
R 2
1/T
K 2 H 1 1
ln K =
1 R T1 T2
EQUILIBRIUM CONSTANT AS PER KINETICS :

Kf
A(g) Kb B (g) + C(g)
d (A)
= Kf [A] Kb [B] [C]
dt
d[ A] K f [B][C]
At eqm =0 Kc
dt Kb [ A]
where k = A e Ea / RT ; A : pre-expotential factor

Ea ( f ) / RT
kf = Af e Ea : activation energy
Ea ( b ) / RT
kb = Ab e
Ea(f) Ea(b)
E a ( f ) / RT P.E.
kf A f .e
Keq = k = E / RT
b A b .e a ( b )
H
Reaction Coordinate

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k = A eH/RT
where H = Ea(f) Ea(b)
H
ln K1 = ln A RT
1
H
ln K2 = ln A RT
2
K 2 H 1 1
ln
K1 R T1 T2
SIMULTANEOUS EQUILIBRIA :
X(s) l A(g) + B(g) K P1 ( x y) x
(x + y) x
Y(s) l A(g) + C(g) K P2 ( x y) y
(y + x) y
K P1 x
Ptotal 2x 2 y
K P2 y
SEQUENTIAL EQUILIBRIUM :
A(s) B (g) + C(g) K C1 ( x )( x y)
ax x xy
y
C(g) D(g) K C2
xy
xy y
PHASE DIAGRAM FOR WATER:
P
Solid Liquid
O Gas

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THE ATLAS
IONIC EQUILIBRIUM
CLASSIFICATION OF SUBSTANCES
On the basis of their dissociation nature :
(i) Strong electrolytes :Substances which are largely dissociatedand are strong electrolytes. e.g. HCl,
H2SO4, HNO3 etc.
(ii) Weak electrolytes Substances which dissociate only to a small extent in aqueous solution.e.g. HCN,
H3BO3 etc.
(iii) Non electrolytes Which do not dissociate.
Note: The above classification of substances in weak electrolyte and strong electrolyte is based on their dissociation
nature in aqueous medium. However, such classification suffers a great drawback in the sense that a

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particular electrolyte, though strong in water, might behave as a weak one when dissolved in some other
solvent or vice-versa. For example, sodium chloride acts as strong electrolyte in water but it acts as weak
electrolyte in methanol. On the other hand, acetic acid a weak electrolyte in water acts as strong electrolyte
in ammonia. NaCl is also strong electrolyte in ammonia.
ARRHENIUS THEORY OF ELECTROLYTE DISSOCIATION

A chemical equilibrium exists between the undissociated electrolyte molecules and the ions that result from
dissociation
Consider ionisation of a weak electrolyte say a monoprotic acid, acid HA
HA l H + + A
Moles before dissociation 1 0 0
Moles after dissociation c(1) c c
where, is degree of dissociation of weak acid HA. Let 'c' mole litre1 be concentration of acid HA, then
[HA] = c (1 ) ; [H+] = c ; [A] = c
According to equilibrium constant expression
[H ][A ] (cc)
Ka =
[HA] c(1 )
c 2
Ka = ....(i)
(1 )
where, Ka is dissociation constant of an acid.
FACTORS INFLUENCING DEGREE OF DISSOCIATION
Moles dissociate d at any time
= Total moles dissolved initially
(1) Nature of solute

(2) Nature of solvent
(3) Temperature
(4) Ostwald dilution law
Consider ionisation of a weak electrolyte say a monoprotic acid, acid HA
HA l H + + A
Moles before dissociation 1 0 0
Moles after dissociation c(1) c c
c 2
Ka = ....(i)
(1 )
where, Ka is dissociation constant of an acid. Since for weak electrolytes, is small and thus, 1 1
Ka
Ka = c2 or a= = KaV ... (ii)
c
where, V is the volume in litre containing 1 mole of electrolyte. Thus it may be concluded that degree of
dissociation of a weak electrolyte is inversely proportional to square root of its concentration.
(5) Common ion effect

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The phenomenon in which degree of dissociation of a weak electrolyte is suppressed by the addition of a
substance having an ion common to weak electrolyte is known as common ion effect.
IONIC PRODUCT OF WATER

Pure water is weak electrolyte and dissociates as:
H2O l H+ + OH
Before dissociation 1 0 0
After dissociation c(1) c c
Applying law of mass action to dissociation equilibrium of water.
[H ][OH ]
Keq =
[H 2O]
where, Keq is dissociation constant or equilibrium constant of water. Since, dissociation of water is too less
and thus, [H2O], i.e., undissociated H2O can be taken as constant, therefore
K [H2O] l [H+] [OH]
Kw = [H+] [OH]
The new constant Kw is known as ionic product of water. The numerical value of Kw increases considerably
with temperature from 0.11 1014 at 0C to 50 1014 at 100C. It is 1.0 1014 at 25C which we will
use frequently. The variation of ionic product of water with temperature is given by
K w2 H [T2 T1 ]
2.303 log = R TT
K w1 1 2
pH CONCEPT
Sorenson used a new term pH [small p, capital H, the H stands for hydrogen ion and the p for 'puissance'
(French), 'potenz' (German) and power (English)] to express the hydrogen ion concentration.
i.e. [H+] = 10 pH
or pH = log [H+]
1
or pH = log
H

Alternatively pH is negative logarithm of magnitude of H+ concentration.

Note : The term pH comes from pure voir hydrogene which implies potential of hydrogen.
One should be very clear that no doubt pH is a measure of acidic nature but as pH goes up, the acidic nature
goes down. Not only the relationship between pH and acidic nature is inverse but also a logarithmic one. A
decrease of a single pH unit corresponds to a ten folds increase in acidic nature and when pH goes down by
two units, acidic nature increases by a factor of 100.
Also hydrogen ion in a solution are not free floating portion of course. They are actually attached to
molecules of solvent. For this reason H+ ions in water are often written as hydronium isons (H3O+) and
acidic nature is expressed in terms of (H3O+) . For simplicity hydrogen ions are simply written as H+ , with
the understanding that H+, ions in solution are always solvated.
Furthermore, Sorenson original definition of pH is still the one most widely used, but it is not complete
satisfactory in all cases. As [H+] increases, the effective concentration of H+ ions becomes progressively
less than might be expected, because of increased inter ionic attractions at the higher concentrations. A
more precise definition of pH is

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pH = log a H
Where, a H is the hydrogen ion activity (or the effective H+ concentration). The H+ activity is obtained by
multiplying [H+] by a suitable activity coefficient based on thermodynamic measurements. They approach
1.0 for very dilute solutions but get smaller as concentration increases.
It is therefore, clear that highly precise pH calculations require the use of activity coefficients but ordinarily
pH is calculated from the simple relationship pH = log [H+], even though it tends to become less valid at
higher concentrations .
SALIENT FEATURES OF PH CONCEPT

1. Theoretically pH values greater than 14 are possible for concentrated strong base and negative pH values
are possible for concentrated strong acids, but it is for dilute solutions that pH scale is most useful. The pH
for concentrated solution should be derived by pH = log a H where a H represents active mass of H+
ions.
2. For any aqueous solution at 25C it must be true that [H+][OH] = 1014
No matter how acidic or basic a solution might be, it must contain H+ and OH ions and the product of
effective molar concentration equal to 1014 or Kw
Also log [H+]+ log [OH] = 14
or log [H+]+ (log [OH] = 14
or pH + pOH = 14
ACIDS AND BASES

The initial classification of substances as acid was suggested by their sour taste (Latin acidus-sour) and
alkalies (alkali-ashes of a plant). Later on different nomenclature and classification of acids and base were
given. Some important ones covering the present syllabus are given ahead.
ARRHENIUS CONCEPT (1880-1890)
(i) An arrhenius acid is a substance which furnishes hydrogen ion (H+ ions) in aqueous solution,
e.g., HCl H+ + Cl (strong acid)
CH3COOH l CH3COO + H + (weak acid)
(ii) An arrhenius base is a substance which furnishes hydroxyl (OH) ions in aqueous solution, e.g.,
NaOH Na+ + OH (strong base)
NH4OH l NH4+ + OH (weak base)
(iii) The strength of an acid or base depends upon its tendency to furnish H+ or OH ions in solution
respectively.
BRONSTED-LOWRY CONCEPT (1923)

(i) A Bronsted acid is proton donor whereas, a Bronsted base is proton acceptor.
(ii) A pair of Bronsted acid-base which differ by a proton is known as conjugate pair of Bronsted
acid and Bronsted base.

Acid H
Conjugate Base Base H
Conjugate acid
HCl Cl NH3 NH4+
C2H2 C2H C2H5 C2H6
C6H5OH C6H5O Al(OH)3 Al(OH)2+ (aq)

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C6H5NH2 C6H5NH3+
LEWIS CONCEPT (1923)

(i) A lewis acid is an electron pair acceptor. A Lewis base is an electron pair donor.
BF3 + NH3 (H3N BF3)
BF3 + F [BF4]
Ag+ + 2CN [Ag(CN)2]
(ii) Simple cations: Fe2+ , Fe3+, K+ etc. are all Lewis acids.
(iii) Compounds whose central atom has incomplete octet : All compounds having central atom
with les than a full of electrons are Lewis acid, e.g. BF3, BCl3, AlCl3, RMgX, MgCl2 etc.
(iv) Lewis base : Compounds having electron pair available for co-ordination show Lewis base
nature, e.g. NH 3 etc.
pH CALCULATUION
Case (i) A weak acid in water

Ka
(a) if is < 0.1, then [H+] K a C .
C
(b) General Expression : [H ] 0.5(K a K a2 4K a C )
Similarly for a weak base, substitute [OH] and Kb instead of [H+] and Ka respectively in
these expressions.
Case (ii) A weak acid and a strong acid : Due to strong acid degree of dissociation of weak acid decreases.
Case (iii) Two (or more) weak acids

The accurate treatement yields a cubic equation. Assuming that acids dissociate to
a negligible extent [ i.e. C x C] [H+] = (K1C1 + K2C2 + ...+ Kw)1/2
Case (iv) When dissociation of water becomes significant:

Dissociation of water contributes significantly to [H+] or [OH] only when for
(i) Strong acids (or bases) : 108M < C < 106M. Neglecting ionisation of water at
106M causes 1% error (approvable). Below 108M, contribution of acid (or base) can be neglected and pH
can be taken to be practically 7.
(ii) Weak acids (or bases) : When KaC < 1012, then consider dissociation of water as well.
Case (v) pH of solution involving a polytropuic acid or base depend upon K1 , K2 . Succesive dissociation can
be neglected.
SALT HYDROLYSIS
The phenomenon of interaction of cations and anions of a salt with H2O in order to produce acidic nature
or alkaline nature is known as salt hydrolysis.
Salt + Water l Acid + Base
The process of salt hydrolysis is actually the reverse process of neutralization.

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(i) Salts of strong acids and strong bases do not undergo hydrolysis.
(ii) Salts of a strong acids and weak bases give an acidic solution.
e.g. NH4Cl when dissolved, it dissociates to give NH4+ ions.
NH4+ + H2O l NH3 + H3O+ ; Kh = [NH3][H3O+] / [NH4+] = Kw/Kb
Important ! In general : Ka(of an acid). Kb(of its conjugate base) = Kw

If the degree of hydrolysis(h) is small (<<1), h = K h /C .
1
pH = (pkw pkb log C)
2
K h K 2h 4K h C
Otherwise h = , [H+] = Ch
2C
(iii) Salts of strong base and weak acid give a basic solution (pH>7) when dissolved in water, e.g. NaCN,
CN + H2O l HCN + OH
[OH] = Ch, h= K h /C
1
pH = (pkw+ pka + log C)
2
(iv) Salts of weak base and weak acid

Assuming degree of hydrolysis to be same for the both the ions,
Kh = Kw / (Ka.Kb), [H+] = [Ka Kw/Kb]1/2
1
pH = (pkw+ pka pkb)
2
(v) Amphiprotic salts

e.g. NAHCO3
1
pH = (pk1+ pk2)
2
Note: Exact treatment of case (iv) & (v) is difficult to solve. So use this assumption in general cases.
Also, degree of anion or cation will be much higher in the case of a salt of weak acid and weak base. This is
because each of them gets hydrolysed, producing H+ and OH ions. These ions combine to form water and
the hydrolysis equilibrium is shifted in the forward direaction.
BUFFER SOLUTIONS
A solution whose pH does not change significantly on addition of a small amount of acid or alkali.
Type of Buffers
1. Simple buffers
(i) A salt of weak acid and weak base in water e.g.CH3COONH4, NH4CN
(ii) Proteins and amino acids
2. Mixed buffers
These are of two types :

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(i) Acidic buffer mixtures ; A weak acid with its conjugate base :
NaHCO3 + H2CO3(H2CO3 ; is weak acid and HCO3 is its conjugate base );
CH3COOH + CH3COONa ; NaH2 PO4 + H3PO4.
The pH of the buffer solution of this category not necessarily lie in between 0 to 7. It may be in the range of
7 to 14 depending upon the dissociation constant of acid.
Henderson's Equation
pH = pKa + log {[salt] / [acid]} for weak acid with its conjugate base.
(ii) Basic buffer mixtures ; A weak base with its conjugate Acid :
NH4OH + NH4Cl ( NH4OH is weak base and NH4+ is its conjugate acid.)
Henderson's Equation
pOH = pKb + log {[salt] / [base]} for weak base with its conjugate acid.
Important : For good buffer capacity, [salt] : [acid] ratio should be as close to one as possible. In such a
case, pH = pKa. (This also is the case at midpoint of titration)
Buffer capacity = (no. of moles of acid (or base) added to 1L) / (change in pH)
INDICATORS
Indicator is a substance which indicates the point of equivalence in a titration by undergoing a change in its
colour. They are weak acids or weak bases.
Theory of Indicators. The ionized and unionized forms of indicators have different colours. If 90 % or
more of a particular form (ionised or unionised) is present, then its colour can be distinclty seen.In general,
for an indicator which is weak acid, HIn l H+ + In, the ratio of ionized to unionized form can be determined
from
[In ]
pH = pKa + log
[HIn]
So, for detectable colour change, pH = pKa 1
This roughly gives the range of indicators. Ranges for some popular indicators are
Table 1 : Indicators
Indicators pH range Colour
acid medium basic medium
Methyl Orange 3.1-4.4 pink yellow
Methyl red 4.2-6.3 red yellow
Litmus 5.5-7.5 red blue
Phenol red 6.8-8.4 yellow red
Phenolphathlene 8.3-10 colourless pink
Thymol blue 1.2-2.8 red yello
Equivalence point. The point at which exactly equivalent amounts of acid and base have been mixed.
Acid Base Titration. For choosing a suitable indicator titration curves are of great help. In a titration
curve, change in pH is plotted against the volume of alkali to a given acid. Four cases arise.
(a) Strong acid vs strong base. The curve is almost vertical over the pH range 3-10.
(b) Weak acid vs strong base. The curve is almost vertical over the pH range 5-10. So, phenolphathlene is
suitable.

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(c) Weak base vs strong acid . The curve is almost vertical over the pH range 9-3. Methyl red or methyl
orange suitable.
(d) Weak acid vs weak base. No sharp change in pH. No suitable indicator.
SOLUBILITY PRODUCT (Ksp).

For sparingly soluble salts (eg. Ag2C2O4) an equilibrium which exists is
Ag2C2O4l 2Ag+ (aq.) C2O42 (aq.)
Then Ksp= [Ag+]2[C2O42]
Common ion effects. Suppression of dissociation by adding an ion common with dissociation products.
e.g. Ag+ or C2O42 in the above example.
Simultaneous solubility. AgCl l Ag+ + Cl K sp

1
AgBr l Ag+ + Br K sp
2
Precipitation. Whenever the product of concentrations (raised to appropriate power) exceeds the solubility
product, precipitation occurs.
Effect of complex formation on solubility.

AgCl (s) l Ag+ (aq) + Cl (aq)Ksp
Ag+ + 2NH3 l Ag(NH3)2+ Kform
Effect of hydrolysis on solubility
MA (s) l M+ (aq) + A (aq) Ksp
Kw
A (aq) + H2O l HA + OH Ka
[H ]
S= K sp 1

K a

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THE ATLAS
Ionic Equilibrium
&
two
&
&
&

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1. General Mistake : pH of a neutral water solution is always equal to 7.

pK w
Explanation : pH of neutral water depend on temperature. Since pH (neutral point) = ; pKw decreases
2
with temperature hence pH of neutral solution.
2. General Mistake : If a solution is diluted half times pH of solution becomes double.

Explanation : Infact pH increases by 0.3010 unit. If it is diluted x times pH increases by log x.
e.g. If solution is diluted 10 times pH increases by log1010 = 1 unit.
3. General Mistake : For calculation of pH of 106 M CH3COOH the formula (H+) = K a c will give pH =
log 1.8 10 5 10 6 = 5.37.

K a K 2a 4K a c
Explanation : 5.37 is incorrect answer. pH should be calculated by taking =
2c
4. General Mistake : If 103 mole CH3COONa and 1 mole CH3COOH is added in 104 litres water the pH of
103
resulting solution is equal to pH = pKa + log = 7.74.
1
Explanation : 7.74 is incorrect answer. The CH3COOH concentration is too low to be taken as constituent
of buffer solution. Use salt hydrolysis formula instead to calculate the pH.
5. General Mistake : The equilibrium concentration of anion and cation of a sparingly soluble salt (A2C3) are
a and c moles lit1 respectively. The solubility product is (2a)2 (3c)3 = Ksp
Explanation : Ksp = a2c3.
6. General Mistake : pH of 108 M HCl is equal to 8.

Explaination : pH = 8 means basic solution. Contribution of water can not be neglected in this case.
7. General Mistake : If NaOH is added to NH4Cl so that NaOH is limiting, the resulting solution is containing
some remaining conc. of NH4Cl. Now use salt hydrolysis condition to calculate pH of solution.
Explanation : The addition of NaOH in NH4Cl results in a basic buffer solution.
8. General Mistake : Do not use the K1K2 form of equation unless you have an independent method of
calculating [H+] or [S2]
Explanation : Determine the [S2] in a saturated H2S solution to which enough HCl has been added to
produce a [H+] of 2 104.
[H ]2 [S2 ] (2 10 4 ) 2 [S2 ]
Sol. : K1K2 = [H S] = = 1.0 1021 or
2 0 .10
1.0 10 22
[S2] = = 2.5 1015.
4 10 8

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ELECTROCHEMISTRY
ELECTROCHEMICAL CELLS
An electrochemical cell consists of two electrodes (metallic conductors) in contact with an electrolyte (an
ionic conductor).
An electrode and its electrolyte comprise an Electrode Compartment.
Electrochemical Cells can be classified as:
(i) Electrolytic Cells in which a nonspontaneous reaction is driven by an external source of current.
(ii) Galvanic Cells which produce electricity as a result of a spontaneous cell reaction
Note: In a galvanic cell, cathode is positive with respect to anode.
In a electrolytic cell, anode is made positive with respect to cathode.
GALVANIC CELL
This cell converts chemical energy into electrical energy.
Galvanic cell is made up of two half cells i.e., anodic and cathodic. The cell reaction is of redox kind.
Oxidation takes place at anode and reduction at cathode. It is also known as voltaic cell. It may be
represented as shown in Fig. Zinc rod immersed in ZnSO 4 behaves as anode and copper rod immersed in
CuSO4 behaves as cathode.
Oxidation takes place at anode:
Zn Zn2+ + 2e (loss of electron : oxidation)
Reduction takes place at cathode:
Cu2+ + 2e Cu (gain of electron ; reduction)
Over all process:
Zn(s) + Cu2+ Cu(s) + Zn2+
In galvanic cell like Daniell cell; electrons flow from anode (zinc rod) to the cathode (copper rod) through
external circuit; zinc dissolves as Zn2+ ; Cu2+ ion in the cathode cell picks up two electron and become
deposited at cathode.
REPRESENTATION OF A CELL ( IUPAC CONVENTIONS ):

Let us illustrate the convention taking the example of Daniel cell.
(i) Anodic half cell is written on left and cathodic half cell on right hand side.
Zn(s) | ZnSO4 (sol) || CuSO4 (sol) | Cu(s)
(ii) Two half cells are separated by double vertical lines: Double vertical lines indicate salt bridge or any type of
porous partition.
(iii) EMF (electromotive force) may be written on the right hand side of the cell.
(iv) Single vertical lines indicate the phase separation between electrode and electrolyte solution.
Zn | Zn2+ || Cu2+ | Cu
(v) Inert electrodes are represented in the bracket
Zn | ZnSO4 || H+ | H2, Pt
RELATIONSHIP BETWEEN G AND ELECTRODE POTENTIAL

Let n, Faraday charge is taken out from a cell of e.m.f. (E) then electrical work done by the cell
may be calculated as,

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Work done = Charge x Potential = nFE

From thermodynamics we know that decrease in Gibbs free energy of a system is a measure of
reversible or maximum obtainable work by the system if there is no work due to volume expansion
G = nFE
Under standard state G0 = nFE0 (i)
(i) From thermodynamics we know, G = negative for spontaneous process. Thus from eq.(i) it is
clear that the EMF should be +ve for a cell process to be feasible or spontaneous.
(ii) When G = positive, E = negative and the cell process will be non spontaneous.
Reactions G E
Spontaneous () (+)
Non- spontaneous (+) ()
Equilibrium 0 0
Standard free energy change of a cell may be calculated by electrode potential data.
Substituting the value of E0 (i.e., standard reduction potential of cathode- standard reduction potential of
anode) in eq. (i) we may get G0.
CONCEPT OF ELECTROMOTIVE FORCE (EMF) OF A CELL

Electron flows from anode to cathode in external circuit due to a pushing effect called or electromotive
force (e.m.f.). EMF is called as cell potential. Unit of e.m.f. of cell is volt.
EMF of cell may be calculated as :
Ecell = reduction potential of cathode Reduction potential of anode
Similarly, standard e.m.f. of the cell (E) may be calculated as
Ecell = Standard reduction potential of cathode Standard
SIGN CONVENTION OF EMF

EMF of cell should be positive other wise it will not be feasible in the given direction .
Zn | ZnSO4 || CuSO4 | Cu E = +1.10 volt (Feasible)
Cu | CuSO4 || ZnSO4 | Zn E = 1.10 volt (Not Feasible)
SALT BRIDGE
Two electrolyte solutions in galvanic cells are separated using salt bridge as represented in the Fig. salt
bridge is a device to minimize or eliminate the liquid junction potential. Saturated solution of salt like KCI,
KNO3, NH4Cl and NH4NO3 etc. in agar-agar gel is used in salt bridge. Salt bridge contains high concentration
of ions viz. K+ and NO3 at the junction with electrolyte solution. Thus, salt bridge carries whole of the
current across the boundary ; more over the K+and NO3 ions have same speed. Hence, salt bridge with
uniform and same mobility of cations and anions completes the electrical circuit & permits the ions to
migrate.
NERNST EQUATION
Walter Nernst derived a relation between cell potential and concentration or Reaction quotient.
G = G + RT ln Q ..(1)
where G and G are free energy and standard free energy change; Q is reaction quotient.
G = nFE and G = nFE
Thus from Eq. (i),we get nFE = -nFE + RT lnQ
0.0591
At 25C, above equation may be written as E E0 log Q
n
Where n represents number of moles of electrons involved in process.
E, E are e.m.f. and standard e.m.f. of the cell respectively.

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In general , for a redox cell reaction involving the transference of n electrons

aA + bB cC + dD, the EMF can be calculated as:
0.0591 [C]c [D]d

ECell = ECell log
n [A ]a [B]b
THERMODYNAMIC TREATMENT OF NERNST EQUATION

(i) Prediction and feasibility of spontaneity of a cell reaction.
Let us see whether the cell (Daniell) is feasible or not: i.e. whether Zinc will displace copper or not.
Zn | (s) | ZnSO4 (sol) || CuSO4 (sol) | Cu(s)
E 0Zn 2 / Zn 0.76volt ; E 0Cu 2 / Cu 0.34volt
E 0 cell E 0Cu 2 / Cu E zn
0
2
/ Zn
=0.34 (0.76) = +1.10 volt

Since E0 = +ve , hence the cell will be feasible and zinc will displace copper from its salt solution. In the
other words zinc will reduce copper.
(ii) Determination of equilibrium constant : We know, that

0.0591
E E0 logQ ..(i)
n
At equilibrium, the cell potential is zero because cell reactions are balanced, i.e. E = 0
From Eq. (i), we have
0.0591 nE 0
0 K eq anti log
0E logK eq or
n 0.0591
(iii) Heat of Reaction inside the cell: Let n Faraday charge flows out of a cell of e.m.f. E, then
G = nFE (i)
Gibbs Helmholtz equation (from thermodynamics ) may be given as,
G
G = H + T T (ii)
p
From Eqs. (i) and (ii), we have
nFE E
nFE HT HnFT
T p T p
E
H nFE nFT
T p
(iv) Entropy change inside the cell : We know that G = H - TS or G = H TS ...(i)
where G = Free energy change ; H = Enthalpy change and S = entropy change.
According to Gibbs Helmoholtz equation,
G
GH T ....(ii)
T p
From Eqs. (i) and (ii), we have

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G G
TST or S
T p T p
E
or SnF
T p
E
where T is called temperature coefficient of cell e.m.f.
p
DIFFERENT TYPES OF HALF-CELLS AND THEIR REDUCTION POTENTIAL

(1) Gas-Ion Half Cell:
In such a half cell, an inert collector of electrons, platinum or graphite is in contact with gas and a solution
containing a specified ion. One of the most important gas-ion half cell is the hydrogen-gas-hydrogen ion
half cell. In this half cell, purified H2gas at a constant pressure is passed over a platinum electrode which is
in contact with an acid solution.
H+(aq) + e l 1/2 H2
E E 0
0.0591
log
pH 2
1/ 2
1 H
H /H H /H
2 2

(2) Metal-Metal Ion Half Cell:
This type of cell consist of a metal M in contact with a solution containing Mn+ ions.
Mn+(aq) + ne l M(s)
0.0591 1
E n
E 0 n
log
M /M M /M n M n

(3) Metal-Insoluble Salt - Anion Half Cell:
In this half cell, a metal coated with its insoluble salt is in contact with a solution containing the anion of the
insoluble salt. eg. Silver-Silver Chloride Half Cell:
This half cell is represented as Cl/AgCl/Ag. The equilibrium reaction that occurs at the electrode is
AgCl(s) + e l Ag(s) + Cl(aq)
0.0591
E Cl / AgCl / Ag E 0Cl / AgCl / Ag log Cl
1
potential of such cells depends upon the concentration of anions. Such cells can be used as Reference Electrode.
(4) Oxidation-reduction Half Cell:
This type of half cell is made by using an inert metal collector, usually platinum, immersed in a solution
which contains two ions of the same element in different states of oxidation. eg. Fe2+ - Fe3+ half cell.
Fe3+(aq) + e l Fe2+(aq)
0 0.0591 [Fe 2 ]
E Fe 3 / Fe 2 E 3 2 log
Fe / Fe 1 [Fe 3 ]
CONCENTRATION CELL
The cells in which electrical current is produced due to transport of a substance from higher to lower
concentration. Concentration gradient may arise either in electrode material or in electrolyte. Thus there
are two types of concentration cell .

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(i) Electrode Gas concentration cell :

Pt, H2(P1) | H+(C) | H2(P2), Pt
Here, hydrogen gas is bubbled at two different partial pressures at electrode dipped in the solution of same
electrolyte.
Cell process : 1 / 2H 2 ( p1 )H (c)e (Anode process)

H (c )e 1 / 2H 2 (p 2 )
1/ 2
1 / 2 H 2 ( p1 ) 1 / 2 H 2 ( p 2 ) 2.303RT p 2
E log
F p1
2.303RT p 2 0.059 p1
or E log
, At 25 C ,
0 E log
2F p1 2F p
2
For spontanity of such cell reaction, p1>p2
(ii) Electrolyte concentration cells:

Zn(s) | ZnSO4 (C1) || ZnSO4 (C2) | Zn(s)
In such cells, concentration gradient arise in electrolyte solutions. Cell process may be given as,
Zn s Zn 2 C1 2e (Anodic process)
Zn 2 (C 2 ) 2e Zn (s)
(Over all process)
Zn 2 (C 2 ) Zn 2 (C1 )
From Nernst equation, we have
2.303RT C1 2.303RT C 2
E0 log or E log
2F C 2 2F C1
For spontanity of such cell reaction, C2> C1
COMMERCIAL VOLTAIC CELLS
Batteries can be classified as primary and secondary. Primary batteries can not be returned to their original
state by recharging, so when the reactants are consumed, the battery is "dead" and must be discarded.
Secondary batteries are often called storage batteries or rechargeable batteries. The reactions in these
batteries can be reversed; thus, the batteries can be recharged.
PRIMARY BATTERIES :
DRY CELLS AND ALKALINE BATTERIES
Zinc serves as the anode, and the cathode is a graphite rod
placed down the center of the device. These cells are often
called "dry cells" because there is no visible liquid phase.
However, water is present, so the cell contains a moist paste
of NH4Cl, ZnCl2 and MnO2. The moisture is necessary because
the ions present must be in a medium in which they can migrate
from one electrode to the other. The cell generates a potential
of
1.5 V using the following half-reactions:

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Cathode, reductions: 2NH4+ (aq) + 2e 2NH3(g) + H2(g)

Anode, Oxidation : Zn (s) Zn2+(aq) + 2 e
The two gases formed at the cathode will build up pressure and could cause
the cell to rupture. This problem is avoided, however, by two other reactions
that take place in the cell. Ammonia molecules bind to Zn2+ ions, and hydrogen
gas is oxidized by MnO2 to water.
Zn2+(aq) + 2NH3(g) + 2Cl (aq) Zn(NH3)2 Cl2(s)
2MnO2 (s) + H2 (g) Mn2O3(s) + H2O(l)
LeClanche cells were widely used because of their low cost, but they have several disadvantages. If current
is drawn from the battery rapidly, the gaseous products cannot be consumed rapidly enough, so the cell
resistance rises, and the voltage drops. In addition, the zinc electrode and ammonium ions are in contact in
the cell, and these chemicals react slowly. Recall that zinc reacts with acid to form hydrogen. The ammonium
ion, NH4+ (aq), is a weak Bronsted acid and reacts slowly with zinc. Because of this reaction, these voltaic
cells cannot be stored indefinitely. When the zinc outer shell deteriorates, the battery can leak acid and
perhaps damage the appliance in which it is contained.
At the present time alkaline batteries are used the chemistry of alkaline cells is quite similar to that in a
LeClanche cell, except that the material inside the cell is basic (alkaline). Alkaline cells use the oxidation of
zinc and the reduction of MnO2 to generate a current, but NaOH or KOH is used in the cell instead of the
acidic salt NH4Cl.
Cathode, reductions: 2MnO2 (s) + H2O(l) + 2e Mn2O3(s) + 2OHO(aq)
Anode, Oxidation : Zn (s) + 2OH(aq) ZnO(s) + H2O(l) + 2 e
Alkaline cells, which produce 1.54 V (approximately the same voltage as the LeClanche cell) , have the
further advantage that the cell potential does not decline under high current loads because no gases are
formed.
SECONDARY OR RECHARGEABLE BATTERIES

An automobile battery the lead storage battery is probably
the best - known rechargeable battery figure. The 12 -V version
of this battery contains six voltaic cells, each generating about
2V. The lead storage battery can produce a large initial current,
an essential feature
when starting an automobile engine.
When the cell supplies electrical energy, the lead anode is oxidized to lead (II) sulfate, an insoluble substance
that adheres to the electrode surface. The two electrons produced per lead atom move through the external
circuit to the cathode, where PbO2 is reduced to Pb2+ ions that, in the presence of H2SO4,also form lead (II)
sulfate.
Cathode, reduction : PbO2 (s) + 4H+(aq) + SO42 (aq) + 2e PbSO4(s) + 2 H2O(l)

Anode, oxidation : Pb(s) + SO42 (aq) PbSO4(s) + 2e
----------------------------------------------------------------------
Net ionic equation Pb(s) + PbO2(s) + 2H2SO4(aq) 2PbSO4(s) + 2H2O(l)

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Nickel - Cadmium ("Ni - Cad") batteries, used in variety of cordless appliances such as telephones,
video camcorders, and cordless power tools, are lightweight and rechargeable. The chemistry of the cell
utilizes the oxidation of cadmium and the reduction of nickel (III) oxide under basic conditions. As with the
lead storage battery, the reactants and products formed when producing a current are solids that adhere to
the electrodes.
Cathode, reduction : NiO(OH) (s) + H2O(l) + e Ni(OH)2(s) + OH(aq)

Anode, Oxidation: Cd(s) + 2 OH Cd(OH)2(s) + 2e
FUEL CELLS AND HYBRID CARS
An advantage of voltaic cells is that they are small and portable, but their size is also a limitation. The
amount of electric current produced is limited by the quantity of reagents contained in the cell. When one of
the reactants is completely consumed, the cell will no longer generate a current. Fuel cells avoid this limitation
because the reactants (fuel and oxidant) can be supplied continuously toe the cell from an external reservoir.
In a Hydrogen - Oxygen fuel cell figure, hydrogen is pumped onto the anode of the cell, and O2 (or air) is
directed to the cathode where the following reactions occur :
Cathode, reduction : O2(g) + 2 H2O(l) + 4 e 4OH(aq) E = 1.23 V
Anode, Oxidation : +
H2(g) 2H (aq) + 2 e E = 0 V
Schematic diagram
of a modern
hydrogen-oxygen
fuel cell.
Commonly used
electrolytes are
NaOH solution,
phosphoric acid, or
solid oxides. A
major limitation of
any oxygen-
consuming fuel cell
is the slow rate of
the reduction of
this element at a
cathode. The best
cathode surfaces
are usually made
of platinum, which
is a major cost
factor in fuel cell
design.
CORROSION CELLS AND REACTIONS
Corrosion can be defined as the deterioration of materials by chemical processes. Of these, the most important
by far is electrochemical corrosion of metals, in which the oxidation process M M++e is facilitated by
the presence of a suitable electron acceptor, sometimes referred to in corrosion science as a depolarizer.

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In a sense, corrosion can be viewed as the spontaneous return of metals to their ores; the huge quantities of
energy that were consumed in mining, refining, and manufacturing metals into useful objects is dissipated by
a variety of different routes.
The special characteristic of most corrosion processes is that the oxidation and reduction steps occur at
separate locations on the metal. This is possible because metals are conductive, so the electrons can flow
through the metal from the anodic to the cathodic regions. The presence of water is necessary in order to
transport ions to and from the metal, but a thin film of adsorbed moisture can be sufficient.
A corrosion system can be regarded as a short-circuited electrochemical cell in which the anodic process is
something like
Fe(s) Fe2+(aq) + 2 e
and the cathodic steps can be any of
O2 + 2 H2O + 4e 4 OH
H+ + e H2(g) M2+ + 2 e M(s)
where M is a metal. Which parts of the metal serve as anodes and cathodes can depend on many factors, as
can be seen from the irregular corrosion patterns that are commonly observed. Atoms in regions that have
undergone stress, as might be produced by forming or machining, often tend to have higher free energies,
and thus tend to become anodic.
CONTROL OF CORROSION
Since both the cathodic and anodic steps must take place for corrosion to occur, prevention of either one
will stop corrosion. The most obvious strategy is to stop both processes by coating the object with a paint
or other protective coating. Even if this is done, there are likely to be places where the coating is broken or
does not penetrate, particularly if there are holes or screw threads.
A more sophisticated approach is to apply a slight negative charge to the metal, thus making it more difficult
for the reaction M M2+ + 2 e to take place.
SACRIFICIAL COATINGS
One way of supplying this negative charge is to apply a coating of a more active metal. Thus a very common
way of protecting steel from corrosion is to coat it with a thin layer of zinc; this process is known as
galvanizing.The zinc coating, being less noble than iron, tends to corrode selectively. Dissolution of this
sacrificial coating leaves behind electrons which concentrate in the iron, making it cathodic and thus inhibiting
its dissolution.
The effect of plating iron with a less active metal provides an interesting contrast. The common tin-plated
can (on the right) is a good example. As long as the tin coating remains intact, all is well, but exposure of
even a tiny part of the underlying iron to the moist atmosphere initiates corrosion. The electrons released
from the iron flow into the tin, making the iron more anodic so now the tin is actively promoting corrosion
of the iron! You have probably observed how tin cans disintegrate very rapidly when left outdoors.
CATHODIC PROTECTION
A more sophisticated strategy is to maintain a continual negative electrical charge on a metal, so that its
dissolution as positive ions is inhibited. Since the entire surface is forced into the cathodic condition, this
method is known as cathodic protection. The source of electrons can be an external direct current power
supply (commonly used to protect oil pipelines and other buried structures), or it can be the corrosion of

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another, more active metal such as a piece of zinc or aluminum buried in the ground nearby.
ELECTROLYSIS
The decomposition of electrolyte solution by passage of electric current, resulting into deposition of metals
or liberation of gases at electrodes is known as electrolysis.
ELECTROLYTIC CELL
This cell converts electrical energy into chemical energy.
The entire assembly except that of the external battery is
known as the electrolytic cell
ELECTRODES
The metal strip at which positive current enters is called anode; anode is positively charged in electrolytic
cell. On the other hand, the electrode at which current leaves is called cathode. Cathodes are negatively
charged.
Anode Positive Loss of electron Positive
or oxidation current
takes place enters
Cathode Negative Gain of electron Current
or reduction leaves
takes place
ELECTROLYSIS OF MOLTEN SODIUM CHLORIDE
NaCl(molten) Na+ + Cl
Reactions at anode (oxidation) : cathode (reduction)

2Cl Cl2(g) + 2e : 2Na+ + 2e 2Na(l)
There are two types of electrodes used in the electrolytic cell, namely attackable and non - attackable. The
attackable electrodes participitate in the electrode reaction. They are made up of reactive metals like Zn,
Cu, Ag etc. In such electrodes, atom of the metal gets oxidised into the corresponding cation, which is
passed into the solution. Thus, such anodes get dissolved and their mass decreases. On the other hand, non-
attackable electrodes do not participate in the electrode reaction as they made up of unreactive elements
like Pt, graphite etc. Such electrodes do not dissolve and their mass remain same.
FARADAYS LAWS OF ELECTROLYSIS:
(i) First law of electrolysis :
Amount of substance deposited or liberated at an electrode is directly proportional to amount of charge
passed (utilized) through the solution.
wQ
W = weight liberated, Q = charge in coulomb
w = ZQ
Z = electrochemical equivalent
when Q = 1 coulomb, then w = Z
Thus, weight deposited by 1 coulomb charge is called electrochemical equivalent.
Let 1 ampere current is passed till t seconds .
Then, Q = It w = ZIt
1 Faraday = 96500 coulomb = Charge of one mole electrons
One faraday is the charge required to liberate or deposit one gm equivalent of a substance at corresponding
electrode.

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Let E is equivalent weight then E gm will be liberated by 96500 coulomb.

E E
1 Coulomb will liberate gm ; By definition, Z
96500 96500
ItE
W
96500
When a gas is evolved at an electrode, then above formula changes as,
ItV e
V
96500
where V = volume of liberated gas, Ve = equivalent volume of gas.
Equivalent volume may be defined as:
The volume of gas liberated by 96500 coulomb at STP.
(ii) Second law of electrolysis :
When same amount of charge is passed through different electrolyte solutions connected in series then
weight of substances deposited or dissolved at anode or cathode are in ratio of their equivalent
weights. i.e. w1/w2 E1/E2
QUALITATIVE ASPECTS OF ELECTROLYSIS

In the electrolysis process we have discussed above, we have taken molten salt as electrolyte, which contains
only one cation and anion. Now, if the electrolyte taken contains more than one cation and anion (for
example, aqueous solution of the ionic electrolyte), then the cation and anion that will get discharged
depends on the ability of cation to get reduced and the ability of anion to get oxidised.
The ability of an ion to get oxidised or reduced depends upon the size, mass, positive charge, negative charge
etc. Thus, it is not possible to predict qualitatively that which ion would be discharged first, as one factor might
enhance the ability to discharge while the other factor may hamper it. This can only be predicted on the basis
of quantitative value assigned based on the cumulative effect of all the factors responsible for an ion's ability to
discharge. The value is referred as standard potential, which is determined by keeping the concentration of ion
as 1 M, pressure of gas at 1 atm, and the measurement done at 25C. For a cation, the standard reduction
potential (SRP) values are compared. The cation having higher standard reduction potential value is discharged
in preference to cation with lower SRP value provided the ions are at 1 M concentration. For an anion, the
standard oxidation potential (SOP) values are compared and anion having higher SOP is preferentially discharged,
if the concentration is 1 M for each of the ion. The SRP values at 25C for some of the reduction half reactions
are given in the table below.
S.NO. Reduction half cell reaction E in volts at 25C
1. F2 + 2e 2F + 2.65
2. S 2 O 82 + 2e 2SO 24 + 2.01
3+ 2+
3. Co + e Co + 1.82
4. PbO2 + 4H+ + SO 24 + 2e PbSO4 + 2H2O + 1.65
5. MnO 4 + 8H+ + 5e Mn2+ + 4H2O + 1.52
6. Au3+ + 3e Au + 1.50
7. Cl2 + 2e 2Cl + 1.36
8. Cr2 O 72 + 14H+ + 6e 2Cr3+ + 7H2O + 1.33
9. O2 + 4H+ + 4e 2H2O + 1.229
10. Br2 + 2e 2Br + 1.07
11. NO 3 + 4H+ +3e NO + 2H2O + 0.96
12. 2Hg2+ + 2e Hg22 + 0.92

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13. Cu2+ + I + e CuI + 0.86

14. Ag+ + e Ag + 0.799
15. Hg 22 + 2e 2 Hg + 0.79
3+ 2+
16. Fe + e Fe + 0.77

17. I2 + 2e 2I + 0.535
+
18. Cu + e Cu + 0.53
2+
19. Cu + 2e Cu + 0.34

20. Hg2Cl2 + 2e 2Hg + 2Cl + 0.27

21. AgCl + e Ag + Cl + 0.222
2+ +
22. Cu + e Cu + 0.15
4+ 2+
23. Sn + 2e Sn + 0.13
+
24. 2H + 2e H2 0.00
25. Fe3+ + 3e Fe 0.036
S.NO. Reduction half cell reaction E in volts at 25C
2+
26. Pb + 2e Pb 0.126
2+
27. Sn + 2e Sn 0.14

28. AgI + e Ag + I 0.151
2+
29. Ni + 2e Ni 0.25
2+
30. Co + 2e Co 0.28
2+
31. Cd + 2e Cd 0.403
3+ 2+
32. Cr + e Cr 0.41
2+
33. Fe + 2e Fe 0.44
34. Cr3+ + 3e Cr 0.74
35. Zn2+ + 2e Zn 0.762

36. 2H2O + 2e H2 + 2OH 0.828
2+
37. Mn + 2e Mn 1.18
3+
38. Al + 3e Al 1.66

39. H2 + 2e 2H 2.25
2+
40. Mg + 2e Mg 2.37
+
41. Na + e Na 2.71
2+
42. Ca + e Ca 2.87
2+
43. Ba + 2e Ba 2.90
44. Cs+ + e Cs 2.92
+
45. K + e 2.93
+
46. Li + e Li 3.03
When solution of an electroyte contains more than one type of cations and anions at concentrations
different than 1 M, the discharge of an ion does not depend solely on standard potentials but also
depends on the concentration of ion in the solution. This value is refered as potential, called as reduction
potential for cation and oxidation potential for anion. The relation between reduction potential and
standard reduction potential is given by Nernst equation, as
RT [concentration of product ]
ERP = ERP ln
nF [concentration of reac tan t ]
where ERP = Reduction potential of cation and ERP = Standard reduction potential of cation.
Thus, it is possible that a cation (A+) with lower standard reduction potential getting discharged in
preference to cation (B+) having higher standard reduction potential because their concentration might
be such that the reduction potential of A+ is higher than that of B+.
When two metal ions in the solution have identical values of their reduction potentials, the simultaneous

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deposition of both the metals will occur in the form of an alloy.
CONDUCTANCE
Introduction: Both
metallic and electrolytic conductors obey Ohm's law
i.e. V = IR
where V = Potential difference in volt; I = Current in ampere ; R = resistance in Ohm
We know, resistance is directly proportional to length of conductor and inversely proportional to c r o s s
sectional area of the conductor.
l l
R or R ( = Specific resistance )
A A
Specific resistance is the resistance of a conductor having lengths of 1 cm and cross sectional
area of 1 cm2.
Unit of R is ohm and unit of specific resistance is ohm cm
Reciprocal of resistance is called as conductance and reciprocal of specific resistance is called as specific
conductance.
1 1A A
or CK
R l l
where C = conductance ohm1 ; K = specific conductance ohm1cm1 .
Mho and siemens are other units of conductance
l
K C
A
Specific conductance= Cell constant x Conductance
SPECIFIC CONDUCTANCE IS CONDUCTANCE OF 1 CM3 OF AN ELECTROLYTE SOLUTION.

In case of electrolytic solution, the specific conductance is defined as the conductance of a solution of
definite concentration enclosed in a cell having two electrodes of unit area separated by 1 cm apart.
1. Equivalent Conductance
Equivalent conductance is the conductance of an electrolyte solution containing 1 gm equivalent
of electrolyte. It is denoted by .
=Kx V
( = ohm cm1 x cm3 = ohm1 cm2)
1
Usually concern ration of electrolyte solution is expressed as C gm equivalent per litre.

1000
Thus, V
C
Volume having1 gm equivalent electrolyte in the solution Thus, K 1000
C
2. Molar Conductance
Molar conductance may be defined as conductance of an electrolyte solution having 1 gm mole
electrolyte in a litre. It is denoted by m .
m=KV
Usually concentration of electrolyte solution is expressed as M gm mole elecrtrolyte per litre.
1000
Thus, V
M
1000
Hence, m K x
M
Relation between and m : m= n

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DETERMINATION OF 0m OR 0
A plot of m vs C as found experimentally is as shown below graphically..
The m vs C plot of strong electrolyte being linear it can be extrapolated to zero concentration. T h u s ,
m values of the solution of the test electrolyte are determined at various concentrations the concentrations
should be as low as good.
m values are then plotted against C when a straight line is obtained. This is the extrapolated to zero
concentration. The point where the straight line intersects m axis is 0m of the strong electrolyte.
However, the plot in the case weak electrolyte being non linear, shooting up suddenly at some low
concentration and assuming the shape of a straight line parallel to m axis. Hence extrapolation in this case
is not possible. Thus, 0 of a weak electrolyte cannot be determined experimentally. It can, however, be
done with the help of Kohlrausch's law to be discussed later.
Kohlrausch's Law of Independent Migration of Ions
Kohlrausch determined 0 values of pairs of some strong electrolytes containing same cation say KF and
KCl, NaF and NaCl etc., and found that the difference in 0 values in each case remains the same:
0m (KCl) 0m (KF) = 0m (NaCl) 0m (NaF)
He also detemined 0 values of pairs of strong electrolytes containing same anion say KF and NaF, KCl and
NaCl etc.and found that the difference in 0 values in each case remains the same.
0m (KF) 0m (NaF) = 0m (KCl) 0m (NaCl)
This experimental data led him to formulate the following law called Kohlrausch's law of independent
migration of ions.
At infinite dilution when dissociation is complete, every ion makes some definite contribution towards
molar conductance of the electrolyte irrespective of the nature of the other ion which with it is associated
and that the molar conductance at infinite dilution for any electrolyte is given by the sum of the contribution
of the two ions. Thus,
0m = 0 0
Where 0 is the contribution of the cation and 0 is the contribution of the anion towards the molar conductance
at infinite dilution. These contributions are called molar ionic conductances at infinite dilution. Thus, 0 is the
molar ionic conductance of cation and 0 is the molar ionic conductance of anion, at infinite dilution. The
above equation is, however, correct only for binary electrolyte like NaCl, MgSO4 etc.
Application of Kohlrausch's law :
(1) Determination of 0m of a weak electrolyte:

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In order to calculate 0m of a weak electrolyte say CH3COOH, we determine experimentally 0m values of

the following three strong electrolytes:
(a) A strong electrolyte containing same cation as in the test electrolyte, say HCl
(b) A strong electrolyte containing same anion as in the test electrolyte, say CH3COONa
(c) A strong electrolyte containing same anion of (a) and cation of (b) i.e. NaCl.
0m of CH3COOH is then given as:
0m (CH3COOH) = 0m (HCl) + 0m (CH3COONa) 0m (NaCl)

Proof:
0
0m (HCl) = H Cl ......................(i)
0
0m (CH3COONa) = CH3COO Na ......................(ii)
0 0
0m (NaCl) = Na Cl ......................(iii)
Adding equation (i) and equation (ii) and subtracting (iii) from them:
0 0 0
0m (HCl) + ( CH 3COONa ) ( NaCl) (H ) (CH3COO0 ) 0( CH3COOH)
0
(2) Determination of degree of dissociation () :

No. of moleculesionised
= m
total numberof moleculesdissolved 0m
(3) Determination of solubility of sparingly soluble salt
The specific conductivity of a saturated solution of the test electrolyte (sparingly soluble) made in conductivity
water is determined by the method as described above. From this the specific conductivity of conductivity
water is deducted. The molar conductance of the saturated solution is taken to be equal to 0m as the
saturated solution of a sparingly soluble salt is extremely dilute. Hence from equation (4).
1000
0m = ,
C
where C is the molarity of solution and hence the solubility.

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ATLAS

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CHEMICAL KINETICS
CHEMICAL KINETICS :
It is a branch of physical chemistry deals with the "Rate of Chemical Reactions" including the effect of temperature,
pressure, concentration, etc., on the rates, and the mechanism by which the reaction takes place.
RATE OF CHEMICAL REACTION is defined as the change in concentration of a reactant (or a product) in a
particular time interval.
For a general reaction carried out at constant volume.

aA + bB cC + dD,
Decrease in conc. of A d [A ] [A]
The rate of disappearance of A = = or
Time taken dt t
Decrease in conc. of B d [B] [B]

Rate of disappearance of B = = or
Time taken dt t
Increase in conc. of C d [C] [C ]

Rate of appearance of C = = or
Time taken dt t
Increase in conc. of D d [ D] [ D]
Rate of appearance of D = = or
Time taken dt t
The positive sign shows that concentrations of C and D increases with time and the negative sign indicates
that concentrations of A and B decreases with time.
Units of Rate are unit of concentration divided by the unit of time (mol L1 s1 ormol L1 min1
or so on).
1 d[ A ] 1 d[ B] 1 d[C] 1 d[ D]
Rate of reaction : = = = .
a dt b dt c dt d dt
All the above rates can be further classified into
1. Average rate. The rate of reaction measured over a long time interval is called average rate of
reaction. It is equal to x/t as shown in fig.(a).
[R]0
[P]
[R] [C2 C1] d[P]

concentration
concentration
rav= = slope =rinst=

C1 t [t2 t1 ] dt
C2
t1 t2 time time
(a) (b)
Average & Instantaneous rate of reaction
2. Instantaneous rate. It is the rate of reaction when the average rate is taken over a very small
interval of time. It is equal to dx / dt as shown in fig.(b).

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FACTORS AFFECTING REACTION RATES :

(i) Nature of reaction components
(ii) Concentration of reactants
(iii) Reaction temperature
Besides these presence of catalyst, surface area, intensity of light also affect the reaction rates depending
upon reactions.
RATE LAW AND RATE CONSTANT :

An expression which relates the rate of a reaction to the active masses of the reactions component
is called the Rate law.
Consider a general reaction
aA + bB cC + dD
Rate (aA)x (aB)y
= k (aA)x (aB)y
where
aA = active mass of component 'A'
aB = active mass of component 'B'
x & y can have any numerical value.
Active mass for gases can be replaced either by molar concentration or partial pressure.
Active mass for substance dissolved in a solvent can be replaced by molar concentration.
Active mass for solids / pure liquid / solvent is constant.
The constant of proportionality, 'k' is known as the Rate Constant (or specific reaction rate) and may be
defined as the rate at unit concentrations of the reactants. For a particular reaction 'k' depends only on the
temperature, catalytic condition and is independent of the initial concentrations of the reactants. At a fixed
temperature, 'k' is constant characteristic of the reaction. Large value of 'k' indicates fast reaction and small
'k' indicates slow reactions.
ORDER OF REACTION :
It is defined as the sum of the exponents (powers) of the molar concentrations of the reaction components
in the experimentally determined rate equations.
If rate [A]p [B]q [C]r
Rate = k [A]p [B]q [C]r
Order of reaction = p + q + r
The order w.r.t. A, B & C are p, q & r respectively.
For a "Reaction of nth order", the order of the reaction is n and the rate equation (or Rate law) is
rate [A]n = k [A]n.
The order of a reaction is obtained from the experimentally determined rate law and may be zero, an integer
or a fraction.
MOLECULARITY :
The number of reacting species (atoms, ions or molecules) taking part in an elementary reaction, which
must collide simultaneously in order to bring about a chemical reaction is called molecularity of a reaction.
The reaction can be unimolecular when one reacting species is involved, for example, decomposition of
ammonium nitrite.
NH4NO2 N2 + 2H2O
Bimolecular reactions involve collision between two species, for example, dissociation of hydrogen iodine.
2HI H2 + I2
Trimolecular or termolecular reactions involve simultaneous collision between three reacting species, for

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example,
2NO + O2 2NO2
Molecularity of a reaction is :
(i) Always a whole number (not zero) and never a fraction.
(ii) The probability that more than three molecules can be collide and react simultaneously is very
small. Hence, the molecularity greater than three is not observed.
Thus, from the above discussion we can conclude the following:
(a) Order of a reaction is an experimental quantity. It can be zero and even a fraction but
molecularity cannot be zero or a non integer.
(b) Order is defined to elementary as well as complex reactions whereas molecularity is
defined only for elementary reactions. For complex reaction molecularity has no
meaning.
(c) For an elementary reaction order and molecularity are same.
ZERO ORDER REACTIONS

Consider of general reaction.
nA products
Rate = k [A]
[A]t = [A]0 kt.
Characteristics of zero order reactions:
(i) Concentration of reactant decreases linearly with time.
(ii) Units of k are mol l1 time1.
[ A ]0
(iii) Time required for the completion of reaction is
k
[A ]0
(iv) t1/2 =
2k
(v) Zero order reaction must be complex reaction
(vi) Graph related with zero order reactions.
conc. conc. Rate t1/2

[P]
[A]
time time time a
Examples :
(i) H2(g) + Cl2 (g) h 2HCl (g)
hot Pt . 1
(ii) N2O(g) N2 (g) + O (g)
Surface 2 2
Mo or W
(iii) 2NH3 (g) N2 + 3H2
surface
(iv) Enzyme catalysed reaction
Substrate(S) Enzyme

( E)
product(P).
FIRST ORDER REACTIONS

Consider of general reaction.

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nA products
at time t = 0 concentration of A = a or [A]0
at time t = t concentration of A = (a x) or [A]t
Rate [A]
d[A] dx
= k [A] or = k(a x)
dt dt
Exponential form of 1st order equation is [A]t = [A]0 e kt
2.303 a
or k= log .
t ax
Characteristics of First Order Reaction :

(i) Unit of rate constant is time1.
0.693
(ii) t1/2 = (Half-life)
k
k
(iii) log (a x) v/s t is a straight line with slope .
2.303
(iv) Graph related with first order reactions.
conc. conc. Rate

[P]
[A]
time time time
t1/2 In [A]t
a t
Examples:
(i) Radioactive disintegration is a first order reaction.

H catalysed hydrolysis
(ii) C12H22O11 + H2O C6H12O6 + C6H12O6.
Inversion
(glucose) (fructose)
(iii) Mineral acid catalyzed hydrolysis of esters.
(iv) Decomposition of H2O2 in aqueous solution.
SECOND ORDER REACTION :

(i) For the given reaction.
nA products
dx
Differential rate equation = k(a x )2
dt
1 x 1 1
Integrated rate equation k = . or kt = .
t a (a x ) ax a
(ii) For the given reaction.

A + B products
at time t = 0 a b

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at time t = t ax bx
dx
differential rate equation =k (a x) (b x).
dt
2.303 b(a x)
Integrated rate equation k = log10
t (a b) a (b x )
1 1
If a = b , then kt =
ax a
Characteristics of Second Order Reaction :

(i) Unit of rate constant L mol1 time 1.
(ii) t1/2 a1 (In general t1/2 a(1n); n = order of reactions).
(iii) 2nd order reaction conforms to first order when one of the reactant in excess.
t1/2
slope = k
1/[A]
1/[A]0
t 1/a
Examples:
(i) Saponification (hydrolysis of esters catalysed with alkali).
CH3COOC2H5 + NaOH CH3COONa + C2H5OH
(ii) Hydrogenation of ethane C2H4+ H2 100
C
C2H6.
(iii) 2 O3 3 O2.
nth ORDER REACTION.

Consider the reaction
nA Product
1 1 1
kt = n 1 n 1
n 1 [n 1, n = order]
a x a
1 2 n 1 1
.
t1/2 = k ( n 1) n 1
a
n1
1/[A] t1/2
slope = (n 1)
n1
1/[A]0
t 1/an1
METHODS OF DETERMINATION OF ORDER OF REACTIONS :

A few methods commonly used are given below :
1. Hit & Trial Method : It is method of using integrated rate equations, where the experimental
values of a, x & t are put into these equations. One which gives a constant value of k for different
sets of a, x & t correspond to the order of the reaction.
2. Graphical Method :

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(i) A plot of log (a x) versus 't' gives a straight line for the First order reaction.
(ii) A plot of (a x) (n1) versus 't' gives a straight line any reaction of the order n
(exceptn = 1).
3. Half Life Method : The half life of nth order reaction is given by t1/2 1/an1
By experimental observation of the dependence of half life on initial concentration we can determine
log( t1 / 2 ) 2 log( t1 / 2 )1
n, the order of reaction. n = 1 + .
log(a 0 )1 log( a 0 ) 2
4. Initial rate method. Initial rate method is used to determine the order or reaction in cases
where more than one reactant is used. It involves the determination of the order of different
reactants separately. A series of experiments are performed in which concentration of one particular
reactant is varied whereas conc. of other reactants are kept constant. In each experiment the
initial rate is determined from the plot of conc. vs. time, e.g., if conc. of A is doubled, and initial
rate of reaction is also doubled, order of reaction w.r.t A is 1.
CALCULATION OF FIRST ORDER RATE CONSTANT USING DIFFERENT PARAMETERS

(I) In terms of pressure
A(g) B (g) + C(g)
2.303 P0
k= log
t 2P0 PT
where
P0 = Initial partial pressure of A
PT = Total pressure of gaseous system at time 't'
(II) Decomposition of H2O2 in aqueous solution (In terms of volume of reagent KMnO4 required in
titration against H2O2 ).
H2O2 H2O + O2
2.303 V
k= log 0
t V1
where
V0 = Volume of KMnO4 required in titration of H2O2 sample taken initially
Vt = Volume of KMnO4 required in titration of same volume of at H2O2 sample at time 't'.
(III) Acid catalysed hydrolysis of ester( In terms of volume of reagent NaOH required in titration)

CH3COOC2H5 + H2O H CH3COOH + C2H5OH
NaOH reacts with H+ and CH3COOH.
2.303 V V0
k= log
t V Vt
where
V0 = volume of NaOH required in titration when reacted with H+ (at start)
Vt = volume of NaOH required in titration when reacted with H+ and CH3COOH at time 't'.
V = volume of NaOH required in titration when reaction is completed
(IV) Inversion of cane sugar (In terms of angle of rotation)

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H catalysed hydrolysis
C12H22O11 + H2O C6H12O6 + C6H12O6.
Inversion
(glucose) (fructose)
2.303 r0 r
k= log
t r
t r
where
r0 = initial angle of rotation of the sample
rt = angle of rotation after time t
r= angle of rotation after completion of reaction
(V) Oxide layer formation:

1 max
k = t ln
max
where
max = Thickness of oxide layer after times
= Thickness of oxide layer at time 't'.
(VI) Bacterial Growth:

1 ax
k = ln
t a
MISCELLENEOUS REACTIONS
(i) Parallel Reactions
[A]0 [B] k1
; ln [A] = (k1 + k2) t ;
t [C ] k 2
k1[A 0 ] k1t k 2 [A 0 ] k 2t
[A] = [A0] ekt; [B] = k k (1 e ) ; [C] = k k (1 e )
1 2 1 2
(ii) Consecutive Reaction

k1
A k2
B C
k1[A ]0
[A]t = [A]0 e k1t ;
[B]t = (k k ) e k1t e k 2 t
2 1

[C]t = [A0] ( [A] + [B] )
k2
1 k1 k k 2 k1
tmax = ( k k ) ln k ; [B]max = [A0]. 1
1 2 2 k2

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conc.
[C]
[B]
[A]
time
(iii) Reversible reaction

Consider the reaction
kf
A B
kb
At time t = 0 a b
At time t = t a x x
At time t = teq a xeq xeq
x eq x eq kf

ln x x = (kf + kb) t ; a x eq = k
eq b
THRESHOLD ENERGY AND ACTIVATION ENERGY :
Threshold energy : For a reaction to take place the reacting molecules must colloid together, but
only those collisions, in which colliding molecules possess certain minimum energy
is called threshold energy (ET) or the total minimum energy that reacting species
must possess in order to undergo effective collision to form product molecules
is called threshold energy.
Activation energy : It is extra energy which must be possessed by reactant molecules so that collision
between reactant molecules is effective and leads to formation of product
molecules.
Ea Eb
ET = Threshold energy
Ea = Activation energy of forward reaction
Energy
Eb= activation energy of backward reaction ET

P1 = Potential energy of reactants Reactants
Product
P2 = Potential energy of products P1 P2
Reaction Co-ordinates
Activated complex. It is formed between reacting molecules which is highly unstable and readily changes
into product.
INFLUENCE OF TEMPERATURE ON REACTION RATES :

Temperature coefficient :
The temperature coefficient of a chemical reaction is defined as the ratio of the reaction rates at two
temperatures differing by 10C. Its value usually lies between 2 & 3.
k t 10
Temperature coefficient = k .
t
Arrhenius Equation :
A quantitative relationship was proposed by Arrhenius
k = A. eEa/RT
where
k = rate constant ; A = frequency factor (or pre exponential factor);
R = gas constant ; T = Temperature (kelvin) ; Ea =Activation energy.

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k2 Ea 1 1
log
k1 2.303 R T1 T2
Graphical representations are :
COLLISION THEORY :
(i) This theory was given by Arrhenius and Von't Hoff.
(ii) This theory is mainly applicable for the bimolecular gaseous reactions.
(iii) A chemical reaction takes place due to the collisions between the reactant molecules. Bond
cleavage as well as bond formation takes place at the time of collision between the molecules.
(iv) The number of molecular collisions taking place per second unit volume of the reaction mixture
is known as collision frequency (Z11 or Z12).
(v) Under normal conditions, the value of Z 11 or Z12 is about 106 mol l1 s1. Normally, the reactions
are not so fast. It represents that all molecular collisions do not response reaction. Reaction
occurs due to a very small fraction of collisions.
(vi) The collisions that actually produce products are called effective collision. For a collision to be
effective, the following two barriers should be crossed by the molecules.
(I) Energy Barrier :

(a) According to the kinetic theory of gases, in any gaseous system, different gas molecules may
travel with different speeds. The molecular collision with low energy can never cause bond
cleavage and hence can not result the product formation. Only those molecular collision result
the formation of product in which the molecules collides with a certain minimum energy.
(b) The minimum amount of energy, which the colliding molecules must posses in order to make the
chemical reaction to occur, is known as Threshold energy, ET.
(c) The minimum amount of energy required to make active partcipitate of almost all molecules in a
reaction is called Activation energy, EA. The activation energy is equal to ET ER, where ER is
the average energy level of reactant molecules.
(d) The activation energy of reaction depends on the nature of reactant and temperature. It decreases
with increase in temperature but the decrease is so small that it is normally considered temperature
independent.
(e) The fraction of molecules having energy equal to threshold energy or more is given by the Berthelot's
factor, e Ea / RT .
(II) Orientation Barrier :

(a) The reacting molecules must collide in proper direction to make the collision effective. The
colliding molecules must be in the direction of maximum overlapping.
(b) The orientation factor is not much significant in all reactions. But, is become important when
different products may form at molecular collisions at different places.
(c) The fraction of molecular collision at right place is given by orientation or probability factor, P.
(III) On considering these barriers for reaction, the rate of reaction may be given by the collision theory as
Rate = Collision frequency fraction of effective collision

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= Collision frequency fraction of collisions with fraction of molecules in

sufficient energy proper orientation
or , r = (Z11 or Z12) e Ea / RT P
But, for bimolecular elementary reaction of type, 2A products, the experimental rate of reaction should
be r = k [A]2 = Z11. e Ea / RT . P
or, k = A . e Ea / RT
Z11 1
where, A = 2
2CN 2A is called pre-exponential factor. For any reaction, its value will depend on
[ A] 2
temperature but due to very small change in its value, it is also considered temperature independent. The
equation is called Arrhenius equation and is used to represent temperature dependence of reaction rate.
However, in actual Arrhenius equation, the term P was not present. This is why, the equation is simply
represented as : k = A . e Ea / RT
MECHANISM OF REACTIONS :
The path way by which reactants are converted into the products is called the reaction mechanism. It should
be clear that experimentally determined rate expression cannot be predicted from the stiochiometry of the
reaction. For example for the reaction ;
d
NO2(g) + CO (g) CO2 (g) + NO(g), the rate expression is ; rate = [NO2 ] = k[NO2 ]2 ,
dt
i.e. the expression is independent of CO (g) concentration.
The reason is that the reaction occurs by a series of elementary steps.
The mechanism proposed for the above reaction is a two step one.
NO2 + NO2 NO + NO3 (step 1 : slow)
NO3 + CO CO2 + NO2 (step 2 : fast)
The sum of the two gives the stiochiometry & the slow step decided the rate expression.

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THE ATLAS
Some basic concept
1.Rate of reaction.
2.Average and instantaneous
rate of reaction.
3.Rate law expression.
4.Order and molecularity of reaction.
CHEMICAL
KINETICS
Experimental Theoretical
Aspects Aspects
1.Determination of order of reaction. 1. Temperature depedence

(a) Graphical method. of rate of reaction
(b) Initial rate method. 2.Collision theory of rate
(c) Half life method. of reaction
2. Differential and integerated 3. Mechanism of reaction
expressions for and steady state approximation
(a) Zero order
(b) First order
(c) nth order reaction
(d) t1/2 of a reaction.
(e) Rate constant expression in which
conc. terms is replaced by other
variables litre pressure, volume of
reagent etc.
(f) Parallel reaction
(g) Consecutive or sequential reaction
(h) Reversible reaction

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RADIOACTIVITY
RADIOACTIVITY
The spontaneous emission of particles, electromagnetic radiation or both by unstable nuclei, is known as
radioactivity.
PROPERTIES OF ,-PARTICLES AND -RAYS.
Properties Alpha Beta Gamma

Fast moving He Fast moving High energy
1 Nature
nuclei electrons radiations
4 0 0
2 Representation 2 He or 1 e or 1 or 00
3 Charge 2 unit ( ve) 1 unit ( ve) No charge

33% to 90% of Same as light
4 Velocity 1/10 of light
light waves
Relative penetrating 1 or (0.01 mm of 100 or (0.1 cm of 10000 or (8 cm lead
5
power Al foil) Al foil) or 25 cm steel)
Travel distance
6 2 4 cm 200 300 cm 500 m
in air
7 Kinetic energy high low
8 Effect on ZnS plate Luminosity Little effect
9 Mass g/particle 6.65 10 24 9.11 10 28

Relative ionising
10 10000 100 1
power
Kinetic of nuclear distintegration

dN
Radioactive decay is a first order process. Hence
dt
= N or N = N0 et
where N = number of radioactive nuclei at any time t ;

N0= number of radioactive nuclei at t = 0 ;
= decay constant.
dN
Activity activity (A) =
dt
= N
S.I. units :
Disintegration per second (symbol s1 or dps). 1 dps = 1 Bq (Becquerel)
Other units:
1Ci (Curie) = 3.7 1010dps.
1 Rd (Rutherford) = 106 dps
Specific activity = dps / gm
Half life (t) The time taken by half the nuclei (originally present) to decay. t = 0.693/
1
Note : After n halflives have passed, activity is reduced to n of its initial value.
2

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Average life (t av)
1 t1 / 2
Tavg = = = 1.44 t1/2
0.693
APPLICATION OF NUCLEAR DISINTEGRATION :

* Determination of volume of blood
* Carbon dating
* Rock dating
THEORIES REGRANDING NEUCLEAR STABILITY

(A) Even odd theory of nuclear stability
The number of stable nuclides is maximum when both p and n are even number.
p n No. of stable nucleus

even even 165
even odd 55
odd even 50
odd odd 5
(B) Magic numbers and nuclear stability

Nuclei with 2, 8, 20, 50, 82 or 126 protons or neutrons are exceptionally stable and have a larger
number of stable isotopes than neighboring nuclei in the periodic table. These numbers are called magic
numbers. They are supposed to represent completely filled nuclear shells of energy levels.
e.g. 50Sn having 10 stable isotopes while 51Sb has only two stable isotopes.
Nuclei with magic number of protons as well as neut rons have notably high stabilities.
[eg. 42 He , 16 40
8 O , 20 Ca and
208
82 Pb ]. 165 such stable nuclei are known.
(C) Packing Fraction

Aston expressed relation between
isotopic mass & mass number in terms
of packing fraction.
Packing Fraction
Atomic mass Mass number
= 104
Mass number
* pcking fraction of C12 is
exactly zero.
* packing fraction may be
positive or negative
* negative packing fraction
implies that nuclei is stable
* positive packing fraction
implies that nuclei is unstable
* Some lighter nuclei have
positive packing fraction
although nucleus is stable
* Mo, Ru, Rh, Pd have lowest
packing fraction

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(D) Binding Energy : It is defined energy required to break the nucleus into its compoennt protons & neutrons.
Binding energy per nucleon gives a quantitiative measure of nuclear stability.
* Mass defect (m) = mass of neutron + mass of proton mass of nucleus
Binding energy of nucleus = m c2
* The binding energy for a nucleus containing Z protons and N neutrons can be calculated as
A
Binding energy = (ZMH + Nmn ZM
)c2
Note that above equation does not include Zmp, the mass of Z protons. Rather, it contains ZMH, the mass of
Z protons and Z electrons combined as Z neutral 11 H atoms, to balance the Z electrons included in AZ M , the
mass of the neutral atom.
If m = 1 a.m.u then B.E. = 931.5 MeV

B.E.
B.E. per nucleon = No. of nucleons
* A very heavy nucleus, say A = 240, has lower

binding energy per nucleon compared to that
of a nucleus with
A = 120. Thus if a nucleus A = 240 breakes
into two A = 120 nuclei, energy would be
released in the process. This implies nucleons
get more tightly bound. It has very important
applications for energy production
through fission.
* Consider two very light nuclei (A 10) joining

to form a heavier nucleus. The binding energy
per nucleon of the heavier nuclei is more than
the binding energy per nucleon of the lighter
nuclei, again energy would be released in such
a process of fusion.
* Nuclear binding energy is maximum for mass number 50 60.
* Fe, Co, Ni very high nuclear binding energy.
(E) Neutron / proton ratio and stability belt

For atomic number < 20, most stable nuclei have n: p ratio nearly
p
1 : 1 (except H & Ar).

n=
For n/p ratio > 1.52, nucleus is unstable. Largest stable nucleus is
209
83 Bi for which n/p ratio is 1.52.
For atomic number > 83, there are no stable nuclei.

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Expected emissions from unstable nucleus:
1. n/p ratio above stability belt : Those nucleus which have high value of of n/p ratio (lie above the
0
stability belt) undergoes 1
decay..
n p + 0 (antineutrino)
1
32 32 0
15 P
16 S 1
+

energy
* Beta decay is possible whenever the mass of the original neutral atom is greater than the final
atom.
* The difference between the rest mass energy of the initial constituents and that of the final
products is called the Q-value of the process. Thus, if Ui is the rest mass energy of the initial
constituents and Uf is that of the final products,
Q = Ui Uf
Q value is positive i.e. isolated nuctron may decay into proton.
* The energy released is shared by antineutrino and beta particle.
* The energy of particle can be any thing between zero & Q.
* Such transformation takes place because of weak forces operating within the nucleus.
2. n/p ratio below stability belt :
(a) -decay
212 208
83 Bi
81 T l 42 He
* Observed in nuclei with A > 210

* Mass number & the atomic number of the daughter nucleus decreases by 4 & 2 respectively compared to
parent nucleus.
* Alpha decay may takes place spontaneously or it can be initiated.
* Alpha decay is possible whenever the mass of the original neutral atom is greater than the sum of the
masses of the final neutral atom and the neutral helium-4 atom.
* All the alpha particles coming from a particular decay reaction have the same kinetic energy.
Positron decay
0
1
0
p n + 1
+ (neutrio)
0
* Those nucleus which have low value of of n/p ratio (lie below the stability belt) undergoes 1
decay..
* Q value is negative i.e. isolated proton will not decay into neutron.
* Positron decay is possible whenever the mass of the original neutral atom is greater than at lest two
electron masses larger than the final atom.
K electron capture
A 0 A
Z X 1e
Z1Y
106 0 106
47 Ag 1e
46 Pd
p + e n + (neutrino)

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* Electron capture can occur when ever the mass of original neutral atom is larger than that of final atom.
* Those nucleus having low n/p ratio can capture K shell electron.
* X-rays are emitted during the process.
-decay
When an or decay takes place, the daughter nucleus generally formed is in excited state & comes to
ground state by a single or successive transitions by emitting electromagnetic radiations i.e. rays.
60
27 Co 6028m Ni

1
60 m
60
28 Ni 28 Ni 00
60 0
27 Co 1 emission
E = 1.17 MeV
E = 1.33 MeV
60
28 Ni
* Life time of metastable nucleus thus form as life time less than 109 sec.
* No. of neutron and proton is unchanged while quantum state of nucleon changes.
RADIOACTIVE DISINTEGRATION SERIES :

Many radioacitve necleus (Z > 82) are obtained in naturee as a member of natural decay series.
The series of nuclear reaction is known as radioacitve disintegration series.
Series Parent Nucleus Last Nucleus No. of No. of

4n or Th232 Pb208 6 4
Thorium series
(4n+1) or Pu241 Bi209 8 5
Neptutinum series
4n+2 U238 Pb206 8 6
or Uranium series
4n+3 U235 Pb207 7 4
or Actinium series
4n, 4n + 3 and 4n + 3 series are natural while (4n +1) is artifical.
THE THORIUM SERIES :
332 228 228 228 224

90Th 88Ra 89Ac 90Th 88Ra
212 212
84Po

82Pb
208

212 216 220
82Pb 83Bi
208 84Po 86Em
216
81Tl
85At

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THE NEPTUNIUM SERIES :
241

241 95Am
237 233 229
94Pu
233
93Np 91Pa 92U 90Th
237

92U
213
225
84Po 221 225
88Ra
217
89Ac
209
87Fr
209 213
82Pb 85At
83Bi 83Bi
209

81Tl
THE URANIUM SERIES :
238 234 234 230

234
92U 90Th 91 Pa 92U 90Th
214 214

210
84Po 82Pb
214 222
82Pb
218 226
83Bi 84Po 86 Em 88Ra
210 218

81Tl

85At
210 210 206

83 Bi 84Po 82Pb
THE ACTINIUM SERIES :
227
235 231 231 227 90Th 223
92 U 90Th 91 Pa 89Ac 88Ra
223

87Fr
211 211
82 Pb
219
84Po
207 211 215 86Em
219
82Pb 83 Bi 84 Po 85At
207 215
215
81Tl
85At
83Bi

NUCLEAR REACTIONS
The reactions in which nuclei of atoms interact with other nuclei or elementary particles such as
-particle, proton, neutron, deutron, etc, resulting in the formation of new nuclei with or without liberation
of one or more elementary particles, are called nuclear reactions. The particles resulting nuclear reactions
are also called projectiles. In all the nuclear reactions, the total number of protons and neutrons are conserved.
Nuclear reactions may be expressed as similar as chemical reactions, like
14
+ 2He4 8O17 + 1H1
7N
Here, the nucleus of nitrogen atom is converted in to the nucleus of oxygen atom by a-particle and proton
is also produced as a by-product. These reactions may be expressed by short hand notation, in which the

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projectile and the liberating particle are expressed by their symbols, in a small bracket in between the parent
and the product nucleus. For example, the above reaction may also be expressed as:
14 17
7N ( , p) 8O
Some differences between nuclear and chemical reactions
No. Chemical reaction Nuclear reaction

1. No new element is formed New element is formed
2. Valence electrons of atoms participates Only the nucleus of atoms participates
3. Balanced by the conservation of atoms Balanced by the conservation of nuclear charge and
mass number (total number of neutrons and protons)
4. Mass conservation is obeyed Disobey mass conservation
5. May be exothermic or endothermic, liberating May be exothermic or endothermic, liberating or
or absorbing relatively small amount of energy absorbing relatively very high amount of energy
6. May be reversible Irreversible
7. May obey kinetics of any order Obeys only first order kinetics
8. Rate depends on external factors like Rate is independent from any external condition
temperature and the catalytic conditions
TYPES OF NUCLEAR REACTIONS:
1. Projectile Capture Reactions:

238 + 0n1 239
92U 92U +
27 + 0n1 28
13Al 13Al +
2. Particle - particle reactions:

23 + 1H1 23 + 1n1
11Na 12Mg
23 + 1H2 24 + 1H1
11Na 11Na
3. Spallation reactions: High speed projectiles with 400Mev bombarded on high nucleus giving smaller
nucleus.
63 + 2He4 17Cl37 + 141H1 + 16 0n1
29Cu
4. Fission reactions: It is the nuclear reaction in which a heavy nucleus is broken down by a slow or thermal
neutron (energy about 0.04 eV) into two relatively smaller nuclei with the emission of two or more neutrons
and large amount of energy. For example,
the reaction of atom bomb: 235 + 0n1 141 92 + 3 0n1 + 200 MeV
92U 56Ba + 36Kr
It is also found that the products of nuclear fission reactions are not unique. Some more products are
formed. The most probable mass numbers of the two nuclides formed are around 95 and 140 and an average
of 2.5 neutrons is emitted out per fission.
235 + 0n1 139 95 + 2 0n1
92U 54Xe + 38Sr
53I137 + 39Y97 + 2 0n1, etc

The destructive action of atom bomb is due to the following reasons:
(i) As some neutrons are produced in each fission, they may collide efficiently with the other U235 nuclei to
produce more neutrons and thus the reaction occurs in chain like fashion. It results the emission of a large
amount of energy in very small time.

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(ii) Each product of fission is radioactive and hence increases the intensity of radiation in that region, resulting
the problems due to radiations.
5. Fusion reactions: It is the nuclear reaction in which two or more light nuclei fused together to form heavier
nuclei, with the evolution of tremendous amount of energy. In such reactions, relatively more stable nucleus
having higher binding energy per nucleon is formed. Such reaction is difficult to occur because when the
nuclei of different atoms come closer, they repel each other strongly. This is why, very high temperature of
the order 106K is needed for the occurrence of such reactions. However, the overall reaction is highly
exothermic due to large mass defect. Some examples of nuclear fusion reactions are:
2 2 4
Probable reaction of hydrogen bomb: 1H + 1H 2He + 24.9 MeV
Probable reaction occurring at the surface of sun: 4 1H2 2He4 + 2 + +1e0 + 24.7 MeV
NUCLEAR REACTOR
A nuclear reactor is the furnace, place where nuclear fission reaction is performed to get energy. The
essentials of a nuclear reactor are:
1. Fuel : Nuclear fuels are of two types:

(i) Fissile materials : These are the nuclides which directly results chain reaction on bombardment with slow
neutrons. Such nuclides are U235, Pu239, U233, etc.
(ii) Fertile material : These are the nuclides which are non-fissile, but they may be converted in to a fissile
material by the action of neutrons. Such nuclides are U238 and Th232.

U238 + 0n1 92U239*
92 93
Np239 94
Pu239

Th232 + 0n1
90
Th233*
90
Pa233
91 92
U233
Such conversions are performed in a special type of nuclear reactor called Breeder Reactor.
2. Moderator: It is used to slow down the fast neutrons without absorbing them. Example: water, graphite,
helium, D2O etc.
3. Control rods: These are the rods of material which can absorb neutrons and hence control the fission
reaction. Example: Cadmium, boron, etc.
4. Coolant: These are the material which transforms the energy produced in the fission reaction in to heat
energy. Example: Liquid alloy of sodium and potassium, heavy water, polyphenyls, etc
ARTIFICAL TRANSMUTATION
It is the method of conversion of atom of one element in to the atom of other element with the help of some
particles like alpha particle, proton, deutron, neutron, etc (called projectiles). The first such transmutation
was performed by Rutherford. When N 14 atoms were bombarded by very fast moving
-particles, the nitrogen atom has changed in to oxygen atom and proton is produced simultaneously
14 4 17 1
7N + 2He 8O + 1H

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Later on, Rutherford and Chadwick shown that most of the nuclei may be transmuted by the suitable
projectile. After the discovery of cyclotron, a particle accelerating machine, such transmutations become
more easier.
ARTIFICAL RADIOACTIVITY
When Irene Curie and F. Juliot bombarded the atoms of Al27, B10 or Mg24 by fast moving -particles,
protons, neutrons and positrons were produced. They observed that the emission of protons and neutrons
stop on stopping the bombardment but the emission of positron continues. They also observed that the rate
of emission of positron decreases exponentially in the manner similar to natural radioactivity. They named
the isotope emitting positron as artificial radioisotope and the phenomenon as artificial radioactivity.
27 + 2He4 14Si30 + 1H1
13Al
15P30 + 0n1
30 + +1e0
14Si
NUCLEAR TRANSMUTATION
An experiment performed by Rutherford in 1919, however, suggested the possibility of producing radioactivity
artifically. When he bombarded a sample of nitrogen with particles, the following reaction took place:
14 4 17 17
7 K 2
8O 11p represented as 14
7 N ( , p ) 8 O
An oxygen-17 isotope was produced with the emssion of a proton. This reaction demonstrated for the first
time the feasibility of converting one element into another, by the process of nuclear transmutation. Nuclear
transmutation differs from radioactive decay in that the former is brought about by the collision of two
particles.
TRANSURANIUM ELEMENTS
Particle accelerators made it possible to synthesize the so-called transuranium elements, elements with
atomic numbers greater than 92. Neptunium (Z = 93) was first prepared. Since then, many other transuranium
elements have been synthesized. All isotopes of these elements are radioactive.
NEUTRON ACTIVATION ANALYSIS

Quantities of elements that are for too small for chemical analysis can be detected by this method. When
0
bombarded with neutrons, many stable nuclides absorb a neutron to becomes unstable & then undergo 1
decay. The energies of 0

1
& 00 depend on the unstable nuclide & provide a means of identifying its
original stable nuclide.

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SOLID STATE
AMORPHOUS SOLIDS:
Amorphous solids are those whose constitutent particles are randomly arrange and have no ordered long
range structure. example: Rubber, Glass etc.
CRYSTALLINE SOLIDS:
Crystalline solids are those whose atom, molecules or ions have an ordered arrangement extending over a
Long Range. example-NaCl,diamond, graphite etc.
TYPES OF CRYSTALLINE SOLIDS:
Type of Solid Intermolecular forces Properties Examples
Brittle, hard, high Melting point

Ionic Ion-Ion forces Insulator in solid but conductance NaCl, KCl, MgCl2
fused and aqueous solution
Dispersion
Molecular forces/Dipole-Dipole Soft, low melting point, Insulators H2 O, Br2 , CO 2 , CH4
/H-bond
Covalent
Covalent bonds Hard, Very high melting point C-Diamond SiO 2
network
Variable hardness and melting
Metallic Metallic bonds point, malleable and ductile, Na, Zn, Cu, Fe
conducting
1. UNIT CELL:
Collection of lattice points, whose repetition produce whole lattice is called
a unit cell. The whole lattice can be considered to be made by
repetion of unit cell.
TYPES OF UNIT CELL:

Unit Cell Parameters
Crystal Systems Bravais Lattice Example
Intercepts Crystal Angles
Primitive, Face Centered,
1 Cubic a=b=c NaCl, Zinc blend, Cu
Body Centered
Primitive, Face Centered, Rhombic sulphur, KNO 3 ,
2 Orthorhombic abc
Body Centered, End Centered BaSO 4
White tin, SnO 2 , TiO 2 ,
3 Tetragonal Primitive, Body Centered a=bc
CaSO 4
Monoclinic sulphur,
4 Monoclinic Primitive, End Centered abc
Na2 SO 4 .10H2 O
Caccite (CaCO 3 ), HgS
5 Rhombohedral or Trigonal Primitive a=b=c
(Cinnabar)
K 2 Cr2 O7 , CuSO 4 .5H2 O,
6 Triclinic Primitive abc
H3 BO 3
7 Hexagonal Primitive a=bc Graphite, ZnO, CdS
SEVEN CRYSTAL SYSTEM

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Rhombohedral
abc
90
BRAVAIS LATTICE
Although there are only 7 crystal systems or shapes, there are 14 different crystal lattices, called Bravais
Lattices.(3differentcubictypes,2differenttetragonaltypes,4differentorthorhombictypes,2different
monoclinic types, 1 rhombohedral, 1 hexagonal, 1 triclinic).
1.1 Primitive or simple cubic (PS/SC) unit cell: Spheres in one layer sitting directly on top of those in
previous layer, so that all layers are identical. Each sphere is touched by six other, hence coordination
number is 6. 52% of available space occupied by spheres.
Example: Polonium crystallises in simple cubic arrangement.

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Z = 1 ; C.N. = 6
1.2 Body Centered cubic (BCC) unit cell: Spheres in one layer sit in the depression made by first layer in
a-b-a-b manner. Coordination number is 8, and 68% of available space is occupied by atoms.
Example: Iron, sodium and 14 other metal crystallises in this manner.
Z = 2 ; C.N. = 8
1.3 Face centered cubic (FCC) unit cell:

Examples : Al, Ni, Fe, Pd all solid noble gases etc.
Z = 4 ; C.N. = 12
1.4 Hexagonal primitive unit cell

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Example : Be, Mg, Ti, Zr etc.
PACKING TYPES AMONG THE METALS
2. TYPE OF PACKING IN TWO DIMENSION :

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Square close packing Hexagonal close packing
3. PACKING OF ATOMS IN THREE DIMENSIONS:
(i) Hexagonal close pack (A-B-A-B) type packing :

Each layer has hexagonal arrangement of touching sphere and 3rd layer is similar (exactly on top) of first
layer.
(ii) Cubic close pack (A-B-C-A-B-C):

AB layers are similar to HCP arrangement but third layer is offset from both A and B layers. The fourth layer
is exactly on top of first layer.

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4. TYPES OF VOIDS IN CLOSEST PACKING:

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4.1 Tetrahedral void in FCC
4.2 Octahedral void in FCC
Circles labeled O represent centers of the Circles labeled T represent the centers of
octahedral interstices in the ccp the tetrahedral interstices in the ccp
arrangement of anions (fcc unit cell). The arrangement of anions. The cell "owns" 8
cell "owns" 4 octahedral sites. tetrahedral sites.

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5. RADIUS RATIO:
5.1 Radius ratio for co-ordination number 3

r
(Triangular Arrangement): = 0.155
r
5.2 Radius ratio for coordination number 4

(Tetrahedral arrangement):
r
= 0.225
r
5.3 Radius ratio for coordination number 6:

r
(Octahedral Arrangement) or = 0.414
r
Radius ratio for coordination number 4
(Square plannar arrangement)

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5.4 Radius ratio for coordination number 8 :

(Body centered cubic crystal)
r
= 0.732
r
6. TYPES OF IONIC STRUCTURES:

6.1 Rock salt structure:(NaCl) Larger atom formic ccp arrangement and smaller atom filling all octahedral
voids.
Cl
+
Na
Rock salt structure
6.2 Zinc blende (sphalerite) structure:(ZnS) Larger atom formic ccp arrangement and smaller atom filling
half of alternate tetrahedral voids
2
S
+2
Zn
Zinc blende structure

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6.3 Cesium halide structure: (CsCl) Cl at the corners

of cube and Cs+ in the center.
6.4 Fluorite structure:(CaF2) Ca2+ forming ccp arrangement and F filling all tetrahedral voids.
6.5 Antifluorite structure :(Li2O) O2 ion forming ccp and Li+ taking all tetrahedral voids.
6.6 Corundum Structure: (Al2O3) O2 forming hcp and Al3+ filling 2/3 octahedral voids.
6.7 Rutile structure: (TiO2) O2 forming hcp while Ti4+ ions occupy half of the octahedral voids.
6.8 Pervoskite structure:(CaTiO3) Ca2+ in the corner of cube O2 at the face center and Ti4+ at the centre of
cube.
6.9 Spinel and inverse spinel structure: (MgAl2O4)O2 forming fcc, Mg2+ filling 1/8 of tetrahedral voids and
Al3+ taking half of octahedral voids.In an inverse spinel structure, O2 ion form FCC lattice, A2+ ions
occupy 1/8 of the tetrahedral voids and trivalent cation occupies 1/8 of the tetrahedral voids and 1/4 of the

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octahedral voids.
7. CRYSTAL DEFECTS:
Real crystals are never perfect: they always contain a considerable density of defects and imperfections that
affect their physical, chemical, mechanical and electronic properties. The existence of defects also plays an
important role in various technological processes and phenomena such as annealing, precipitation,
diffusion,sintering, oxidation and others. It should be noted that defects do not necessarily have adverse
effects on the properties of materials. There are many situations in which a judicious control of the types
and amounts of imperfections can bring about specific characteristics desired in a system.
The electrical behavior of semiconductors, for example, is largely controlled by crystal imperfections. The
conductivity of silicon can thus be altered intype (n or p) and by over eight orders of magnitude through the
addition of minute amounts of electrically active dopant elements. In this case, each atom of
dopant,substitutionally incorporated, represents a point defect in the silicon lattice. The fact that such small
amounts of impurity atoms can significantly alter the electrical properties of semiconductors is responsible
for the development of the transistor and has opened up the entire field of solid state device technology.
POINT DEFECTS : When some ion's are missing from ionic crystals from their theoretical lattice point, the
crystal is defected structure.
Defect due to missing of ions from theoretical lattice point is called point defect.
Point defect increases with increase in temperature. At absolute zero temperature, ionic
crystal may not have any defect.
POINT DEFECTS ARE OF TWO TYPES :

(i) Stoichiometric defect : Defects due to which overall formula of ionic compound do not change is
called stoichiometric defect.
(ii) Non- Stoichometric defects are those due to which overall formula of compound changes.
Stoichiometric defect :(i) Schottky defect (ii) Frenkel defect
Schottky :- When pair of holes exist in crystal lattice due to missing of positive and negative ions in
pair, the defect is called schottky defect.
Schottky defect
This defect is common in ionic compounds with high coordination number. It absolute zero temperate
crystalstends to have perfectly order arrangement. As temperature is increased, some vacancies are always

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created in crystal lattice.

Ex. of crystals showing schottky defect: NaCl, KCl, NaBr etc.
Frenkel defect : In this type of defect, holes are created due to transfering of an ion from usual lattice
site to a interstitial site. This type of defect very common in compounds in which there
is large difference between size of cation and anion.
Frenkel defect e.g.ZnS ; AgBr; etc
Consequence of defects:
- Due to schottky defect density of crystal decreases
- Crystal can conduct electricity to a small extent.
Non-stoichiometric defects :
Non stoichiometric compounds are those in which the ratio of positive and negative ions present in the
compounds differ from that indicated by their chemical formula. eg. Fe0.95O, Cu1.97S, etc.
These defects arise due to excess of metal or non-metal atoms
(i) Metal excess defect (ii) Metal deficiency defect
Metal excess defect arise due to
(i) Missing of a negative ion from lattice site and position taken by an electron. This defect is similar to schotty
defect and also found in crystals showing schotty defect. Ex. When sodium vapours passed over NaCl
crystal a yellow non-stoichiometric form of NaCl is obtained. Vaccant lattice site occupied by electron's is
called F-centre (Farbe colour). Which is responsible for colour of crystal.
(ii) An extra metal occupy interstitial site and to maintain electrical neutrality, electrons occupy another interstitial site.
This type of defect is very close to Frenkel defect and found in ZnO.
When ZnO is heated, it turns yellow as it's loses some oxygen. The Zn2+ ion move to an interstitial site.
Note: In this defect there is no hole in the crystal.
Crystals with metal excess defect contain free electrons and if these migrate, they conduct an
electric current.
As amount of current carried is very small, they behave like semiconductor's. (n-type
semiconductor)
Metal deficiency defect:
(i) A metal ion is missing from it's normal lattice point the electrical neutrality is maintained by extra positive
charge of same of the remaining metal ions.
FeO, FeS, NiO - exhibit this type of defect.
(ii) An extra negative ion is present in the interstial position and electrical neutrality is maintained by extra
positive charge on remaining metal ions. This type of defect is not known.
Crystal with metal deficiency defect behaves like p-type semiconductors.

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A+ B A+ B
B e B A2+
A+ B A+ B
(a) Ex. FeO, NiO, FeS

Metal deficency defect

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THE ATLAS
TYPES OF SOLIDS
Crystalline Solids Amorphous Solids

Crystalline solids have long range order i.e. the
constituent particles are arranged in a regular
fashion and this symmetrical arrangement extends
throughout the crystal length.
Lattice - Unit Cells

(i) A unit cell is the smallest repeating structural unit the crystalline solid. Bravais has
predicted that there are only 14 unit cells that exists in nature.
(ii)The relation between the edge length (a) and the radius of atom (r) forming lattice
are as follows. PC :a=2r, BCC: 3a=4r;FCC:2a=4r& HP:a=2r height(c) =4r 2
3
Packing fraction and density determination

(i) The ratio of volume occupied by the effective atoms to the volume of the unit cell
is called packing fraction. Its values for various unit cells are PC = 0.52,
BCC = 0.68, FCC & HP = 0.74.
(ii)Density () of cubic crystal is calculated using the relation = zM 3 where
NAVa
z=number of effective atoms, M=Atomic mass,NAV=Avogadro's number and
a= Edge length.
Type of void and radius ratio rule

(i) Tetrahedral & octahedral voids are present only inclosest packed structures. The
effective number of octahedral voids in a unit cell is equal to the effective
number of atoms in the unit cell & effective number of tetrahedral voids is equal
to double the number of effective atoms in the unit cell.
(ii)The sum of radius of the atom of host lattice (rh) and the radius of atom occupying
void(rf(t)or rf(o)) is given by
For octahedral void, rh+rf(o)= a & for tetrahedral void,rh+r f(t)= 3a
2 4
(iii)Limiting radius is defined as the minimum ratio of cation to anion radius. It is
defined when cation is in contact with anions and anions are also in contact
with each other.
(iv)Radius ratio depends on the co-ordination number. The limiting radius ratio for
the various co-ordination numbers are
C.N.3 : 0.155, C.N.4 (Tetrahedral) : 0.225, C.N.4(Square planar) : 0.414,
C.N.6 (Octahedral) : 0.414, C.N.8 (BCC) : 0.732, C.N.12 (Ideal FCC) : 1
Defects in Solids
Ionic lattice has 2 major defects. Schottky defect
occurs due to the cation-anion pair vacancy,
which decreases the density of crystal. Frenkel defect
occurs when an ion leaves its lattice site and fits
into an interstitial space. Due to Frenkel defect,
density of crystal remains unaffected.

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PERIODICITY
Along a Period ( )
Along a Group ( )
Max. Z
Constant Z* (effective due to screening)
Max.
rn (atomic, ionic radius) Cation smaller than atom, anion larger than atom
Fe, Co, Ni have equal size
Be > B, N > O, inert gas max, I 1 < I 2 < I 3 .....................

(I.P.)
Inert gas zero
(Electronegativity)
Zr & Hf, Al & Ga have equal size
(Electron-affinity) Inert gas zero, Cl > F, S > O, P > N
(for cations)
(Hydration and Hydration Energy) (for anions)
(Size of Hydrated ion) (for cations)
(Acidic nature of oxides)

K+ < Na+ < Li+
(Basic nature of oxides)
(Reducing Nature)
Isoelectronic ions have different size.

Reducing nature of hydride increases in a group and decreases in a period.

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PartA (Periodic Table)

INTRODUCTION :
Many attempts were made to classify the known elements from time to time . These are :
(i) Lavoisier classification (ii) Dobereiners Triad law (iii) Newlands Octave law
(iv) Lother Meyer's curve (v) Mendeleev Periodic law (vi) Mosley experiment
(vii) Modified mendeleev periodic table (viii) Modern periodic law
PERIODIC LAW (1869) :

The physical and chemical properties of elements are periodic functions of their atomic weight.
MODERN PERIODIC LAW :

The physical and chemical properties of elements are periodic functions of their atomic number.
LONG FORM OF PERIODIC TABLE : [ BOHR'S TABLE ]

based on modern periodic law and Bohr Burry Scheme of E.C.
CLASSIFICATION OF ELEMENT INTO GROUPS AND PERIODS :

OLD CLASSIFICATION
s and p block elements, representative elements. IA to VII A and zero group.
Group A : s and p block elements. Group I A to VII A .
Group B : d and f block elements, transition and inner transition elements IB to VII B and VIII groups.
Total 16 Groups
Period 1 to 7 classified as short, shortest, long, longest and incomplete period.
NEW CLASSIFICATION
Total 18 Groups
CLASSIFICATION OF ELEMENTS INTO s , p , d & f BLOCK ELEMENTS :

s block :
(i) configuration n s 1 2 (ii) last e enters in s orbital
(iii) two groups I A or 1 ; II A or 2
p block :
(i) configuration n s2 n p 1 6 (ii) last e enters in p orbital
(iii) six groups III A , IV A , V A , VI A , VII A , zero or 13 , 14 , 15 , 16 , 17 , 18
d block : [ Transition Elements ]
(i) configuration (n 1) d 1 10 n s 0 2 (ii) last e enters in d orbital
(iii) their two outermost shell are incomplete
(iv) 10 groups III B , IV B , V B , VI B , VII B , VIII (Triad) , I B , II B or
3 , 4 , 5 , 6 , 7 , (8 , 9 , 10) , 11 , 12 .
(v) four series 3 d , 4 d , 5 d , 6 d belong to 4th, 5th, 6th & 7th period respectively in long form of
Periodic table.
f block : [ Inner Transition ]

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(i) configuration (n 2 ) f 0 14 (n 1) d 0 2 ns2

(ii) last e enters in f orbital
(iii) two series 4 f Lanthanides & 5 f Actinides belong to 6th & 7th period respectively in
long form of Periodic table.
ESTIMATING POSITION OF AN ELEMENT FROM ITS ELECTRONIC CONFIGURATION:

The last electron enters which subshell gives idea of its block.
[ Think :1s1 and 1s2 belongs to which block]
Period number = Principal quantum number of valence shell electron in ground state electronic
configuration.
Group number for s block = number of valence shell electron
Group number for p block = 10 + number of valence shell electron
Group number for d block = number of [ns + (n1) d] electron
Group number for f block = 3
[ Use these carefully while locating the position.]
COMMONLY ASKED PROPERTIES :

1. Atomic Volume : Volume occupied by one gm atom of an element .
Atomic weight
Atomic volume =
density
Lower atomic volume leads to higher density , increased hardness higher melting point, boiling point,
less malleability & ductility.
2. Atomic Radius : Problem in calculating actual size of atom and hence distance between nuclei is calculated
giving rise to three type of radii for atoms.
d
(a) Covalent radius : Cr = Cr < actual atom size [Slight difference]
2
[Used for H2, Cl2 and such molecules]

d
d
(b) Metallic Radius : Mr =
2
[Used for metals]
d
d
(c) Vanderwaal radius : Vr = Vr >> actual size [very large difference]
2
In general for an element Vr > Mr > Cr

(d) Ionic Radius : A cation is smaller than parent atom . An anion is larger than parent atom.

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FACTORS AFFECTING ATOMIC SIZE :

(a) n increase size increases
(b) Zeff increase size decrease [Zeff = Z ]
CALCULATION OF Zeff (using slaters rule)

To calculate the shielding constant () for an electron in an np or ns orbital :
1. Write out the electronic configuration of the element in the following order and groupings :
(1s), (2s, 2p) (3s, 3p) (3d) (4s, 4p), (4d) (4f) (5s, 5p), etc.
For s and p electrons :

2. Electrons in any group to the right of the (ns, np) group contribute nothing to the shielding constant.
3. All of the other electrons in the (ns, np) group, shield the valence electron to an extent of 0.35 each. (Except
for the 1s orbital for which value is 0.30).
4. All electrons in the (n 1) shell shield to an extent of 0.85 each.
5. All electrons (n 2) or lower group shield completely ; that is, their contribution is 1.00 each.
For d and f electrons :

2. Electrons in any group to the right of the nd or nf group contribute nothing to the shielding constant.
3. All of the other electrons in the nd or nf group, shield the valence electron to an extent of 0.35 each.
5. All electrons in groups lying to the left of the nd or nf group contribute 1.00.
General Trend :
Along a period, size decrease [n constant, Zeff ]
Exceptions :
(1) Noble gases have largest atomic sizes [Vander waal radii]. However, their covalent radii are smaller e.g. Xe.
(2) Size of Ga and Al are same, [Zeff increasing]
(3) Size of Hf & Zr are same (lanthanide contraction)
ATOMIC RADIUS
ALKALI METALS ALKALINE EARTH METALS GROUP III-A
2.5 1.8
Cs, 2.35 2.5
Rb, 2.16 1.6 Tl, 1.55
2 K, 2.03 Ba, 2.22 In, 1.5
Sr, 2.15 1.4
2 Ca, 1.97
1.2 Al, 1.24 Ga, 1.24
1.5 Na, 1.57
Mg, 1.6
(in )
1.5 1
in
(in )
Li, 1.23
0.8 B, 0.8
1 1
Be, 0.89 0.6
0.5 0.5 0.4
0.2
0 0 0
Be Mg Ca Sr Ba B Al Ga In Tl
Li Na K Rb Cs
CARBON FAMILY NITROGEN FAMILY (PNICOGENS)

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1.6 1.6
Bi, 1.52
1.4 Sn, 1.41 Pb, 1.44 1.4 Sb, 1.41
1.2 Ge, 1.22 1.2 As, 1.21
Si, 1.11 Pb, 1.1
1 1
(in )
(in )
0.8 C, 0.77 0.8 N, 0.74
0.6 0.6
0.4 0.4
0.2 0.2
0 0
C Si Ge Sn Pb N Pb As Sb Bi
CHALCOGENS HALOGENS
1.6 1.4
I, 1.33
1.4 Te, 1.37 1.2
Br, 1.14
1.2 Se, 1.14 1 Cl, 0.99
1 S, 1.04
(in )
0.8
(in )
F, 0.72
0.8 O, 0.74 0.6
0.6
0.4
0.4
0.2
0.2
0
0
F Cl Br I
O S Se Te
[ what can you predict or say about the increment in size along a group and decrement along a period]
ISOELECTRONIC MONOATOMIC SPECIES [Size 1/Z]:

(i) S 2 , Cl , K + , Ca 2 + , Sc 3 + (ii) H , He , Li +
radius of cation Z of Anion
(iii) O2 , F , Na+ , Mg+2, Al+3 (iv) = eff
radius of anion Zeff of Cation
ISOELECTRONIC MOLECULAR SPECIES

(i) NO3 , CO32 , SO2 (ii) N2 , CO , CN
(iii) NH3 , H3O + (iv) CH4 , NH4 +
Size of these species cannot be compared.
IONISATION ENERGY :
Amount of energy required to remove the most loosely bounded electron from an isolated gaseous atom form its
ground state electronic configuration.
Units : kJ mol1, k cal mol1, eV per atom.
Ionisation is endothermic (endoergic) i.e. requires energy hence Hionsation is +ve
M + Energy (IE1) M + e +
M M+ + e H = IE1
+
M M + e +2 H = IE2
M+2 M+3 + e H = IE3
IE3 > IE2 > IE1 always
FACTORS AFFECTING IONISATION ENERGY :

(1) Atomic size : Varies inversely
(2) Screening effect : varies inversely
(3) Nuclear charge (Z) : varies directly
(4) Special electronic configuration of outermost electron (half filled / fully filled)
(5) Type of orbital involved in Ionisation :s > p > d > f.

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Half fillness and full fillness of inner orbitals. [affects d block and f block trends]
General Trend: Along period I.E. increases [with some exception] [Zeff ]
Along a group I.E. decrease [Zeff constant, n ]
Exception :
(1) Along a period, half filled and fully filled have higher I.E.
e.g. Be > B and N > O.
(2) along a group, Ga > Al
PROPERTIES AFFECTED BY IONISATION ENERGY:

(1) Metallic character
(2) Reducing power
(3) Tendency to stay in which state A+1. A+2 or A+3
IONISATION ENERGY
ALKALI METALS ALKALINE EARTH METALS GROUP III A
6 10 900
Li, 5.4 9 Be, 9.32
800 B, 801
5 Na, 5.1
8 Mg, 7.64 700
K, 4.3 Rb, 4.2 7
4 Cs, 3.9 600 Tl, 589
(in kJ/mol)
Ca, 6.11 Al, 577 Ga, 579 In, 558

6
(in eV)
(in eV)
Sr, 5.7 500

3 5 Ba, 5.2
400
4
2 3 300
2 200
1
1 100
0 0 0
Li Na K Rb Cs Be Mg Ca Sr Ba B Al Ga In Tl

12 400
C, 11.2
350 N, 336
10
300
(in kcal/mol)
8 Si, 8.1 Ge, 7.8

Sn, 7.3 Pb, 7.4 250 Pb, 253
(in eV)
As, 231
6 200 Sb, 199 Bi, 184.9
4 150
100
2
50
0 0
C Si Ge Sn Pb N Pb As Sb Bi
CHALCOGENS HALOGENS
16 20
14 18 F, 17.4
O, 13.6
16
12
14
S, 10.4 Cl, 13
10 12
(in eV)
Se, 9.75 Br, 11.8

(in eV)
Te, 9.01 Po, 8.43 10 I, 10.4

8
8
6 6
4 4
2 2
0
0
F Cl Br I
O S Se Te Po
ELECTRON AFFINITY :
Amount of energy released when an electron is added to an isolated gaseous atom.

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Units : k J mol 1 , k Cal mol 1 and eV per atom.

Addition of electron results in release of energy in most of the cases but 2nd E. A. is always energy
required. The sum of EA1 & EA2 is energy required.
1
EA Zefff . Cl has the highest E.A.
atomic size
ELECTRON GAIN ENTHALPY : (EGE)

When expressed in terms of enthalpy change (Heg ) then it is termed as EGE Remember that
H=veforexothermicchange.
For EA1, energy is released Heg1 = ve (Not always)
For EA2, onwards is required Heg2 = + ve (always)
In general EA1 + EA2 , energy is required. ( H eg1 H eg 2 ) 0
FACTORS AFFECTING ELECTRON AFFINITY :
(1) Atomic size : varies inversely
(2) Nuclear change : varies directly
(3) Stable electronic configuration i.e. half filled and fully filled shells.
General Trend : Along a period, electron affinity increases [with exception] as Zeff .
Along a group, electron affinity decreases after 3rd period. Between 2nd and 3rd period in p block electron
affinity of 2nd period is lesser due to high electron density.
Exception :
(1) A fully filled and half filled which have low values or even sometimes energy is required rather than getting
released.
(2) 2nd period has lower value than 3rd owing to repulsion between electrons.
egH(kJ mol1) values for s and p block

1 18
H He
72 2 13 14 15 16 17 48
Li Be B C N O F Ne
60 0 27 122 8 141 328 116
Na Mg Al Si P S Cl Ar
53 0 43 134 72 200 349 96
K Ca Ga Ge As Se Br Kr
48 2 29 116 78 195 325 96
Rb Sr In Sn Sb Te I Xe
47 5 29 116 103 190 295 77
ELECTRO NEGATIVITY : [ Properties of an atom in a molecule]
F has highest electronegativity in periodic table. Decreasing order F > O > Cl = N > Br > S = C >
I > H.
Pauling Scale: XA XB = 0.208 AB in kcal/mol
XA XB = 0.102 A B in kJ/mol
= EA B (EA A x EB B)1/2

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IP EA
Mulliken's Scale : XA = (e v) .
2
Mulliken's values of E N are about 2.8 times as large as Pauling .
XM
i.e. XP =
2. 8
XP = 0.336 (XM 0.615)
0.359 Z eff
AllredRochows : XA = + 0.744
r2
r = covalent radius of atom in
Zeff = Effective nuclear charge on periphery
FACTOR AFFECTING ELECTRO NEGATIVITY :
(1) Nuclear attraction : varies directly
(2) Atomic radius : varies inversely
(3) Charge on ions : More positive charge more electronegativity and more ve charge less electronegativity.
(4) Hybridisation : to be discussed later in bonding.
General Trends : Along a period, electronegativity increases

Along a group, electronegativity decreases
Exceptions : None noteworthy.
FACTORS DEPENDENT ON ELECTRO NEGATIVITY :

(1) % ionic character varies directly. (2) Strength of bond varies directly.
(3) B.L. : varies inversely. (4) Nature of hydrides
(5) Nature of hydroxide.
ELECTRONEGATIVITY
ALKALI METALS ALKALINE EARTH METALS GROUP III A
1.2 1.6 2.5

Be, 1.47
1.4
1 Li, 1 2 B, 2
Na, 0.9 1.2 Mg, 1.23
In, 1.7 Tl, 1.8
0.8 K, 0.8 Rb, 0.78 1 Ca, 1.04 Sr, 1 Ga, 1.6
Cs, 0.7 Ba, 0.97 1.5 Al, 1.5
E. N.
E.N.
E.N.
0.6 0.8
0.6 1
0.4
0.4
0.2 0.5
0.2
0 0 0
Li Na K Rb Cs Be Mg Ca Sr Ba B Al Ga In Tl
3 3.5
3 N, 3
2.5 C, 2.5
Electronegativity
2.5
2 Ge, 2
Si, 1.8 2 Pb, 2.1 As, 2
Sn, 1.7
E.N.
Pb, 1.6 S b, 1.9 Bi, 1.9

1.5
1.5
1
1
0.5
0.5
0
0
C Si Ge Sn Pb
N Pb As Sb Bi

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CHALCOGENS HALOGENS
4 4.5
3.5 O, 3.5 4 F, 4
3 3.5
3 Cl, 3
2.5 S, 2.5 Br, 2.8
Se, 2.4
E. N.
2.5 I, 2.5
E. N.
2 Te, 2.1 Po, 2 2

1.5 1.5
1 1
0.5 0.5
0
0
F Cl Br I
O S Se Te Po
MISCELLANEOUS CHEMICAL PROPERTIES :

1. Periodicity of hydra acids :
(a) Acidic character of hydra acid increases from left to right in a period.
(b) Acidic character of hydra acid increases from top to bottom in a group.
2. Periodicity of oxy acids :

(a) Acidic character of oxy acid increases from left to right in a period.
(b) Acidic character of oxy acid decreases from top to bottom in a group.
3. Periodicity of nature of oxide :

(a) On moving from left to right in a period acidic nature of oxide generally increases.
e.g. CO2 < P2O3 < SO2 < ClO2
(b) On moving from top to bottom in a group acidic nature of oxide generally decreases.
4. General trends
(a) Hydration energy decreases along a group.
(b) Lattice energy decreases along a group.
SOME POINTS TO REMEMBER : (without considering radioactive elements)

1. Second most electronegative elementOxygen
2. Hydrogen is the lightest element and Lithium is lightest metal.
3. Helium has the highest value of I.P.
4. In periodic table metalloids are only in p-block.
5. Total gaseous elements are 11 (He, Ne, Ar, Kr, Xe, Rn, H2, N2, O2, Cl2, F2)
6. Liquid metal is Hg.
7. Diamond is hardest natural substance.
8. Halogens have highest electron affinity and in that to Cl has the highest amongst them.
9. The largest cation of the periodic table = Cs+.
10. The smallest cation of the periodic table = H+.
11. The largest monovalent anion of the periodic table = I.
12. The smallest anion of the periodic table = F.
13. The biggest element of periodic table = Fr.
14. The smallest element of periodic table = H.
15. Br is liquid non-metal element.

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16. Osmium is the heaviest element known.

17. Fluorine is the most electronegative element.
SOME COMMONLY USED TERMS :

1. Noble Gases : Element of group 18 are called noble gases. These are also called as inert gases because their
outermost ns and np orbitals are completely filled (except He and 1s 2 ) and these gases are
non-reactive in nature under ordinary conditions.
2. Representative elements : All the s and p block elements are known as representative elements except zero
group.
3. Transition elements : All the d-block elements (except IIB group) are called transition element. It comprises
into 4th, 5th, 6th and 7th period. They lie between s and p block elements.
4. Inner transition elements : All the f-block elements or 4f and 5f block elements are called inner transition
element. Total number of these elements is 28. They lie in IIIB and placed at the bottom of periodic table.
5. Typical elements : Elements second and third period are known as typical elements.
6. Diagonal relationship : Properties of elements of second period resemble with the element of third period.
These resemblance between properties of 2nd & 3rd period are called diagonal relationship.
IA IIA IIIA IVA
2nd period Li Be B
3rd period Na Mg Al Si
NOMENCLATURE OF THE ELEMENT :
The names are derived by using roots for the three digits in the atomic number of the element and adding the
ending ium. The roots for the number are
Digit Name Abbreviation
0 nil n
1 un u
2 bi b
3 tri t
4 quad q
5 pent p
6 hex h
7 sept s
8 oct o
9 enn e
Thus element with atomic number 109 will be named as une (u for 1, n for 0 and e for 9). Table summarises
the names of the elements with atomic number above 100.

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CHEMICAL BONDING
approach Decrease in Potential energy
Ionic
s
1 1 bond
2
Bond Bond 3 Multicentre bond
: Bond Bond (a). Banana bond (3C2e)
or (b). (3C-4e) bond
,7
at C.A.
4
3 s
s
b / bad
Hard,
, Brittle
/B.P.
in polar solvent
Electronic theory of valency
4
Covalent character c
in ionic compounds:
Fajans rule
5 : Fajans rule
(6) Ionic character

in covalent compounds

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KEY CONCEPT
Reasons for Bond formation:
Decrease in potential energy due to attractions.

Attainment of Octet [ns2 np6], assumed to be most stable.
Types of bonds : Ionic, covalent, co-ordinate
IONIC BOND [ELECTROVALENT]

Complete removal and acceptance of electrons to form cation and anion respectively.
Electrostatic attraction between the resulting ions.
s-block elements show fixed electrovalency.
Elements of p & d block may show variable electrovalency due to
(a) Inert Pair effect (for p block): The reluctance of s electron pair to take part in bond formation on moving
down a group in p block elements. (will be discussed in class XII th)
Finds application in
Stable oxidation state of a particular atom of an element.

Oxidizing & reducing power of compounds.
(b) Unstability of core: For d block elements the core may either have pseudo inert configuration (having 18
electrons in outermost shell )or any other.
Properties of Ionic compounds
Ionic bonds are non directional in nature
High Melting points / Boiling points.
In solid state they do not conduct electricity ( due to absence of charge carrier) while in aqueous & molten
state they are good conductor of electricity.
Soluble in polar solvents
Show isomorphism.(Compounds having same crystal structure)
No special theories to understand bond formation.
characteristics like various crystal lattices to be done in solid state.
COVALENT BOND
Sharing of electrons
Overlapping of orbitals
Types : single, double, triple, polar, nonpolar bonds.
Variable covalency : Shown by elements having vacant d orbitals (caused due to excitation of the electron.)
Properties:
Covalent bonds are directional in nature
Low melting point & boiling point. (except Diamond / Graphite, due to their peculiar structure)
Electrical conductivity due to auto-protolysis or self ionisation.
Show isomerism.
CO-ORDINATE BOND
Bonding between lewis acid & lewis base or electron deficient & electron rich species.
Lewis base: Species with lone pair on central atom available for donation. eg. NH3, H2O

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ch arg e
Lewis acid: Electron deficient due to incomplete octet, vacant p or d orbital & high + ve ratio.
size
Lewis Dot structures:
Arrangement of various atoms in a molecule & types of bonding present in it but no idea of geometry of the
molecule.
Selection of central atom [least E.N. of all elements excluding hydrogen]
In oxy acids all H atoms are attached to oxygen as OH groups except in H 3 PO 3 (dibasic),
H3PO2(monobasic) & H4P2O5 (dibasic). Which are directly bonded to central atom.
Applications:
To know various linkages present
To calculate formal charge of various elements.
Various Theories For Explaining Bonding
Electronic theory of valency (Kossel, Lewis).

Singlet linkages (Sudgen theory)
Valence bond theory (Heitler, London, Pauling, Slater).
M.O.T. (Hund , Mulliken). (will be discussed in class XII th)
DIPOLE MOMENT
Dipole moment is a vector quantity = = q d. Units = coulomb m (S.I.) or esu cm(CGS) or Debye
(common unit) 1 D = 1018 esu cm = 3.33 1030 coulomb m
observed D.M.
% ionic character = 100 %
calculated D.M.(for 100 % ionic )
% ionic character = [ 16 (XA XB) + 3.5 (XA XB)2 ] % [Hanny & Smyth equation]
Dipole moment depends on
Electronegativity difference between bonded atoms
Direction of bond dipole moment
Angle between various bonds
Influence of unshared e pairs
Magnitude of polarity of the molecule
Symmetrical / Unsymmetrical shape.
Bond Moments:
HF (1.9 D) HO (1.5 D) C C (0 D) CF (1.4 D)
HCl (1.1 D) HN (1.3 D) C = O (2.3 D) CCl (1.5 D)
H Br (0.8 D) H C (0.4 D) C Br (1.4 D)
H I (0.4 D) C I (1.2 D)

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SHAPES OF MOLECULES BASED ON VSEPR THEORY

Total no. No. of b.p. No. of General Type of Stereo Shape Exam.
of hybrid (bond pairs) unshared formula hybridisation chemical
orbitals pair i.e. lp formula/str.
2 2 0 AB2 sp 180
linear BeCl2
BAB
B 120 B
3 3 0 AB3 sp2 A Trigonal
B planar
A
3 2 1 AB2 sp2 <120
V or Bent or
B B
angular
B
10928
4 4 0 AB4 sp3 A Tetrahedron
B B
B
4 3 1 AB3 sp3 A Trigonal NH3
B B
B <109 pyramid CH 3
4 2 2 AB2 sp3 A V or Bent or H2O

B <109 B angular SF2
B bond
angle
A N.A.
4 1 3 AB sp3 linear ClO
B
B
5 5 0 AB5 sp3d B
90
A 120 Trigonal
B
bipyramidal
B
B
B
5 4 1 AB4 sp3d A 120
Seesaw SF4
B B
B
<90
B A
5 3 2 AB3 sp3d T-shaped ClF3,
B BrF3
B
5 2 3 AB2 sp3d A Linear
B
B B
B
6 6 0 AB6 sp3d2 A 90 Octahedral SF6

B B B
All bond = 90 I F6
B B
B
6 5 1 AB5 sp3d2 A <90
Square
B pyramidal
B
All less than 90
B B
6 4 2 AB4 sp3d2 A 90 Square
B B
planar

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B B
7 7 0 AB7 sp3d3 B 90 72 Pentagonal IF7
B
A bipyramidal
B B B
B
B B
A B
7 6 1 AB6 sp3d3 Pentagonal ---
B B
pyramidal
B B
A B
7 5 1 AB5 sp3d3 Pentagonal XeF5
B B planar
HOW TO DECIDE THE TYPE OF HYBRIDISATION :

Type of hybridisation = (number of bonds + number of lone pairs)
SUMMARY OF THE THREE MAIN TYPES OF BONDS
Metallic
Li
Ag Na3Bi
Sn Na3Sb
As Na3As
Te Na3P
S Na3N
I2ClFOF2NF3CCl4BF3BeF2Na2O
F2 IF7 SF6 PF5 SiF4 AlF3 MgF2 CsF

Covalent Ionic
RESONANCE
Delocalisation of electron cloud in orbitals of various atoms in a molecule
Exists where more than one Lewis dot structures are possible for a given molecule.
Resonance causes stablisation of the molecule & difference in the energies of hybrid & the most stable
structure is termed as Resonance energy.
R.E. Experimental heat of formation Theoretical heat of formation.
The properties of the actual structure (Resonance hybrid) are decided by the weighed average (depending
on stability) of the contributing molecule.
More the resonating structures more will be the stability to the molecule.
FORCES OF ATTRACTION (WEAKER BONDS)
Hydrogen bonding: When a hydrogen atom is bonded to a highly electronegative atom (like F, O or N)
comes under the influence of another strongly electronegative atom, then a weak electrostatic force of
attraction is developed between them, which is called as hydrogen bond.
Types of H-bonding:
Intermolecular H-bond
Intramolecular H-bond

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Applications in:
(a) Abnormal behaviour of water.
(b) Association of molecules eg. association of CH3COOH, HCOOH
(c) Dissociation of a polar species.
(d) Abnormal melting point & boiling point.
(e) Enhanced solubility in water.
Ion dipole attraction
Dipole-dipole attraction
Ion-induced dipole attraction
Dipole-Induced Dipole attraction
Instantaneous dipole-induced dipole attraction.
Metallic bonds: Electron gas model or sea model, with metal atom existing as kernels along with less
firmly held valence es & bonds between various kernels ( at the lattice site) & valence es is known as
metallic bonds.
MISCELLANEOUS CONCEPT
1. Comparison of bond angles.

(a) In case central atoms are in different hybridisations then it can be compared.
(b) If same hybridisation but different central atoms then bond angle would be more of the molecule in which
central atom is more E.N. eg. OF2 , SF2
O S
103 98
F F F F
(c) Molecules having same C.A. but different substituent then bond angle increases as the attached atom size
increases except in symmetrical molecules and H2O / F2O , NH3 / NF3
2. Bond strength , Bond length & Paramagnetic nature
(a) Using concepts of resonance. Bond order Bond strength
1
bond length
(b) Use of Lewis dot structure for the rest.

If at least one unpaired eleectron is present in the molecule then it will be paramagnetic.

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s - Block Element
The elements in which the last electron enters the outermost s-orbital are called s - block elements. The
group 1 and 2 of periodic table belong to the s-block.
Group - I Elements : (Alkali Metals)
(1) The Elements : are Li , Na, K, Rb, Cs, Fr (Radioactive : t1/2 of Fr233 = 21 minutes)
group - I elements are called alkali metals because they from hydroxides on reaction with water, which are
alkaline in nature.
(2) Outer Electronic configuration : ns1
(3) Atomic and Ionic radii

Li < Na < K < Rb < Cs.
Increase down the group, because value of n (principal quantum number) increases.
(4) Density
Li < K < Na < Rb < Cs.
(5) Ionization Energy

Li > Na > K > Rb > Cs.
As size increases, I.E. decreases down the group (so Cs have lowest I.P.)
(6) Hardness and melting points / boiling points

* These metals are very soft and can be cut with a knife. Lithium is harder than any other alkali metal.
The hardness depends upon cohesive energy
* Cohensive energy Force of attraction between atoms.
M.P. Li > Na > K > Rb > Cs
B.P. Li > Na > K > Cs > Rb
(7) Electropositive character or metallic character

Alkali metals are strongly electropositive and metallic. Down the group electropositive nature increase so
metallic nature also increases.
i.e. M M+ + e
1
Metallic Nature : Electropositive character
I.P.
Li < Na < K < Rb < Cs.
(8) Oxidation state

Show +1 oxidation state because by loosing one electron they get stable noble gas configuration.
(9) Photoelectric effect

The phenomenon of emission of electrons when electromagnetic rays strikes against them is called
photoelectric effect; Alkali metal have low I.P. so show photoelectric effect.
* Cs and K are used in Photoelectric cells.
Chemical Properties
(1) Reactions with air
The alkali metals tarnish in dry air due to the formation of their oxides on their surface, which in turn react
with water to form hydroxides

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4M + O2 2M2O
M2O + H2O 2MO
They react vigorously in oxygen forming following oxides.
4 Li + O2 2 Li2O (Monoxide)
2 Na + O2 Na2O2 (Peroxide)
M + O2 MO2 ( Superoxide) where M = K, Rb, Cs
(2) Solutions in liquid NH3

Alkali metals dissolve in liquid ammonia (high conc. 5 M) and give blue solution which is conducting,
reducing and paramagnetic in nature.
Reason
On dissolving Metal in NH3
M(s) M+ + e
NH 3
M+ + x(NH3) [M(NH3)X ]+ Ammoniated cation

e + y(NH3) [e(NH3)y ] Ammoniated electron
The blue colour is due to Ammoniated electron
The paramagnetic nature is due to Ammoniated electron
The conducting nature is due to Ammoniated M+ + Ammoniated electron
* On standing the colour fades due to formation of amide

1
M+ + e + NH3 MNH2 (amide) + H
2 2 (g)
In the absence of impurities like. Fe, Pt, Zn etc, the solutions are stable.
* In concentrated solution, the blue colour changes to bronze colour and diamagnetic due to the formation of
metal clusters and ammoniated electrons also associate to form electron pairs
2 e (NH3)y [ e (NH3)4]2
(3) Reducing Nature
* Reducing agent is electron donor.
Alkali metals are strong reducing agents with lithium being the strongest and sodium the least prowerful
reducing agent. Na < K < Rb < Cs < Li
Note : Lithium is expected to be least reducing agent due to it's very high IE. However it is strongest. (due to high
hydration energy).
(4) Reaction with H2O

The reaction with water to form the hydroxides having the formula MOH
2M + 2H2O 2MOH + H2
(Highly reactive)
(5) Reaction with H2

They react with H2 forming metal hydride with formula MH which are of ionic nature. Stability of hydride
decreases down the group.
(6) Reaction with N2

Only Lithium reacts with N2 to form ionic lithium nitride Li3N.
3
3Li + N 2 Li3N
2

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(7) Reaction with halogens X2

The alkali metals react vagariously with halogens to form ionic halides M+X
2M + X2 2MX
(8) Sulphides
All metals react with S forming sulphides such as Na2S and Na2Sn (n = 2, 3, 4, 5 or 6). The polysulphide
ions are made from zig-zag chains of sulphur atoms.
S S S S S
S S S S S S S
(9) Crown Ethers and Cryptands:
O
O O O
M
+
O O N
N
O O
O O
O
Cryptand - 222
Dibenzo-18-Grown-6
[Na (Cryptand 222)]+ Na [Contains Na (sodide ion)]

[(s+(Cryptand - 222)] [(Cyrptand-222)e] [electride]
Group II Elements (Alkaline Earth Metals)

(1) The Elements are Be, Mg, Ca, Sr, Ba Ra,
(2) Outermost Electronic configuration : - ns2
(3) Atomic and ionic sizes

* The atomic and ionic radii of the alkali earth metal are smaller than corresponding alkali metals
Reason : higher nuclear charge (Zeff)
* On moving down the group size increase, as value of n increases.

Be < Mg < Ca < Sr < Ba
(4) Ionization Enthalpy

Be > Mg > Ca > Sr > Ba
Down the group IE decreases due to increase in size
Q. IE1 of AM < IE1 of AEM

IE2 of AM > IE2 of AEM
[where AM = Alkali metal, AEM = Alkaline earth metal]
Reason : IE1 of AEN is large due to increased nuclear charge in AEM as compared to AM but IE2 of AM
is large because second electron in AM is to be removed from cation which has

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already acquired noble gas configuration.
(5) Melting and Boiling points

The have low m.p. and b.p. but are higher than corresponding value of group I.
Reason : They have two valency electrons which may participate in metallic bonding compared with only
one electron in AM. Consequently group II elements are harder and have higher cohesive energy and
have much higher m.p./ b.p. than A.M.
M.P. Be > Ca > Sr >Ba > Mg
B.P. Be > Mg > Ca > Ba > Sr
(6) Electropositive and Metallic character

Due to low IE they are strong electropositive but not as strong as AM because of comparatively high IE.
The electropositive character increase down the group.
Be < Mg < Ca < Sr < Ba
(7) Oxidation State

Show + 2 oxidation state.
Chemical Properties
(1) Reactivity towards Air or Oxygen
* Be and Mg are kinetically inert towards oxygen becasue of formation of a film of oxide on their surface.
However powdered Be burn brilliantly.
2Be + O2 (air) 2BeO

3Be + N2 (air) Be3N2

Only Mg give the following behaviour.
Mg + Air (N2 + O2) MgO + Mg3N2

(Similar property with Li due to diagonal relation.)
* BeO, MgO are used as refractory, because these have high m.p.
* Other metals (Ba or Sr form peroxide)

M + O2 MO2

(2) Reaction with H2O

AEM have lesser tendency to react with water as compared to AM. They form hydroxides and liberate H2
on reaction with H2O
M + 2H2O M(OH)2+ H2

* Be is inert towards water.

* Magnesium react as
Mg + 2H2O Mg(OH)2 + H2
or Mg + H2O MgO + H2O
MgO forms protective layer, that is why it does not react readily unless layer is removed amalgamating with
Hg.
Other metals react quite readily (Ca, Sr, Ba).
Note: Be(OH)2 is amphoteric but other hydroxides are basic in nature.

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(3) Reaction with Acids & Bases

AEM react with acids & liberate H2
Mg + 2HCl MgCl2 + H2
Be is amphoteric as it also react with NaOH, other metals do not react as they are purely basic.
Be + 2NaOH Be(OH)2 excess 2
NaOH
[Be(OH)4]
(4) Tendency to form Complexes

AEM have tendency to form some stable complexes. Among these Be and Mg have maximum tendency due
to their small size and high charge density.
BeF2 + 2F [BeF4]2
* Chlorophyll contains Mg2+ [Photosynthetic pigment in plants]
* Ca2+ and Mg2+ form complex with EDTA.
(5) Reactivity with NH3

Like AM, the AEM (only Ca, Sr, Ba) dissolve in by NH3 to give deep blue - black solutions having ammoniated
cations, and ammoniated electrons.
(6) Reaction with Carbon

AEM when heated with carbon form carbides
* Be form Be2C
* Mg, Ca, Sr, Ba form carbides of the formula MC2.
GROUP -I & II
OXIDES
Sodium Oxide (Na2O):
Preparation :
(i) It is obtained by burning sodium at 180C in a limited supply of air or oxygen and distilling off the excess of
sodium in vacuum.
1
2Na + O 180 Na2O

2 2
(ii) By heating sodium peroxide, nitrate or nitrite with sodium.
Na2O2 + 2Na 2Na2O
2NaNO3 + 10Na 6Na2O + N2
2NaNO2 + 6Na 4Na2O + N2
Properties :
(i) It is white amorphous mass.
(ii) It decomposes at 400C into sodium peroxide and sodium
2Na2O 400 C
Na2O2 + 2Na
(iii) It dissolve violently in water, yielding caustic soda.
Na2O + H2O 2NaOH
Sodium Peroxides (Na2O2):
Preparation: It is formed by heating the metal in excess of air or oxygen at 300, which is free from moisture
and CO2.
2Na + O2 Na2O2
Properties:
(i) It is a pale yellow solid, becoming white in air from the formation of a film of NaOH and Na2CO3.
(ii) In cold water (~0C) produces H2O2 but at room temperature produces O2. In ice-cold mineral acids also
produces H2O2.

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~ 0C
Na2O2 + 2H2O 2NaOH + H2O2
2Na2O2 + 2H2O 25
C
4NaOH + O2
Na2O2 + H2SO4 ~ 0C
Na2SO4 + H2O2
(iii) It reacts with CO2, giving sodium carbonate and oxygen and hence its use for purifying air in a confined
space e.g. submarine, ill-ventilated room,
2Na2O2 + 2CO2 2Na2CO3 + O2
(iv) It is an oxidising agent and oxidises charcoal, CO, NH3, SO2.
3Na2O2 + 2C 2Na2CO3 + 2Na [deposition of metallic Na]
CO + Na2O2 Na2CO3
SO2 + Na2O2 Na2SO4
2NH3 + 3Na2O2 6NaOH + N2
(v) It contains peroxide ion [OO]2
Uses:
(i) For preparing H2O2, O2
(ii) Oxygenating the air in submarines
(iii) Oxidising agent in the laboratory.
Oxides of Potassium:
K2O, K2O2, K2O3, KO2 and KO3
Colours: White White Red Bright Yellow Orange Solid
Preparation:
(i) 2KNO3 + 10K heating
6K2O + N2
** K2O heating
K2O
(White) (Yellow)
** K2O + H2O 2KOH
Controlled
(ii) 2K + O2 K2O2 [Props: Similar with Na2O2]
air at 300C
(iii) Passage of O2 through a blue solution of K in liquid NH3 yields oxides K2O2 (white), K2O3 (red) and KO2
(deep yellow) i.e
O
K in liq. NH3 2 K2O2 K2O3 KO2
white red yellow
** KO2 reacts with H2O and produces H2O2 and O2 both
2KO2 + 2H2O ~
0C
2KOH + H2O2 + O2
KO3 : KOH + O3 (ozonised oxygen) 10 to 15C
KO3
(Dry powdered) (orange solid)
Magnesium Oxide (MgO):
It is also called magnesia and obtained by heating natural magnesite.
MgCO3 MgO + CO2
Properties:
(i) It is white powder.
(ii) It's m.p. is 2850C. Hence used in manufacture of refractory bricks for furances.
(iii) It is very slightly soluble in water imparting alkaline reaction.
Calcium Oxide (CaO):

It is commonly called as quick lime or lime and made by decomposing lime stone at a high temperature

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about 1000C.
CaCO3 CaO + CO2 + 42000 cal
Properties:
(i) It is white amorphous powder of m.p. 2570C.
(ii) It emits intense light (lime light), when heated in oxygen-hydrogen flame.
(iii) It is an basic oxide and combines with some acidic oxide e.g.
CaO + SiO2 CaSiO3
CaO + CO2 CaCO3
(iv) It combines with water to produce slaked lime.
CaO + H2O Ca(OH)2
Magnesium Peroxide (MgO2) and Calcium Peroxide (CaO2):

These are obtained by passing H2O2 in a suspension of Mg(OH)2 and Ca(OH)2.
Uses: MgO2 is used as an antiseptic in tooth paste and as a bleaching agent.
HYDROXIDES
Sodium Hydroxides:
Preparation:
(i) Electrolysis of Brine :
NaCl l Na+ + Cl
At anode : 2Cl Cl2 + 2e
At cathode : H+ + e H
(ii) Caustication of Na2CO3 (Gossage's method):

Na2CO3 + Ca(OH)2 l 2NaOH + CaCO3
(suspension)
Since the Ksp (CaCO3) < Ksp (Ca(OH)2), the reaction shifts towards right.
Properties:
(i) It is white crystalline, deliquescent, highly corrosive solid.
(ii) It is stable towards heat.
(iii) It's aqueous solution alkaline in nature and soapy in touch.
(iv) NH4Cl + NaOH NaCl + NH3 + H2O
FeCl3 + 3NaOH Fe(OH)3 + 3NaCl
Brown ppt
ZnCl2 + 2NaOH Zn(OH)2 + 2NaCl

Zn(OH)2 + 2NaOH Excess Na2ZnO2 + 2H2O [Same with AlCl3, SnCl2, PbCl2]
soluble
(v) Acidic and amphoteric oxides gets dissolved easily e.g.
CO2 + 2NaOH Na2CO3 + H2O
Al2O3 + 2NaOH 2NaAlO2 + H2O
(vi) Aluminium and Zn metal gives H2 from NaOH
2Al + 2NaOH + 2H2O 3H2 + 2NaAlO2
(vii) Several non metals such as P, S, Cl etc. yield a hydride instead of hydrogen.e.g.
4P + 3NaOH + 3H2O PH3 + 3NaH2PO2 (Disproportionation reaction)
Potassium Hydroxide:
Preparation: Electrolysis of KCl aqueous solution.
Properties: Same as NaOH

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*(a) It is stronger base compared to NaOH.

(b) Solubility in water is more compared to NaOH.
(c) In alcohol, NaOH is sparingly soluble but KOH is highly soluble.
(d) As a reagent KOH is less frequently used but in absorption of CO2, KOH is preferably used compared to
NaOH. Because KHCO3 formed is soluble whereas NaHCO3 is insoluble and may therefore choke the
tubes of apparatus used.
Magnesium Hydroxide: It occurs in nature as the mineral brucite.

Preparation: It can be prepared by adding caustic soda solution to a solution of Mg-sulphate or chloride
solution.
Mg+2 + 2NaOH Na2SO4 + Mg(OH)2
Properties:
(i) It can be dried at temperature upto 100C only otherwise it breaks into its oxide at higher temperature.
Mg(OH)2 MgO + H2O
(ii) It is slightly soluble in water imparting alkalinity.
(iii) It dissolves in NH4Cl solution
Mg(OH)2 + 2NH4Cl MgCl2 + 2NH4OH
** Thus, Mg(OH)2 is not therefore precipitated from a solution of Mg+2 ions by NH4OH in presence of excess
of NH4Cl.
Calcium Hydroxide:
Preparation: By spraying water on quicklime
CaO + H2O Ca(OH)2
Properties:
(i) It is sparingly soluble in water.
(ii) It's solubility in hot water is less than that of cold water. Hence solubility decreases with increase in
temperature.
(iii) It readily absorbs CO2 as used as a test for the gas.
(iv) It is used as a mortar.
[Mortar is a mixture of slaked lime (1 Part) and sand (3 Parts) made into paste with water.]
CARBONATES
Sodium Carbonate:
Preparation:
(i) Leblanc Process:
mild heating
NaCl + H2SO4 (conc.) NaHSO4 + HCl
NaCl + NaHSO4 Strongly
Na2SO4 + HCl
heated
(Salt Cake)
Na2SO4 + 4C Na2S + 4CO
Na2S + CaCO3 Na2CO3 + CaS
(ii) Solvay Process:

NH3 + H2O + CO2 NH4HCO3
NaCl + NH4HCO3 NaHCO3 + NH4Cl
2NaHCO3 150 C
Na2CO3 + H2O + CO2
Properties:
(i) Anhydrous Na2CO3 is called as soda ash, which does not decompose on heating but melts at 852C.
(ii) It forms number of hydrates.
Na2CO3. H2O Crystal carbonate Na2CO3 + moisture in air
Na2CO3. 7H2O

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Na2CO3.10H2O Washing soda

(iii) Na2CO3 absorbs CO2 yielding sparingly soluble sodium bicarbonate which can be calcined at 250 to get
pure sodium carbonate.
Na2CO3 + H2O + CO2 2NaHCO3
(iv) It dissolved in acid with effervescence of CO2 and causticised by lime to give caustic soda.
Na2CO3 + HCl 2NaCl + H2O + CO2
Na2CO3 + Ca(OH)2 2NaOH + CaCO3
Uses: It is widely used in glass making as smelter.
Potassium Carbonate:
By leblance process, it can be prepared but by solvay process it cannot be prepared because KHCO3 is
soluble in water.
Properties: It resembles with Na2CO3, m.p. is 900C but a mixture of Na2CO3 and K2CO3 melts at 712C.
Uses: It is used in glass manufacturing.
Calcium Carbonate:
It occurs in nature as marble, limestone, chalk, coral, calcite etc. It is prepared by dissolving marble or
limestone in HCl and removing iron and aluminium present, by precipitating with NH3 and then adding
(NH4)2CO3 to the solution.
CaCl2 + (NH4)2CO3 CaCO3 + 2NH4Cl
Properties:
(i) It dissociates above 1000C as follows:
CaCO3 CaO + CO2
(ii) It dissolves in water containing CO2 forming Ca(HCO3)2 but is precipitated from the solution by boiling.
CaCO3 + H2O + CO2 Ca(HCO3)2
Magnesium Carbonate:
It occurs in nature as magnesite, isomorphous with calcite. It is obtained as a white precipitated by adding
sodium bicarbonate to a solution of a magnesium salt; but only basic carbonate, called magnesia alba,
having the approximate composition MgCO3, Mg(OH)2, 3H2O is precipitated.
Properties: Same with CaCO3.
BICARBONATES
Sodium bicarbonates:
Preparation: By absorption of CO2 in Na2CO3 solution.
Na2CO3 + H2O + CO2 2NaHCO3
> 100C sparingly soluble
Uses: It is used in medicine and as baking powder.
Potassium bicarbonates:
Preparation: Same as NaHCO3
Properties: Same with NaHCO3
But It is more alkaline and more soluble in water compared to NaHCO3.
Magnesium bicarbonate:
MgCO3 + CO2 + H2O Mg(HCO3)2
Calcium bicarbonate:
CaCO3 + CO2 + H2O l Ca(HCO3)2

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CHLORIDES
Sodium Chloride: Prepared from brine containing 25% NaCl.

Properties:
(i) It is nonhygroscopic but the presence of MgCl2 in common salt renders it hygroscopic.
(ii) It is used to prepare freezing mixture in laboratory [Ice-common salt mixture is called freezing mixture and
temperature goes down to 23C.]
(iii) For melting ice and snow on road.
Potassium Chloride: It is also occurs in nature as sylvyne (KCl) or carnalite (2KCl MgCl2 6H2O)
Uses: It is used as fertiliser.
Magnesium Chloride:
Preparation: By dissolving MgCO3 in dil. HCl
MgCO3 + 2HCl MgCl2 + H2O + CO2
Properties:
(i) It crystallises as hexahydrate. MgCl2. 6H2O
(ii) It is deliquescent solid.
(iii) This hydrate undergoes hydrolysis as follows:
MgCl26H2O Mg(OH)Cl + HCl + 5H2O
Mg(OH)Cl MgO + HCl
** Hence, Anh. MgCl2 cannot be prepared by heating this hydrate.
** Because of this formation of HCl. Sea water cannot be used in marine boilers which corrodes the iron body.
(iv) Anhydrous MgCl2 can be prepared by heating a double salt like. MgCl2 . NH4Cl . 6H2O as follows:
H2O strong
MgCl2 . NH4Cl . 6H2O MgCl2 . NH4Cl MgCl2 + NH3 + HCl

Sorel Cement: It is a mixture of MgO and MgCl2 (paste like) which set to hard mass on standing. This is used
in dental filling, flooring etc.
Calcium Chloride:
(i) It is the by-product in solvay process.
(ii) It may also be prepared by dissolving the carbonate in HCl
CaCO3 + 2HCl CaCl2 + H2O + CO2
Properties:
(i) It is deliquescent crystals.
(ii) It gets hydrolysed like MgCl2 hence anhydrous CaCl2 cannot be prepared.
CaCl2 + H2O l CaO + 2HCl
Hence, anh CaCl2 is prepared by heating CaCl2. 6H2O in a current of HCl (dry)
(iii) Anh. CaCl2 is used in drying gases and organic compounds but not NH3 or alcohol due to the formation of
CaCl2 . 8NH3 and CaCl2 . 4C2H5OH.
SULPHATES
Sodium Sulphate:
Preparation:
It is formed in the 1st step of leblanc process by heating common salt with sulphuric acid.
2NaCl + H2SO4 Na2SO4 + 2HCl
Thus the salt cake formed is crystallised out from its aqueous solution as Na2SO4 . 10H2O. This
called as Glauber's salt.
** One interesting feature of the solubility of glauber's salt is; when crystallised at below 32.4C, then Na2SO4.
10H2O is obtained but above 32.4C, Na2SO4 (anh.) comes out.

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Properties: It is reduced to Na2S when fused with carbon.

Na2SO4 + 4C Na2S + 4CO
Uses: It is used in medicine.
Potassium Sulphate:
It occurs in st assfurt potash beds as schonite K 2 SO 4 MgSO 4 6H 2 O and Kainit e,
KCl MgSO4 3H2O from which it is obtained by solution in water and crystallisation. It separates from the
solution as anh, crystals whereas Na2SO4 comes as decahydrate.
Uses: It is used to prepare alumn.
Magnesium Sulphate:
Preparation:
(i) It is obtained by dissolving kieserite. MgSO4. H2O in boiling water and then crystallising the solution as a
hepta hydrate. i.e. MgSO4. 7H2O. It is called as Epsom salt.
(ii) It is also obtained by dissolving magnesite in hot dil. H2SO4.
MgCO3 + H2SO4 MgSO4 + H2O + CO2
(iii) or by dissolving dolomite (CaCO3, MgCO3) in hot dil. H2SO4 and removing the insoluble CaSO4 by filtration.
(iv) It is isomorphous with FeSO4. 7H2O, ZnSO4.7H2O
Calcium Sulphate: It occurs as anhydrite CaSO4 and as the dihydrate CaSO4. 2H2O, gypsum, alabaster or
satin-spar.
Properties:
(i) Gypsum (CaSO4. 2H2O) 2CaSO4. H2O (Plaster of paris)
(anhydrous)CaSO4.
Dead burnt. plaster
(ii) Solubility of CaSO4 at first increases upto a certain point and then decreases with rise of temperature.
(iii) Plaster paris is used in mould making due to its porous body.

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The p - Block Elements

The elements in which the last electron enters the other most p orbital are called p- block elements. As the
maximum number of electrons that can be accommodated in a set of p-orbitals is six, therefore there are six
groups of p - blocks in the periodic table.
Group 13 Elements : Boron Family
The Elements are B (Non metal), Al, Ga, In, T (Metals)

General electronic configuration [Noble gas] ns2 np1
Atomic and Physical properties.
Atomic radii : B > Ga < Al < In < T
(2) Ionization Enthalpies.

B > T > Ga > Al > In (Sum of three IE values)

M.P. B > Al > Tl > In > Ga
B.P. B > Al > Ga > In > Tl
(4) Electropositive Character

Due to high IE they are less electropositive on moving down the group metallic character increases due to
decrease in IE [ B is nonmetals and other elements are metals.]
B Al Ga In Tl
Non Metals
metal
Note : Boron exists in many allotropic forms. All the allotropes have basic building B12 icosahedral units made up
of polyhedron having 20 faces and 12 corners.For example one is the simplest form : - rhombohedral
boron.
But Al , In & T all have close packed metal structure.

Chemical Properties :
B already discussed.
(1) Reaction with Air at Water
Al should react air to form a very thin oxide film (104 to 106 mm thick) on the surface and protects the
metal from further attack
3
2 Al(s) + O (g) Al2O3(s) H = 1670 kJ/mole (Thermal reaction)
2 2
Ga and In are attacked neither by cold water nor hot water unless oxygen is present. T form an oxide on
surface.
(2) Reaction with Oxides and Bases

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Al dissolve in dilute mineral acids liberating H2

2Al + 6HCl 2AlCl3 + 3H2
Al also dissolves in aqueous NaOH ( amphoteric) liberating H2 and forming aluminates
2Al + 2NaOH + 6H2O 2 Na[Al(OH)4] + H2
or
2NaAlO2 + 2H2O
Ga, In, T dissolve in dilute acids liberating H2 Ga is amphoteric like Al and it dissolves in aq. NaOH
liberating H2 and forming gallates.
Isolation of "B":
(i) Preparation of B2O3 from Borax or Colemanite
Na2B4O7 + HCl/H2SO4 NaX + H2B4O7
H2B4O7 + 5H2O 4H3BO3 B2O3 + H2O
(ii) Reduction of B2O3
B2O3 + Na/K/Mg/Al B + Na2O/K2O/MgO/Al2O3
Chemical Props.:
(i) Burning in air : 4 B + 3O2 2B2O3
4Al + 3O2 2Al2O3
(ii) Reaction with water
B + H2O (Cold & hot) no reaction
2B + 3H2O B2O3 + H2
(red hot)
3
Al + 3H2O Al(OH)3 + H
2 2
(iii) B + HCl no reaction
B + H2SO4 (dil) no reaction
2B + 3H2SO4 (conc.) 2H3BO3 + 3SO2
B + 3HNO3 H3BO3 + 3NO2
2Al + 6H2SO4 Al2(SO4)3 + 3SO2 + 6H2O
Al + HNO3(80%) Al2O3 (passive layer) and does not react further.
(iv) 2B + 2NaOH + 2H2O 2NaBO2 + 3H2
2Al + 2NaOH + 2H2O 2NaAlO2 + 3H2
(v) 2B + N2 2BN 2Al + N2 2AlN
4B + C B4C 4Al + 3C Al4C3
(vi) 3Mg + 2B Mg3B2
Preparation of B2H6 :
(i) Mg3B2 + HCl B2H6 + B4H10 + B5H9 etc.
(10%)

(ii) B4H10 B2H6 + H2 + higher borane
100C
Electric
(iii) BCl3 (or B Br3) + 6H2 B2H6 + 6HCl
discharge at low pressure
(iv) 3LiAlH4 + 4BF3 3LiF + 3AlF3 + 2B2H6
or LiBH4 or 3(BF3)
Reaction of B2H6 :
(i) B2H6 + O2 burns in

B2O3 + H2O
air spontaneously

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(ii) B2H6 + H2O (Cold is enough) H3BO3 + 6H2
anh .
(iii) B2H6 + HCl (dry) B2H5Cl + H2
AlCl3
Orthoboric Acid
H3BO3 is soluble in water and behaves as weak monobasic acid. It does not donate protons like most the
acids, but rather it accepts OH . It is therefore is Lewis acid (B(OH)3)
B(OH)3 + 2H2O H3O+ + [B(OH)4]
or
H3BO3
Since B(OH)3 only partially reacts with water to form H3O+ and [B(OH)4] it behaves as a weak acid. Thus
it cannot be titrated satisfactorily with NaOH as a sharp end point is not obtained. If certain polyhydroxy
compounds such as glycerol, mannitol or sugar are added to the titration mixture then B(OH)3 behaves as
a strong monobasic acid. and hence can now be titrated with NaOH and end point is diluted using
phenolphthalein as indicator.
B(OH)3 + NaOH Na[B(OH)4]
NaBO2 + 2H2O
The added compound must be a as diol to enhance the acidic proprieties in this way the cis-diol forms very
stable complexes with [B(OH)4] formed in forward direction above, thus effectively removing it from
solution. Hence reaction proceeds in forward direction (Le-Chatelier principle.)
C OH HO OH C O OH
+ B B
2H2O
C OH HO OH C O OH
C O O C HO C
B
C O O C 2H2O HO C
* Heating of boric acid :
H3BO3 100C
HBO2 140C
H2B4O7 B2O3
red hot
Metaboric acid tetraboric acid Glassy mass
* H3BO3 + H2O2(H2O)+ (HO)2BOOH NaOH

Na2 6H2O
Sodium peroxy borate used in washing powder

as brightener
Preparation of Borax :
2CaO 3B2O3 + 2Na2CO3 2CaCO3 +Na2B4O7 + 2NaBO2
Colemanite
NaBO2 + Na2B4O710H2O Concentrated Na 2 B4O 7 NaBO 2

in Filtrate
as residue and allowed to
in solution
crystallise out
and filtered

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[4NaBO2 + CO2 Na2B4O7 + Na2CO3]
Na2B4O7 10H2O
as 2nd Crop. of the
reaction.
Uses of borax: (i) In making glass, enamel and glaze of pottery.

(ii) As antiseptic in medicinal soaps preparation.
Al2O3 preparation :
(i) 2Al(OH)3 300

C
Al2O3 + 3H2O

(ii) Al2(SO4)3 Al2O3 + 3SO3

(iii) (NH4)2SO4 Al2(SO4)3 24H2O Al2O3 + 2NH3 + 4SO3 + 25H2O
Uses: (i) In making refractory brick

(ii) as abrasive
(iii) To make high alumina cement
AlCl3 preparation:
(i) 2Al + 6HCl (vap.) 2AlCl3 + 3H2

(over heated) dry

(ii) Al2O3 + 3C + 3Cl2
2AlCl3 (vap.) + 3CO
1000C
Solid anh. AlCl3

Props:
(i) Its anhydrous formed is deliquescent and fumes in air.
(ii) It sublimes at 180C.
(iii) It is covalent and exists in the form of dimer even if in non polar solvents e.g.
alc., ether, benzene, where it is soluble in fair extent.
Uses: (i) Friedel-Craft reaction
(ii) Dyeing, drug. & perfumes etc.
Alumns: M2SO4, M '2 (SO4)3 24 H2O Props: Swelling characteristics
where M = Na+, K+, Rb+, Cs+, As+, Tl+, NH 4

M' = Al+3, Cr+3, Fe+3, Mn+3, Co+3
K2SO4Al2(SO4)324H2O Potash alum
(NH4)2SO4Al2(SO4)324H2O Ammonium alum
K2SO4Cr2(SO4)3 24H2O Chrome alum
(NH4)2SO4Fe2(SO4)324H2O Ferric alum
Preparation: Al2O3 + 3H2SO4 Al2(SO4)3 + 3H2O

Al2(SO4)3 + K2SO4 + aq. soln crystallise
Uses: (i) Act as coagnlant

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(ii) Purification of water

(iii) Tanning of leather
(iv) Mordant in dying
(v) Antiseptic
Group 14 Elements (Carbon Family)

The Elements are C [Non metals] ,
Si, Ge [Metalloids],
Sn, Pb, [Metals]
General electronic configuration [ noble gas] ns2 np2

(I) Atomic and Physical properties
(1) Atomic Radii
Covalent radii : C < Si < Ge < Sn < Pb
(2) Ionizations Enthalpies

C > Si > Ge > Pb > Sn (IE1 values)
(3) Melting and Boiling Points
M.P. C > Si > Ge > Pb > Sn
B.P. Si > Ge > Sn > Pb
(4) Metallic Character
C < Si < Ge < Sn < Pb (Metallic character)
C, Si [Non metal]
Ge [ Metal ]
Sn, Pb [Metal]
(II) Chemical Properties (Discussed in sheet)
* Unique Character of C
* Catenation
The property of forming bonds with atoms of the same element or tendency to self linking called catenation.
Carbon shows maximum catenation. On moving down the group catenation tendency decreases. This because
the strength of C C bond is very high and in case of other elements, strength of M M (where M = Si, Ge,
Sn, Pb) bond is decreases down the group.
Bond Bond Energy (kJmol1)

CC 348
Si Si 297
Ge Ge 260
Sn Sn 240
Types of Carbide
(i) Ionic and salt like:
Classification on basis of (a) C1 unit
no. of carbon atoms (b) C2 unit

present in hydrocarbon (c) C3 unit
found on their hydrolysis
C1 unit: Al4C3, Be2C
Be2C + H2O Be(OH)2 + CH4
Al4C3 + 12H2O 4Al(OH)3 + 3CH4

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C2 unit: CaC2, BaC2

CaC2 + 12H2O Ca(OH)2 + CH CH
C3 unit: Mg2C3
Mg2C3 + H2O 2Mg(OH)2 + CH3C CH : Propyne
(ii) Covalent carbide : SiC & B4C
(iii) Interstitial carbide : MC (Transition element or inner transitional elements forms this kind of carbide)
Interstitial carbide formation doesn't affect the metalic lusture and electrical conductivity.( no chemical
bond is present, no change in property)
SiC
Preparation
2000 to
SiO2 + 2C(coke) Si + 2CO
2500C
2000 to
Si + C SiC diamond like structure colourless to yellow solid in room temp.
2500C

when impurity is present
Properties
(i) It is very hard and is used in cutting tools and abrassive powder(polishing material)
(ii) It is very much inert
(iii) It is not being affected by any acid except H3PO4
CO
How to detect
How to estimate
What are its absorbers
(i) How to detect
(a) burns with blue flame
(b) CO is passed through PdCl2 solution giving rise to black ppt.
CO + PdCl2 + H2O CO2 + Pd + 2HCl
Black metallic
deposition
(ii) How to estimate
I2O5 + 5CO I2 + 5CO2
I2 + S2O32 2I + S4O62
(iii) What are its absorbers
(a) Cu2Cl2 : CuCl + CO + 2H2O [CuCl(CO)(H2O)2]
Uses:
In the Mond's process of Ni - extraction
CO is the purifying agent for Ni
50C
Impure Ni + CO Ni(CO)4 150
C
Ni + 4CO
recycled
Producer gas: CO + N2 + H2
Water gas: CO + H2
Water gas is having higher calorific value than producer gas. in water gas, both CO & H2 burns while in
producer gas N2 doesn't burn.

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Teflon (CF2 CF2

)n
heated with heated Polymerisa tion at
CHCl3 + HF CF2HCl CF2=CF2 (CF2 CF2
)n
SbFCl 4 again high temp. and press
catalyst HCl
Purpose
Temp. withstanding capacity upto 500550C (1st organic compound withstand this kind of high temp.)
SILICON (Si)
Occurrence
Silicon is the second most abundant (27.2%) element after oxygen (45.5%) in the earth's crust. It does not
occur free in nature but in the combined state, it occurs widely in form of silica and silicates. All mineral
rocks, clays and soils are built of silicates of magnesium, aluminium, potassium or iron. Aluminium silicate
is however the most common constituent of rocks and clays.
Silica is found in the free state in sand, flint and quartz and in the combined state as silicates like
(i) Feldspar K2O. Al2O3. 6SiO2
(ii) Kaolinite Al2O3. 2SiO2. 2H2O
(iii) Asbestos CaO. 3MgO. 4SiO2
Preparation
(i) From silica (sand): Elemental silicon is obtained by the reduction of silica (SiO2) with high purity coke in an
electric furnace.
SiO2(s) + 2C(s) high
temperature
Si(s) + 2CO(g)
(ii) From silicon tetrachloride (SiCl4) or silicon chloroform (SiHCl3) : Silicon of very high purity required for
making semiconductors is obtained by reduction of highly purified silicon tetrachloride or silicon chloroform
with dihydrogen followed by purification by zone refining.
SiCl4(l) + 2H2(g) Si(s) + 4HCl(g)
SiHCl3(s) + H2(g) Si(s) + 3HCl (g)
PHYSICAL PROPERTIES :
(i) Elemental silicon is very hard having diamond like structure.
(ii) It has shining luster with a melting point of 1793 K and boiling point of about 3550 K.
28 29 30 28
(iii) Silicon exists in three isotopes, i.e. 14 Si , 14 Si and 14 Si but 14 Si is the most common isotope.
CHEMICAL PROPERTIES:
Silicon is particularly unreactive at room temperature towards most of the elements except fluorine. Some
important chemical reactions of silicon are discussed below.
(i) Action of air : Silicon reacts with oxygen of air at 1173 K to form silicon dioxide and with nitrogen of air
at 1673 K to form silicon nitride,.
Si(s) + O2(g) 1173
K
SiO2(s)
Silicon dioxide
3Si(s) + 2N2(g) 1673
K
Si3N4(s)
Silicon nitride
(ii) Action of steam : It is slowly attacked by steam when heated to redness liberating dihydrogen gas.
Si(s) + 2H2O(g) redness
SiO2(s) + 2H2(g)
(iii) Reaction with halogens: It burns spontaneously in fluorine gas at room temperature to form silicon
tetrafluoride (SiF4).
Si(s) + 2F2(g) Room
Temperatur
e SiF4(l)
However, with other halogens, it combines at high temperatures forming tetrahalides.
(iv) Reaction with carbon : Silicon combines with carbon at 2500 C forming silicon carbide (SiC) known as
carborundum.

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Si(s) + C(s) 2500

C
SiC(s)
Carborundum is an extremely hard substance next only to diamond. It is mainly used as an abrasive and as
a refractory material.
USES:
(i) Silicon is added to steel as such or more usually in form of ferrosilicon (an alloy of Fe and Si) to make it
acid-resistant.
(ii) High purity silicon is used as semiconductors in electronic devices such as transistors.
(iii) It is used in the preparation of alloys such as silicon-bronze, magnesium silicon bronze and ferrosilicon.
COMPOUNDS OF SILICON:
What is silane. SinH2n+2 SiH4 & Si2H6
Only these two are found
Higher molecules are not formed. Si can't show catanetion property
dil. H SO
Hot Mg + Sivap Mg2Si 2
4 MgSO4 + SiH4 + Si2H6 + ...
Ques. SiH4 is more reactive than CH4. Explain
Reasons
(i) Si H in C H
CelectrovethanH
Si less electro-ve than H
So bond polarity is reversed when Nu attacks, it faces repulsion in C but not in Si
(ii) Silicon is having vacant d orbital which is not in case of carbon
(iii) Silicon is larger in size compared to C. By which the incoming Nu doesn't face any steric hindrance to
attack at Si whereas CH4 is tightly held from all sides.
Silicones
It is organo silicon polymer
CCl4 + H2O no hydrolysis
but CCl4 + H2O COCl2 + 2HCl
super heated
steam
SiCl4 + H2O Si(OH)4 + 4HCl
SiO2(3-D silicate)
R R R

| | |
R2SiCl2 + H2O
2 HCl
R2 Si(OH)
2 H O O Si O Si O Si O
2 | | |
R R R
Linear silicone
O
H O
R2CCl2 + H2O 2
R2C(OH)2 ||
2 HCl
looses H 2O R CR
readily
Silicones may have the cyclic structure also having 3, 4, 5 and 6 nos. of silicon atoms within the ring.
Alcohol analogue of silicon is known as silanol

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R R
| |
R Si O Si R
| |
O O
| |
R Si O Si R
| |
R R
cyclic silicone
not planar
H 2O 2 H O
R3SiCl R3SiOH R3Si-O-SiR3

Silanol
R R
H 2O H2O | |
R2SiCl2 + R3SiCl Si O Si
hydrolysis heating
condensati on | |
R R
This end of the chain can't be extended hence
R3SiCl is called as chain stopping unit
* Using R3SiCl in a certain proportion we can control the chain length of the polymer
| |
O R O
| | |

RSiCl3 + H2O R-Si(OH)3 R Si O Si O Si O
| | |
O O R
| |
cross linked silicone
3 dimensional network
It provides the crosslinking among the chain making the polymer more hard and hence controling the
proportion of RSiCl3 we can control the hardness of polymer.
Uses
(1) It can be used as electrical insulator (due to inertness of SiOSi bonds)
(2) It is used as water repellant ( surface is covered) eg. car polish, shoe polish, massonary works in buildings
(3) It is used as antifoaming agent in sewage disposal, beer making and in cooking oil used to prepare potato chips.
(4) As a lubricant in the gear boxes.
SILICA (SiO2)
Occurrence:
Silica or silicon dioxide occurs in nature in the free state as sand, quartz and flint and in the combined state
as silicates like, Feldspar : K2O.Al2O3.6SiO2, Kaolinite : Al2O3. 2SiO2. 2H2O etc.
PROPERTIES:
(i) Pure silica is colourless, but sand is usually coloured yellow or brown due to the presence of ferric oxide as
an impurity.
(ii) Silicon dioxide is insoluble in water and all acids except hydrofluoric acid.
SiO2(s) + 4HF(l) SiF4(l) + 2H2O(l)
(iii) It also combines with metallic oxides at high temperature giving silicates e.g.

SiO2(s) + CaO(s) CaSiO3(s)
(iv) When silica is heated strongly with metallic salts, silicates are formed and the volatile oxides are driven off
as vapours.
SiO2(s) + Na2CO3(s) high temp.
Na2SiO3(s) + CO2(g)

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SiO2(s) + Na2SO4(s) high

temp.
Na2SiO3(s) + SO3(g)
3SiO2(s) + Ca3(PO4)2(s) high
temp.
3CaSiO3(s) + P2O5(g)
The first two examples quoted here are important in glass making.
STRUCTURES OF SILICA :
Silica has a three-dimensional network structure. In silica, silicon is sp3-hybridized and is thus linked to four
oxygen atoms and each oxygen atom is linked to two silicon atoms forming a three-dimensional giant
molecule as shown in figure. This three-dimensional network structure imparts stability to SiO2 crystal and
hence a large amount of energy is required to break the crystal resulting in high melting point.
| | |
Si O Si O Si
| | |
O O O
| | |
Si O Si O Si
| | |
O O O
| | |
Si O Si O Si
| | |
USES:
(i) Sand is used in large quantities to make mortar and cement.
(ii) Being transparent to ultraviolet light, large crystal of quartz are used for making lenses for optical instruments
and for controlling the frequency of radio-transmitters.
(iii) Powdered quartz is used for making silica bricks.
(iv) Silica gel (SiO2.xH2O) is used as a desiccant (for absorbing moisture) and as an adsorbent in chromatography.
TIN & ITS COMPOUND
Sn 1500C
(i) SnO2 [Burns with a bright flame]
O2
(ii) Sn + 2H2O
(iii) Reaction with acid.
Sn
(iv) Sn + 2NaOH + H2O Na2SnO3 + 2H2.

or
KOH [In absence of air Na2SnO2 forms and in contact with air it readity converts into Na2SnO3]
1500C
strongly
Oxides: Sn + O2
heated

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SnO (grey)
& SnO2 (white)
SnC2O4 SnO (grey) + CO + CO2
out of
contact of
air
SnCl2 KOH
Sn(OH)2
Both are amphoteric in nature :
SnO + H2SO4 SnSO4 + H2O
SnO + 2HCl SnCl2 + H2O
SnO + 2NaOH or KOH cold Na2SnO2 or K2SnO2 +H2O
But conc. hot alkali behaves differently.
2SnO + 2KOH or NaOH K2SnO3 or Na2SnO3 + Sn + H2O
* Bi(OH)3 + [Sn(OH)4]2 Bi + [Sn(OH)6]2
(black)
SnO2 + 2H2SO4
Sn(SO4)2 + 2H2O
(Soluble only in hot conc. H2SO4)
SnO2+ 2NaOH Na2SnO3 + H2O
SnCl2 & SnCl4 :
(1) Sn + 2HCl (hot conc.) SnCl2 + H2
SnCl2.2H2O Sn(OH)Cl + HCl + H2O Hence anh. SnCl2 cannot be obtained.

SnO + HCl
{SnCl4 + 4H2O Sn(OH)4 + 4HClfumes comes out}
(2) A piece of Sn is always added to preserve a solution of SnCl2. Explain.
6SnCl2 + 2H2O + O2 2SnCl4 + 4Sn(OH)Cl (white ppt)
SnCl4 + Sn 2SnCl2
SnCl4 + 4H2O Sn(OH)4 (white ppt.) + 4HCl
(3) SnCl2 + HCl HSnCl3 HCl
H2SnCl4
SnCl4 + 2HCl H2SnCl6(Hexachloro stannic (IV) acid)

SnCl4+ 2NH4Cl (NH4)2 SnCl6 (colourless crystalline compound known as " pink salt ")
(4) Red Prop. of SnCl2 :
Sn+2 + 2Fe+3 2Fe+2 + Sn+4
2Cu+2 + Sn+2 2Cu+ + Sn+4
Hg+2 + Sn+2 Hg +Sn+4
PhNO2 + SnCl2 / HCl PhNH2 + Sn+4
K2Cr2O7 + SnCl2 + HCl Cr+3 + Sn+4 + KCl + H2O
(5) Readily combines with I2 SnCl2I2 This reaction is used to estimate tin.
Formation of SnCl4 :
(i) Sn + Cl 2 (Excess) SnCl4 (ii) 2HgCl2 + SnCl2 2Hg + SnCl4
(molten ) (dry)
(iii) Sn + Aq. rigia SnCl4 + NO + H2O
* SnCl4. 5H2O is known as butter of tin used as mordant.
(NH4)2 SnCl6 is known as 'pink salt' used as calico printing.
Mosaic gold : SnS2 yellow crystalline substance :

Sn + 4NH4Cl (NH4)2 SnCl4 + 2NH3 + H2
2(NH4)2 SnCl4 + 2S SnS2 + 2NH4Cl + (NH4)2SnCl6

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* Distinction of Sn+2 / Sn+4 :

2
(i) H2S (ii) Hg+2 (iii) Fe+3 + K3[Fe(CN)6] Sn
Blue ppt.
COMPOUNDS OF LEAD
Oxides of lead :
(i) PbO (ii) Pb3O4 (Red) (iii) Pb2O3(reddish yellow) (Sesquioxide)
(iv) PbO2 (dark brown)
(1) PbO
Laboratory Prepn. :
Pb(NO3)2 2PbO + 4NO2 + O2
above 600C
PbO2 PbO , hot oxide
Pb3O4 easily reduced to Pb by
H 2 or C.
Pb2O3
Preparation of Pb2O3 :
2PbO + NaOCl Pb2O3 + NaCl
Limited
n amount
hot sol .
of it in NaOH
Pb2O3 + 2HNO3 PbO2 + Pb(NO3)2 + H2O

This reaction suggests that Pb2O3 contains PbO2.
(2) Pb3O4 : 6PbO + O2 2Pb3O4 {In the same way, prove that its formula is 2PbO. PbO2}
Pb3O4 + 4HNO3 (cold.conc) or (hot dil.) 2Pb(NO3)2 + PbO2 + 2H2O
But 2Pb3O4 + 6H2SO4 6PbSO4 + 6H2O + O2

Pb3O4 + 8HCl 3PbCl2 + 4H2O + Cl2
(3) PbO2 : Insoluble in water. HNO3, But reacts with HCl + H2SO4(hot conc.) and in hot NaOH / KOH.
(i) Pb3O4 + 4HNO3 2Pb(NO3)2 + PbO2 + 2H2O
(ii) Pb(OAc)2 + Ca(OCl)Cl + H2O PbO2[Brown(dark)] + CaCl2 + 2CH3CO2H

Excess bleaching powder
is being removed by stirring with
HNO3
Reaction : PbO2 + 4HCl PbCl2 + Cl2 + 2H2O

2PbO2 + 2H2SO4 2PbSO4 + 2H2O + O2
PbO2 + 2NaOH Na2PbO3 + H2O
PbO2 : Powerful oxidising agent :
(i) PbO2 + SO2 PbSO4 [spontaneously]
(ii) PbO2 + 2HNO3 + (COOH)2 Pb(NO3)2+ 2CO2 + 2H2O
(iii) 2Mn(NO3)2 + 5PbO2 + 6HNO3 3Pb(NO3)2 + 2PbSO4 + 2HMnO4 + 2H2O
PbCl4 : Exists as H2[PbCl6]

PbO2 + 4HCl PbCl4 + 2H2O
{ice cold conc. saturated with Cl2}
PbCl4 + 2HCl H2PbCl6
TetraEthyl lead :
4NaPb(alloy 10%Na.) + 4C2H5Cl(vap.) 3Pb + Pb(Et)4 + 4NaCl
It is antiknocking agent.

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Group 15 Elements (Nitrogen Family)

The elements are N,P [ Non metal]
As [ Matalloid]
Sb, Bi [Metal]
The General electronic configuration is [noble gas] ns2 np3
(I) Atomic and Physical properties

Covalent radius : N < P < As < Sb < Bi
(2) Ionization enthalpies

N > P > As > Sb > Bi (IE1 values)
(3) Electronegativity N > P > As > Sb = Bi

N P As Sb Bi
Non Metalloid Metals
metal
(5) Catenation
* The group 15 elements also show catenation property but to much smaller extent than carbon. For example
hydrazine (H2NNH2) has two N atoms bonded together HN3 has three N atoms.
HN3 +
HN=N=N
* Among group 15 elements P has the maximum tendency for catenation forming cyclic as well as open chain
compounds consisting of many phosphorous atoms.
P2H4 has tow P atoms bonded together the lesser tendency of elements of group 15 to show catenation in
compression to carbon is their low dissociation enthalpies.
CC 353.3 kJ /mole
NN 16.8 kJ / mole
PP 201.6 kJ / mole
As As 147.4 kJ / mole
(6) Allotropy
Except N and Bi all other elements of this group show allotropy.
Phosphorous : White, Black and Red
Arsenic : Yellow or Grey
Antimony : Yellow or Silvery grey.
Preparation of N2 :
(i) NH4NO2 N2 + 2H2O
(ii) (NH4)2 Cr2O7 N2 + 4H2O + Cr2O3
(iii)
Ba(N3)2 Ba + 3N2 Purest N 2 obtained

2NaN3 2Na + 3N2 by this method
(iv) 2NH3 + 3NaOCl N2 + 3NaCl + 3H2O
(v) 2NO + 2Cu 2CuO + N2
(red,overheated) (Black)
(vi) Cl2 passed into liquor NH3
3Cl2 + 2NH3 N2 + 6HCl
6NH3 + 6HCl 6NH4Cl
-------------------------------

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3Cl2 + 8NH3 N2 + 6NH4Cl

In this method NH3 conc. should not be lowered down beyond a particular limit.
3Cl2 + NH3 NCl3 + 3HCl
(Trimendously explosive)
Properties of N2 :
(i) It is inert due to high bond energy.
(ii) It is absorbed by hot metal like Ca, Mg, Al etc.
3Ca + N2 Ca3N2
Bright hot 2Al + N2 2AlN

Al2O3 + 3C + N2 2AlN + 3CO
(BN)x : Inorganic graphile
White slippery solid having 2D-sheet structure.
3000C
(BN)x (BN)x
3D network structure similar to diamond (Borazon) which is harder than diamond and used for dimond
cutting.

Na2B4O7 + 2NH4Cl 2NaCl + 2NH3 + 2B2O3 + H2O
B2O3 + 2NH3 2BN + 3H2O
(iii) N2 can be absorbed by calcium carbide at the temp around 1000C CaC2
CaC2 + N2 1000
C
CaNCN C

cyanamide ion nitro lim
It is a very good fertiliser.
Cyanamide ion
(iv)
TYPES OF NITRIDE :
(i) Salt like or ionic : Li3N, Na3N, K3N (?), Ca3N2, Mg3N2, Be3N2
(ii) Covalent : AlN, BN, Si3N4, Ge3N4, Sn3N4
(iii) Interstitial : MN (
M Sc, Ti, Zr, Hf , La )

HCP or FCC
No of metal atom per unit cell is equal to no of octahedral voids per unit cell.
All the octahedral voids are occupied by nitrogen atoms. Hence the fornmula is MN.
HCP : Hexagonal closed pack
FCC : Face centred cubic
NH3 preparation :
(i) Nitrate or nitrite reduction : NO3 / NO 2 +Zn or Al + NaOH NH3 + [Zn(OH)4]2 or [Al(OH)4]
(ii) Metal nitride hydrolysis : N3 + 3H2O NH3 3OH
(iii) Haber's process : N2 + 3H2 450C
2NH3
2001000 atm
catalyst Fe / Mo
Q.1 NH3 can't be dried by H2SO4, P2O5 and anh.CaCl2 because:
2NH3 + H2SO4 (NH4)2 SO4
H2O + NH3 + P2O5 (NH4)3 PO4
CaCl2 + 8NH3 CaCl2 . 8NH3

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forms adduct
Quick lime is used for this purpose
CaO + H2O Ca(OH)2 (base) Hence no
NH3 (base) interaction
Properties :
(i) It dissolves several electropositive metals like Li, Na, K, Rb, Cs, Sr, Ba etc.
Eg. : K in liq NH3 (i) Blue in colour
(ii) Conducts electricity
(iii) having reducing property
K in liq
K2[Ni(CN)4] K4[Ni(CN)4]
NH3
Square planar Tetrahedral
complex complex
(ii) Ag(NO3)(aq) + BaCl2(aq) AgCl + Ba(NO3)2
Cl + [Ag(NH3)2]+
BaCl2 +[Ag(NH3)2]+ + NO3

(iii) CH3COOH is strong acid in liq. NH3 while in water is weak acid.

AcOH l Ac O + H+
NH3 + H+ NH 4 H2O + H+ H3O+
Basisity order NH3 > H2O
more solvation of H+ in NH3.
(iv) Hydrolysis and Ammonolysis occurs is a same way.

SiCl4 + 4H2O 4HCl + Si(OH)4 SiO2 + 2H2O
SiCl4 + 8NH3 4NH4Cl + Si(NH2)4 Si3N4 + NH3
Rate of hydrolysis and Ammonolysis will be affected by the presence of HCl vapour & NH4Cl vapour
respectively.
NH 4 Salts Pr eparation
OXIDES OF NITROGEN
Oxides of nitrogen Structure Physical state Colour of gas

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N2O NNO Gas Colourless
NO Gas Colourless
N2O3 ;O N O N Blue liquid (30C)
||
O
NO2 l Gas Brown
N2O5 Colourless solid (no existance in gas phase)
Preparations:
1. N2O
(i) NH4NO3 N2O + H2O
(ii) (NH4)2SO4 + NaNO3 NH4NO3 + Na2SO4
N2O + 2H2O
(iii) Zn + HNO3 Zn(NO3)2 + N2O + H2O
(dil.& cold)
2. NO
(i) Cu + HNO3 (1 : 1) Cu(NO3)2 + NO + H2O
hot
(ii) KNO3 + FeSO4 + H2SO4 Fe2(SO4)3 + K2SO4 + NO + H2O
FeSO4 + NO FeSO4 . NO FeSO4 + NO
(iii) Oswald processRestricted oxidation of NH3.
Industrial process.
6 atm
4NH3 + 5O2 4NO + 6H2O
750C, Pt Cat
3. N2O3
(i) HNO3 + As2O3 H3AsO4 + N2O3
(ii) Cu + HNO3(6M) Cu(NO3)2 + ( NO NO )

2
| Cool (30C)
4. NO2
Blue liq ( N O )
2 3
1
(i) M(NO3)2 MO + 2NO2 + O2
2
M = Pb, Cu, Ba, Ca
(ii) (Cu, Pb, Ag) + HNO3 M-nitrate + NO2 + H2O
(hot & conc.)
5. N2O5
(i) 2HNO3 + P2O5 2HPO3 + N2O5
(ii) 4AgNO3 + 2Cl2(dry gas) 4AgCl + 2N2O5 + O2
Properties:
(I) Decoposition Behaviour
(i) N2O 500
C 900C
2N2 + O2
(ii) 2NO 800
C
N2 + O2

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(iii) N2O3 Room

temp
. NO2 + NO

(Blue liq.) at (30C)
(iv) 2NO2 620

C
2NO + O2

11C
N 2O 4 2 NO 2
( white solid ) Brown gas
at (11C)
1
30 C
N 2O5 40
(v) C
N 2O 5 2NO2 + 2 O2
colourless yellow
solid liq .
(II) Reaction with H2O & NaOH
H2O NaOH
(i) N2O : Fairly soluble in water and
produces neutral solution -------
(ii) NO : Sparingly soluble in water
and produces neutral soln. -------
(iii) N2O3: 2HNO2
Hence it is known as
anhydride of HNO2 NaNO2
(iv) NO2: HNO2 + HNO3
called as mixed anhydride NaNO2 + NaNO3
(v) N2O5: 2HNO3
called as anhydride of NaNO3
HNO3
Other properties:
N2O : 2N2O 2N2 + O2 mixture contains
Hence it is better supporter33% O 2 compared
for combustion to 20% in air
S + N2O SO2 + N2
P + N2O P2O5 + N2
Mg + N2O MgO + N2
Na + N2O Na2O + N2
Cu + N2O CuO + N2
H2 + N2O H2O + N2
1
NO : (i) It burns : NO + O NO2
2 2
(ii) It supports combustion also for molten sulphur and hot phosphorous.
S + 2NO SO2 + N2
5
2P + 5NO P2O5 + N
2 2
(iii) It is being absorbed by FeSO4 solution.
(iv) It is having reducing property.
KMnO4 + NO + H2SO4 K2SO4 + MnSO4 + HNO3 + H2O
HOCl + NO + H2O HNO3 + HCl
(v) NO shows oxidising property also.
SO2 + 2NO + H2O H2SO4 + N2O
H2S + 2NO H2O + S + N2O
3SnCl2 + 2NO + 6HCl 3SnCl4 + 2NH2OH
(Used for NH2OH preparation)
(vi) NO combines with X2 (X2= Cl2Br2F2) to produce NO X

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2NO + X2 2NOX
N2O3 : No more properties.
NO2 : (1) It is having oxidising property.
S + NO2 SO2 + NO
P + NO2 P2O5 + NO
C + NO2 CO2 + NO
SO2 + NO2 + H2O H2SO4 + NO
H2S + NO2 H2O + S + NO
CO + NO2 CO2 + NO
NO not formed : 2KI + 2NO2 I2 + 2KNO2
(2) Reducing property of NO2.
KMnO4 + NO2 + H2SO4 K2SO4 + MnSO4 + HNO3 + H2O
4 5
O30 2 NO 2 O 02 N 2O5

not the reduction product of O3
N2O5 :
I2 + 5N2O5 I2O5 + 10NO2
I2O5 is used for the estimation of CO
I2O5 + 5CO I2 + 5CO2
I2 + 2S2O 32 2I + S4O 62
N2O5 + NaCl NaNO3 + NO2Cl
This likes proves that N2O5 is consisting of ion pair of NO 2 & NO 3
Oxyacids of N :
HNO2 :
Preparation
(i) M-nitrite
dil. acid
HNO2
HCl or H 2SO 4
(ii) N2O3 + H2O 2HNO2

Properties
(i) Oxidising property of HNO2
KI + HNO2 + HCl KCl + H2O + NO + I2
SnCl2 + HNO2 + HCl SnCl4 + NO + H2O
SO2 + HNO2 + H2O H2SO4 + NO
H2S + HNO2 H2O + S + NO
FeSO4 + HNO2 + H2SO4 Fe2(SO4)3 + NO + H2O
Na3AsO3 + HNO2 Na3AsO4 + NO + H2O
(ii) Reducing property of HNO2

KMnO4 + HNO2 + H2SO4 K2SO4 + MnSO4 + HNO3 + H2O
K2Cr2O7 + HNO2 + H2SO4 K2SO4 + Cr2(SO4)3 + HNO3 + H2O
H2O2 + HNO2 H2O + HNO3
HNO2 + urea
+ thiourea
+ sulphamic acid
+ NH3 NH4NO2
+ C2H5NH2 C2H5OH + N2
5 C
+ PhNH2 PhN2+X
Nitric acid (HNO3)

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It was named aqua fortis (means strong water) by alchemists.

Preparation
(i) Laboratory Method
KNO3 + conc. H2SO4 KHSO4 + HNO3(vap)
vapours of nitric acid evolved are condensed in a glass receiver.
(ii) Industrial Preparation
(A) Birkeland Eyde Process or arc process
0
3000 C
step 1 N2 + O2 2NO - heat
Electric Arc
step 2 NO + O2 NO2
step 3 NO2 + H2O HNO2 + HNO3
step 4 HNO2 HNO3 + NO + H2O
(B) Ostwalds Process
Pt . gauze
step 1 NH3 + O2 700 NO + H O + heat
8000 C 2
R .T.( 25 C)
step 2 NO + O2 Air NO2
step 3 NO2 + H2O HNO2 + HNO3
step 4 HNO2 HNO3 + NO + H2O
PROPERTIES
Physical
Nitric acid usually acquires yellow colour due to its decomposition by sunlight into NO2.
4HNO3 Sunlight
4NO2 + 2H2O + O2
The yellow colour of the acid can be removed by warming it to 60-80oC and bubbling dry air through it.
It has extremely corrosive action on the skin and causes painful sores.
Chemical
(a) It is very strong acid. It exhibits usual properties of acids. It reacts with basic oxides, carbonates,
bicarbonates and hydroxides forming corresponding salts.
CaO + 2HNO3 Ca(NO3)2 + H2O
Na2CO3 + 2HNO3 2NaNO3 + H2O + CO2
NaOH + HNO3 NaNO3 + H2O
(b) Oxidising nature: Nitric acid acts as a strong oxidising agent as it decomposes to give nascent oxygen
easily.
2HNO3 H2O + 2NO2 + O
or 2HNO3 H2O + 2NO + 3O
(i) Oxidation of non-metals: The nascent oxygen oxidises various non-metals to their corresponding
highest oxyacids.
(1) Sulphur is oxides to sulphuric acid
S 6HNO 3 H SO + 6NO + 2H O
conc .and hot 2 4 2 2
(2) Carbon is oxidised to carbonic acid

C + 4HNO3 H2CO3 + 4NO2 + 2H2O
(3) Phosphorus is oxidised to orthophosphoric acid.
2P + 10HNO3 2H3PO4 + 10NO2 + 2H2O
conc. and hot
(4) Iodine is oxidised to iodic acid
I2 + 10HNO3 2HIO3 + 10NO2 + 4H2O
conc. and hot
(ii) Oxidation of metalloids
Metalloids like non-metals also form highest oxyacids

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(1) Arsenic is oxidised to arsenic acid

2As + 10HNO3 2H3AsO4 + 10NO2 + 2H2O
or As + 5HNO3 H3AsO4 + 5NO2 + H2O
conc. and hot
(2) Antimony is oxidised to antimonic acid
Sb + 5HNO3 H3SbO4 + 5NO2 + H2O
conc. and hot
(3) Tin is oxidised to meta-stannic acid.
Sn + 2HNO3 H2SnO3 + 4NO2 + H2O
(iii) Oxidation of Compounds:
(1) Sulphur dioxide is oxidised to sulphuric acid
SO2 + 2HNO3 H2SO4 + 2NO2
(2) Hydrogen sulphiode is oxidised to sulphur
H2S + 2HNO3 2NO2 + 2H2O + S
(3) Ferrous sulphate is oxidised to ferric sulphate in presence of H2SO4
6FeSO4 + 3H2SO4 + 2HNO3 3Fe2(SO4)3 + 2NO + 4H2O
(4) Iodine is liberated from KI.
6KI + 8HNO3 6KNO3 + 2NO + 3I2 + 4H2O
(5) HBr, HI are oxidised to Br2 and I2, respectively.
2HBr + 2HNO3 Br2 + 2NO2 + 2H2O
Similarly, 2HI + 2HNO3 I2 + 2NO2 + 2H2O
(6) Ferrous sulphide is oxidised to ferrous sulphate
FeS + HNO3 Fe2(SO4)3 + 8NO2 + 4H2O
(7) Stannous chloride is oxidised to stannic chloride is presence of HCl.
2HNO3 + 14H NH2OH + NH3 + 5H2O
Hydroxylamine
NH3 + HNO3 NH4NO3
------------------------------------------------------------------------------
7SnCl2 + 14HCl + 3HNO3 7SnCl4 + NH2OH + NH4NO3 + 5H2O
(8) Cane sugar is oxidised to oxalic acid.
C12H22O11 + 36HNO3 6(COOH)2 + 36NO2 + 23H2O
(c) Action on Metals: Most of the metals will the exveption of noble metals like gold and platinum are
attacked by Nitric acid plays a double role in the action of metals, i,e, it acts as an acid as well as an
oxidising agent. ARmstrong postulated that primary action of nitric acid is to produce hydrogen in the
nascent form. Before this hydrogen is allowed to escape, it reduces the nitric acid into number of
products like NO2, NO, N2O, N2 or NH3 according to the following reactions:
Metal + HNO3 Nitrate + H
2HNO3 + 2H 2NO + 2H2O
2HNO3 + 6H 2NO + 4H2O
2HNO3 + 10H N2 + 6H2O
2HNO3 + 16 H 2NH3 + 6H2O
The progress of the reaction is controlled by a number of factors:
(a) the nature of the metal,
(b) the concentration of the acid,
(c) the temperature of the reaction,
(d) the presence of other impurities.
--------------------------------------------------------------------------------------------------------
Concentration of Metal Main Products
nitric acid
--------------------------------------------------------------------------------------------------------
Mg, Mn H2 + Metal nitrate
Very dilute HNO3 (6%) ----------------------------------------------------------
Fe, Zn, Sn NH4NO3 + metal nitrate + H2O
--------------------------------------------------------------------------------------------------------
Pb, Cu, Ag, Hg NO + metal nitrate + H2O
----------------------------------------------------------
Dilute HNO3 (20%) Fe, Zn N2O + metal nitrate + H2O

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----------------------------------------------------------
Sn NH4NO3 + Sn(NO3)2
--------------------------------------------------------------------------------------------------------
Zn, Fe, Pb, Cu, Ag NO2 + metal nitrate + H2O
Conc. HNO3(70%) ----------------------------------------------------------
Sn NO2 + H2SnO3
Metastannic acid
--------------------------------------------------------------------------------------------------------
Action on Proteins
(i) Nitric acid attacks proteins forming a yellow nitro compound called xanthoprotein. It, therefore,
stains skin and renders wool yellow. This property is utilized for the test of proteins.
(ii) Oxidation A number of organic compounds are oxidised.
Sawdust catches fire when nitric acid is poured on it. Turpentine oil bursts into flames when treated with
fuming nitric acid. Cane sugar is oxidised to oxalic acid. Toluene is oxidised to benzoic acid with dil.
HNO3.
Structure
Nitric acid is a monobasic acid, i.e., the molecule consist of one hydroxyl group as it is formed by the
hydrolysis of nitryl chloride, NO2Cl. It may be structurally represented as below:
Gaseous nitric aicd is a planar molecule. The bond lengths and bond angles as present in the molecule
are represented in the figure:
PHOSPHOROUS
INTERCONVERSION OF WHITE 'P' & RED 'P'

240 250C
White 'P' Red 'P'
in an inert atm. like
N 2 or CO 2
I 2 : catalyst
heated to 550 C
Red 'P' White 'P'
in an inert atm. and then
rapid cooling to room temp.
PREPRATION OF WHITE 'P'

(i) Bone ash orApatite rock Ca3(PO4)2 + 3SiO2 1200 C
3CaSiO3 + P2O5

both have same formula 2P2O5 + 10C 1500
C
P4 + 10CO
(Coke) white 'P'
(ii) Ca3(PO4)2 + 3H2SO4 (conc.) 3CaSO4 + 2H3PO4
320C
H3PO4 HPO3
H2O
meta phosphoric acid
12C + 4HPO3 1000

C
2H2 + 12CO + P4
Coke white 'P'
REACTIONS OF 'P'
* P + H2SO4 (hot & conc.) H3PO4 + SO2 + H2O
P + KIO3 + H2SO4 H3PO4 + I2 + K2SO4

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* Reaction with hot metal

3Na + P Na3P
3Mg + 2P Mg3P2
3Ca + 2P Ca3P2
2Cu + 2P Cu3P2
Al + P AlP
Ca3P2 + H2O M(OH)n + PH3
or Mg3P2
or AlP
PREPARATION OF PH3 (PHOSPHINE GAS)

(i) 4H3PO3 PH3 + 3H3PO4
(ii) PH4I + KOH KI + PH3 + H2O

(PH3 + HI)
Purest PH 3
(iii) 2AlP + 3H2SO4 Al2(SO4)3 + PH3
PHYSICAL PROPERITIES
(i) It is having 'rotten fish' smell
(ii) It is soluble in CS2 and insoluble in water.
(NH3 is soluble in water)
NH 4 + OH
PH 4 is formed with acids

(iii) Like NH3, PH3 also can form addition product.

CaCl2 8NH3 Cu2Cl2 2PH3, AlCl3 2PH3, SnCl4 2PH3
PH3 can be absorbed by Ca(OCl)Cl.
PH3 + 3Ca(OCl)Cl + 3H2O PCl3 + 3HCl + 3Ca(OH)2
2NH3 + 3Ca(OCl)Cl N2 + 3CaCl2 + 3H2O
OTHER REACTIONS OF PH3
(i) PH3 + O2 150
P2O5 + H2O
(ii) PH3 + 3Cl2 PCl3 + 3HCl
electrical
(iii) PH3 + 4N2O H3PO4 + 4N2
sparking
(iv) 2PH3 + 3CuSO4 Cu3P2 + 3H2SO4

Detection of PH3 Black ppt.
(v) PH3 + 6AgNO3 [Ag3P 3AgNO3] + 3HNO3
yellow ppt.
Ag3P 3AgNO3 + 3H2O 6Ag + 3HNO3 + H3PO3
Black ppt.
(vi) PH3 + 4HCHO + HCl [P(CH2OH)4]+Cl
white/colourless solid
which is used for making
fire-proof cotton fabrics
EXAMPLE OF DEHYDRATING REACTION OF P2O5
HClO3 + P2O5 2HPO3 + Cl2O7
H2SO4 + P2O5 2HPO3 + SO3
HNO3 + P2O5 2HPO3 + N2O5

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Group 16 Elements (Oxygen family)

The Elements are O, S, Se, Te, Po
(Chalcogens)
Atomic and Physical Properties
(1) Atomic radii and Ionic radii

Covalent radius : O < S < Se < Te
(2) Ionization Enthalpies

O > S > Se > Te > Po (IE1 values)

M.P. : Te > Po > Se > S > O
B.P. Te > Po > Se > S > O
(4) Electronegativity
O > S > Se > Te

O < S < Se < Te < Po
(6) Elemental State

Oxygen exist as diatomic molecular gas in this case there is p p overlap thus tow O atoms form double
bond O = O. The intermolecular forces in O2 are weak VB forces. O2 exist as gas . On the other bond,
other elements of family do not form stable p p bonds and do not exist as M2 molecules. Other atoms
are linked by single bonds and form poly atomic complex molecules for
eg. S S8, Se S8
(7) Allotropy
All element exhibit allotropy for e.g.
Oxygen O2 and O3
Liquid O2 - pale base
Solid O2 - blue
Sulphur -
The main allotropic forms are
(i) Rhombic sulphur ( sulphur) (ii) Monoclinic ( sulphur) (iii) Plastic sulphur ( sulphur)
(i) Rhombic Sulphur ( sulphur)

This allotrope is yellow in colour (m.p. 385.8 K).
It is insoluble in water but readily soluble in CS2.
(ii) Monoclinic Sulphur ( sulphur)

It is soluble in CS2
>96C
S() S()
<96C
(iii) Plastic Sulphur ( sulphur) It is insoluble in CS2.
(8) Catenation
In this group only S has a strong tendency for catenation oxygen has this tendency to a limited extent.

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H2O2 HOOH (Poly oxides)

H2S2 HSSH (Polysulphides or polysulphones)
H2S3 HSSSH
H2S4 HSSSSH
SULPHUR CHEMISTRY
* Allotropes: (i) Rhombic or -sulphur.

(ii) Monoclinic or -sulphur.
(iii) -Sulphur
Amorphous forms are
(i) Plastic sulphur
(ii) Milk of sulphur
(iii) Colloidal sulphur
* Viscosity of 'S' with temperature:
m.p. of 'S' 112.8C.
(i) > 112.8C to 160C slow decreases due to
S8 rings slip and roll over one another easily.
(ii) > 160C, increases sharply due to breaking of
S8 rings into chains and polymerses into large size chain.
(iii) 190C, again large chains are being broken into small chain.
* Milk of sulphur :
Powdered 'S' + Ca(OH)2 suspension Solution Acidified
Milk of 'S'
12 S + 3Ca(OH)2 2CaS5 + CaS2O3 + 3H2O
2CaS5 + CaS2O3 + 6HCl 3CaCl2 + 12 S + 3H2O
* Colloidal Sulphur : Na2S2O3 + 2HCl 2NaCl + H2O + SO2 + S
2H2S + SO2 3 + 2H2O
Props. of 'S' : (a) Thin Cu-strip catches fire in sulphur vapour.
Cu + S CuS.
(b) 'S' burns spontaneously in fluorine. S + 3F2 SF6
Cl2 passed into liq. sulphur 2 S + Cl2 S2Cl2
(c) S + 2H2SO4 3SO2 + 2H2O
S + 2HNO3 H2SO4 + 2NO
(d) 4 S + 6 KOH 2K2S + K2S2O3 + 3H2O
(e) Burns in air : S + O2 SO2
H2 S :
Prepn.:FeS + dil. H2SO4 FeSO4 + H2S
FeS + dil. HCl FeCl2 + H2S
Sb2S3 + (conc.)6HCl 2SbCl3 + 3H2S
* Drying agent for this gas : fused CaCl2, Al2O3 (dehydrated)
P2O5 etc. But not H2SO4, because
H2SO4 + H2S 2H2O + SO2 + S
Reducing property of H2S :
Cl2 + H2S 2HCl + S
I2 + H2S 2HI + S
H2O2 + H2S 2H2O + S
SO2 + 2H2S 2H2O + 3 S
2FeCl3 + H2S 2FeCl2 + 2HCl + S
** 4H2O + 4Cl2 + H2S H2SO4 + 8HCl
KMnO4 + H2S + H2SO4 S + Mn2+

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H2Cr2O7 + H2S + H2SO4 Cr3+ + S +

HNO3 + H2S S + NO2 + H2O
With metal (hot)
2Na + H2S Na2S + H2
Cu + H2S CuS + H2
Pb + H2S PbS + H2
With metal oxide (hot)
CaO + H2S CaS + H2O
ZnO + H2S ZnS + H2O
Metal ion + H2S M-Sulphides
** (i) Alkali-sulphide water soluble
(ii) Alkaline earthsulphide sparingly soluble
(iii) Al2S3 & Cr2S3 + 6H2O Al(OH)3 or Cr(OH)3 + 3H2S
Test :
(i) Smell rotten egg.
(ii) Pb Acetate paperblack
(iii) Purple colour when alk. Nitropruside + H2S
Absorbent : NaOH, KOH, PbNO3 solution
Pb(NO3)2 + H2S 2HNO3 + PbS (Black)
SO2
Prepn.:
Industrial : 4FeS2 + 11O2 2Fe2O3 + 8SO2
2ZnS + 3O2 2ZnO + 2SO2
n
Lab prep .: Cu + 2H2SO4 (conc.) CuSO4 + 2H2O + SO2
Hg + H2SO4 HgSO4 + H2O + SO2
2Ag + H2SO4 Ag2SO4 + H2O + SO2
S + 2H2SO4 3SO2 + 2H2O
(Charcoal)C + 2H2SO4 CO2 + 2SO2 + 2H2O
NaHSO3+ H2SO4 NaHSO4 + H2O + SO2
Props: (i) Incombustible gas, but heated K burns in SO2
4K + 3SO2 K2SO3 + K2S2O3
Na2SO3 + SO2
Na2S + 3Na 2SO 4

Reducing Prop.: (Revise from acid radical)
(i) FeCl3 + SO2 FeCl2 + H2SO4
4FeCl2 + SO2 + 4HCl 4FeCl3 + H2O + S

6SnCl2 + 2SO2 + 8HCl 5SnCl4 + 4H2O + SnS2 (Yellow solid)

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150C
(ii) SO2 + 2H2SO3 2H SO + S
sealed tube 2 4
* FeSO4 Fe2O3 + SO2 + SO3

Fe2(SO4)3 Fe2O3 + 3SO3
H2SO4 & SO3 :
Both gas

SO 2 Cl 2 SO2Cl2
H2SO4 + 2PCl5 ..........SO2Cl2 + 2POCl3 + 2HCl
Use of H2SO4 as nitrating mixture:
good chlorinating agent
** P2O5 is stronger dehydrating agent than H2SO4 : H2SO4 + P2O5 2HPO3 + SO3
Properties of H2SO4 :
(a) Dissociation : At 444C. H2SO4 l H2O + SO3
(b) Acidic nature : NaOH + H2SO4 l NaHSO4 + H2O Na2SO4 + H2O
(c) CO 32 + H2SO4 SO 24 + H2O + CO2
Carbonates or bicarbonates

HCO 3 + H2SO4 H 2SO 4 +
H2O + CO2 are getting decomposed
(d) Zn / Fe + H2SO4ZnSO4 & FeSO4+ H2
where as
Cu + 2H2SO4 CuSO4 + SO2 + 2H2O
2Ag + 2H2SO4 Ag2SO4 + SO2 + 2H2O
Hg + 2H2SO4 HgSO4 + SO2 + 2H2O
(e) NaCl HCl
Ca3(PO4)2 H3PO4

FeS H2S
CH3CO2Na H SO AcOH
2 4
NaNO3 HNO 3
CaF2 HF
NaNO2 HNO2
(f) Oxidising Prop.:
HBr / HI + H2SO4 I2/Cl2 + SO2 + H2O
C + 2H2SO4 CO2 + 2SO2 + 2H2O
S + 2H2SO4 3SO2 + 2H2O
2P + 5H2SO4 H3PO4 + 5SO2
(g) Dehydrating agent:
H SO
C12H22O11 2
4 12 C
11 H 2O
H SO
2
C6H12O6 4 6C

6H O 2
2 H SO
(COOH)2 4 CO + CO
H SO
PhH 2
4 PhSO3H
H O 2
2
HCO2H CO
H O 2
SODIUM THIOSULPHATE
Prepn.:
(i) Na2SO3 soln. + S (powder) boiling
Na2S2O3 eavporatio
n Na2S2O3.5H2O, monoclinic crystal

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Na 2 CO 3 2SO 2 H 2 O 2 NaHSO 3 CO 2
2 NaHSO Na CO Na SO H O CO
3 2 3 2 3 2 2
(ii) Na 2SO 4 + 4C roasting

Na2S + 4CO
Salt cake Coke
Na2S2O3 [3SO2 + 2Na2S 2Na2S2O3 + S ]

(iii) 2Na2S + Na2CO3 + 4SO2 3Na2S2O3 + CO2
(iv) 6NaOH + 4S Na2S2O3 + 2Na2S + 3H2O
3Ca(OH)2 + 12 S CaS2O3 + 2CaS5 + 3H2O
(v) Na2SO3 + Na2S + I2 Na2S2O3 + 2NaI
(vi) 2Na2S + 2O2 + H2O Na2S2O3 + 2NaOH [Na2S is readily oxidised in air giving rise to Na2S2O3]

Props : (i) 4Na2S2O3 Na2S5 + 3Na2SO4

(ii) Na2S2O3 + 2H+ H2S2O3 H2O + SO2 + S (White turbidity)
Reaction: (i) Na2S2O3 + I2 S4O62 + 2I
+ Cl2 water SO 24 + S + 2HCl
+ Br2 water SO 24 + S + 2HBr
+ 4OI + 2OH 2 SO 24 + 4I + H2O
+ 4Cl2 + 5H2O Na2SO4 + 8HCl + H2SO4
excess
OZONE
Unstable deep blue, diamagnetic gas, with fishy smell. Toxic enough (more toxic than KCN). It's intense
blue colour is due to the absorption of red light.
2F2 + 2H2O 4HF + O2 Ozonised is separated by passing into spiral tube cooled by liq. F2 +
3H2O 6HF + O3 oxygen
air. Ozone condenses at 112.4C.

[b.p. of O2 183C ; b.p. of liq. air is 190C]
Oxidising property of O3
It is one of best oxidising agent, in acid solution, its standard, reduction potential value is 2.07 V.
O3 + 2H+ + 2e O2 + H2O E = +2.07 V
It is next to F2. [above 2.07 V, only F2, F2O are there]
(i) Metal Sulphides to Sulphates.
MS + 4O3 MSO4 + 4O2 [M = Pb, Cu, Zn, Cd]
(ii) 2HX + O3 X2 + H2O + O2 [X = Cl, Br, I]
(iii) NaNO2 + O3 NaNO3 + O2
Na2SO3 + O3 Na2SO4 + O2
Na2AsO3 + O3 Na2AsO4 + O2
(iv) Moist S, P, As + O3
S + H2O + 3O3 H2SO4 + 3O2
2P + 3H2O + 5O3 2H3PO4 + 5O2
2As + 3H2O + 5O3 2H3AsO4 + 5O2
(v) Moist I2 HIO3 whereas dry iodine I4O9 (yellow)
I2 + 5O3 + H2O 2HIO3 + 5O2
2I2 + 9O3 I4O9 + 9O2
(vi) 2K2MnO4 + O3 + H2O 2KMnO4 + 2KOH + O2
2K4[Fe(CN)6] + O3 + H2O 2K3[Fe(CN)6] + 2KOH + O2
2FeSO4 + O3 + H2SO4 Fe2(SO4)3 + O2 + H2O
(vii)(a) 2KI (acidified) + O3 + 2HCl I2 + 2KCl + H2O + O2

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(b) 2KI (neutral) + O3 + H2O I 2 2KOH + O2

KI KOI

KI + KOI + 2HCl 2KCl + I2 + H2O O3 estimated by this reaction

I2 + 2S2O 32 S4O62 + 2I

KI + 3O3 KIO3 + 3O2
(c) alk .
KI + 4O3 KIO4 + 4O2
(viii) Hg loses its fluidity (tailing of Hg)
2Hg + O3 Hg2O + O2
similarly 2Ag + O3 Ag2O + O2
Brown
(ix) BaO2 + O3 BaO + 2O2
H2O2 + O3 H2O + 2O2
Na2O2 + O3 + H2O 2NaOH + 2O2
(x) 2KOH + 5O3 2KO3 + 5O2 + H2O
In all above reaction O3 gives up O2 but some reactions are there which consumes all O-atom.
(i) 3SO2 + O3 3SO3
(ii) 3SnCl2 + 6HCl + O3 3SnCl4 + 3H2O
Absorbent : (i) Turpentine oil
(ii) Oil of cinnamon
Uses: (i) Sterilising water
(ii) Detection of position of the double bond in the unsaturated compound.
H2O2
Method of preparation:
(i) Na2O2 + H2O (ice cold water) 2NaOH + H2O2
(ii) BaO2 + H2SO4 BaSO4 + H2O2
Instead of H2SO4, H3PO4 is added now-a-days because H2SO4 catalyses the decomposition of H2O2 whereas
H3PO4 favours to restore it.
3BaO2+2H3PO4 Ba3(PO4)2+3H2O2 and Ba3(PO4)2+3H2SO43BaSO4+ 2H3PO4 (reused again)
(iii) Electrolysis of 50% H2SO4 using high current density.
2H2SO4 l 2H+ + 2H 2SO 4
2H 2SO 4 H2S2O8 + 2e. [At anode] [At cathode 2H+ + 2e H2]
H2S2O8 + 2H2O 2H2SO4 + H2O2
H / Pd O
(iv) 2
2
+ H2O2
Properties:
(i) Colourless, odourless liquid (b.p.152)
(ii) Acidic nature: H2O2 + 2NaOH Na2O2 + H2O
H2O2 + Ba(OH)2 BaO2 + 2H2O
H2O2 + Na2CO3 Na2O2 + CO2 + H2O
(iii) It is oxidant as well as reductant.
H2O2 + 2H+ + 2e 2H2O [reaction in acidic medium]
H2O2 + 2e 2OH [rxnn in alkali medium]
Oxidising Properties:
(i) PbS + 4H2O2 + PbSO4 + 4H2O (Used in washing of oil painting)
(ii) NaNO2 + H2O2 NaNO3 + H2O
Na2SO3 + H2O2 Na2SO4 + H2O
Na3AsO3 + H2O2 Na3AsO4 + H2O

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2KI + H2O2 2KOH + I2 X2 + H2O2 2HX + O2 X = Cl, Br..

H2S + H2O2 S + 2H2O S.R.P order of Cl > Br > H O > I
2 2 2 2 2
H2SO4 + 2FeSO4 + H2O2 Fe2(SO4)3 + 2H2O
2 K4[Fe(CN)6] + H2O2 + H2SO4 2K3[Fe(CN)6] + K2SO4 + 2H2O
2[Cr(OH)4] + 3H2O2 + 2OH 2CrO24 + 8H2O
CrO 24 + 2H+ + 2H2O2 CrO5(Blue) + 3H2O
4CrO5 + 12H+ 4Cr+3 + 7O2 + 6H2O
Mn+2 + OH + H2O2 MnO2 + 2H2O This reaction can be utilised to detect NH3
Reducing properties:
(a) Ag2O + H2O2 2Ag + H2O + O2
(b) O3 + H2O2 H2O + 2O2
(c) MnO2 + H2O2 + H2SO4 MnSO4 + 2H2O + O2
(d) PbO2 + H2O2 PbO + H2O + O2
(e) Pb3O4 + 4HNO3 2Pb(NO3)2 + PbO2 + 2H2O
PbO2 + H2O2 PbO + H2O + O2
PbO + 2HNO3 Pb(NO3)2 + H2O
Pb3O4 + H2O2 + 6HNO3 3Pb(NO3)2 + 4H2O + O2
(f) X2 + H2O2 2HX + O2 [X = Cl, Br]
2KMnO4 + 3H2O2 2KOH + 2MnO2 + 2H2O + 3O2
2MnO 4 + 2OH 2MnO 24 + H2O + O
2MnO24 + 2H2O 2MnO2 + 4OH + 2O
2MnO 4 + H2O 2MnO2 + 2OH + 3O
(g) 2KMnO4 + 5H2O2 + 3H2SO4 2MnSO4 + K2SO4 + 5O2 + 8H2O
(h) 2[Fe(CN)6]3 + 2OH + H2O2 2[Fe(CN)6]4 + 2H2O + O2
(i) NaOCl + H2O2 NaCl + H2O + O2
(j) NaIO4 + H2O2 NaIO3 + H2O + O2
Uses: (i) As a rocket propellant:
NH2.NH2 + 2H2O2 N2 + 4H2O [highly exothermic and large increase in volume]
(ii) In detection of Cr+3, Ti+4 etc.
Ti(SO4)2 + H2O2 + 2H2O H2TiO4 + 2H2SO4
Yellow or orange
Pertitanic acid
Group -17 Elements (Halogens Family)

Method of Prepn :
F2 : By electrolysis of KHF2 (which is obtained from CaF2)
CaF2 + H2SO4 CaSO4 + 2HF KF decreases the m.p. of
HF + KF KHF2 the mix. depending upon
the composition.
KHF2 Electrolys
is
2 H (at cathode) + F2 (at anode)
Cl2 : (i) By electrolysis of aq. NaCl :
2NaCl + 2H2O 2 NaOH H 2 + Cl 2

( anode )
at cathode
(ii) 2 NaCl Electrolys
is
2 Na + Cl 2
( Molten ) ( cathode ) ( anode )
(iii) In laboratory : Oxidising HCl by KMnO4 or MnO2
2KMnO4 + 16HCl 2KCl + 2MnCl2 + 5Cl2 + 8H2O
MnO2 + 4HCl MnCl2 + Cl2 + 2H2O
Br2 : From Brine water (contains 65 ppm of Br)

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Cl2 + 2Br 2Cl + Br2 (Br2 is volalite in nature)

Hence it is collected by
(i) removal of Br2 vapour by stream of air.
(ii) absorbing it into Na2CO3 solution.
Br2 + 6OH Br + BrO3 + 3H2O
Then acidified to get pure Br2
5Br + BrO3 + 6H+ 3Br2 + 3H2O
I2 : Chille salt petre contains traces of NaIO3 which is reduced to I by NaHSO3, then
oxidation of I to I2 by IO3 .
2IO3 +6 HSO3 2I + 6SO 24 + 6H+

6H
5I + IO3 3I2 + 3H2O
Q. Liquid I2 conducts electricity. Explain
Ans. Due to its self ionisation 3I2 I3 + I3
Q. X2 + OH X + OX + H2O but on acidification the disproportionated product gives
X + XO3 + H2O back the same element.
X2 = Cl3 Br2 . I2 . But For F2 i.e. X + OX + 2H+ X2 + H2O
5X + XO3 + 6H+ 3X2 + 3H2O
2F2 + 2NaOH 2NaF + F2O + H2O [X = Cl, Br, I ]
F2O + 2NaOH 2NaF + O2 + H2O
----------------------------------------
2F2 + 4NaOH 4NaF + O2 + 2H2O
HALOGEN ACID:
Acidity order: HI > HBr > HCl >> HF.(due to hydrogen bonding & less effective overlap with
H atom)
Q. CaF2 used in HF prepn. must be free from SiO2. Explain.
Ans. CaF2 + H2SO4 CaSO4 + HF
If SiO2 present as impurity
4HF + SiO2 SiF4 + 2H2O Hence presence of one molecule SiO2
SiF4 + 2HF H2[SiF6] consumes 6 molecule of HF
Q. HF can not be stored in glass vessel. Explain same reason.
Q. In the salt-cake method of prepn. of HCl, NH4Cl is being used instead of NaCl. Explain.
NaCl + H2SO4 150C
Ans. NaHSO 4 + HCl
Insoluble
550C
NaCl + NaHSO4 Na 2SO 4 + HCl
(Salt Cake )
2NH4Cl + H2SO4 2HCl + (NH4)2SO4

[NH4HSO4 intermediate is water soluble and easy to handle]
** Another alternative process to avoid the formation of NaHSO4
1
NaCl + SO 2 H 2O O 2 Na2SO4 + 2HCl
2
gaseous mixture
Q. In the similar type of preparation of HBr and HI from bromide ot iodide, H2SO4 can not be used and H3PO4
is used. Explaain.
Ans. Since H2SO4 is an oxidising agent it oxidises HBr & HI to Br2 and I2 respectively.
2HBr + H2SO4 Br2 + SO2 + 2H2O

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Hence. NaBr + H3PO4 NaH2PO4 + HBr

Another process: PBr3 + 3H2O H3PO4 + 3HBr
Q. Boiling point order of HX : HF > HI > HBr > HCl

Due to H-bonding
Q. HCl, H2SO4, HNO3 are bases in liquid HF where HClO4 is acid. Comment.
Ans. HCl + HF H2Cl+ + F ; H2SO4 + HF H 3SO 4 + F ; HNO3 + HF H 2 NO 3 + P
But HClO4 + HF H2F+ + ClO 4

* HF is weak acid but addition of BF3, AsF5, PF5, SbF5 makes it strongly acidic. Explain
OXOACIDS :
HOF : H2O + F2 HOF + HF
HO X: very unstable because
it reacts with both H2O
and F2 as follows :
HOCl HOF + F2 F2O + HF
HOBr X 2 H 2O HOX HX HOF + H2O H2O2 + HF
HOI
OX disproportionates in hot solution eg. 3OCl 2Cl + ClO 3
X = Cl, Br, I
Bleaching Powder :
Prepn.:Cl2(g) + Ca (OH) 2 40C

Ca(OCl)Cl + H2O
Slaked lime
(a) On long standing it undergoes
(i) auto oxiation 6Ca(OCl)Cl Ca(ClO3)2 + 5CaCl2
CoCl
(ii) 2Ca(OCl)Cl 2 2CaCl2 + O2
Cat .
(iii) Ca(OCl)Cl + H2O Ca(OH)2 + Cl2
Oxidising Prop.:
CaOCl2 + H2S S + CaCl2+ H2O
CaOCl2 + 2FeSO4 + H2SO4 Fe2(SO4)3 + CaCl2 + H2O
CaOCl2 + KNO2 CaCl2 + KNO3
3CaOCl2 + 2NH3 3CaCl2 + 3H2O + N2
CaOCl2 + 2KI + 2HCl CaCl2 + 2KCl + H2O + I2
CaOCl2 + 2KI + 2AcOH CaCl2 + 2KOAc + H2O + I2
CaOCl2 + Na3AsO3 Na3AsO4 + CaCl2
Reaction with acid:
CaOCl2 + 2HCl CaCl2 + H2O + Cl2 ; Ca(OCl)Cl + H2SO4 CaSO4 + H2O + Cl2
Ca(OCl)Cl + CO2 CaCO3 + Cl2
HXO2 :
BaO2 + 2ClO2 Ba(ClO2)2 + O2 / Ba(ClO2)2 + H 2SO 4 BaSO4 + HClO2
(dil )
Only Known HClO2. It is stable in alkaline solution but disproportionates in acid solution.
H
5HClO2 4ClO2 + HCl + 2H2O
HXO3 : HClO3 > HBrO3 > HIO3 are known and acidic order is as shown
Prepn:
HClO3 : Cl2 + 6NaOH hot 5NaCl + NaClO3 + 3H2O
Similarly electrolysis of hot halide solution with severe stirring gives the same product.
2Cl + 2H2O Cl2 + 2OH + H2

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NaClO 3 KCl KClO 3 NaCl [KClO 3 prep.n ]

Cl2+6NaOH5NaCl+NaClO3+3H2O on cooling
(recycled)
NaClO 3 BaCl 2 Ba (ClO 3 ) 2 NaCl
first
Properties : Ba (ClO ) H SO BaSO HClO
3 2 2 4 4 3
* 3HClO3 evaporatio
n 2ClO2 + H2O + HClO4
* IO3 + 5I + 6H+ 3I2 + 3H2O
Oxidising property

ClO 3 + 3SO32 Cl + 3SO 24
* Disproportionation: 4KClO3 low

temp
KCl + 3KClO4
absence of catalyst
2KClO3 400
500C
2KCl + 3O2
MnO 2 ( Cat .)
HXO4 : NaClO3 + H2O Electrolys

is
NaClO4 + H2
KClO4 + H2SO4(conc.) HClO4 + KHSO4
A : ClO 3 + H2O ClO 4 + 2H+ + 2e
Electrode reaction
C : 2H+ + 2e H2 KClO4 H2SO
4 HClO4

Props: K+ + HClO4 KClO4 + H+
Zn + 2HClO4 Zn(ClO4)2 + H2
Fe + 2HClO4 Fe(ClO4)2 + H2
Acidity order : HOX < HXO2 < HXO3 < HXO4
Oxidising power : HOX > HXO2>HXO3 > HXO4
Thermal stability: HOX < HXO2 < HXO3 < HXO4
OXIDES OF CHLORINE
(I) +1 +4 +6 +7
Cl 2O ClO 2 Cl 2O 6 Cl 2O 7
( Brownish yellow ) ( Pale Yellow ) colourless
( liq . dark red
solid yellow ) solid
Prepn.:Cl2 does not combine directly to produce its oxides but indirect methods are there.
Cl2O : 2Cl 2 + 2HgO(s) HgO.HgCl 2 + Cl2O (Brownish yellow gas)
dry in cooled tube Basic Hg ( II) chloride |

Condensed to orange liq.
Props.:
(i) It dissolves in water : Cl2O + H2O 2HClO
(ii) Explodes violently with NH3.
3Cl2O + 10 NH3 2N2 + 6NH4Cl + 3H2O
(iii) It is oxidising agent
Cl2O + 2HCl 2Cl2 + H2O

(iv) Structures. Back bonding

(II) ClO2 : Prepn.:
(i) 3KClO 3 + 3H 2SO 4 3KHSO4 + HClO4 + 2ClO 2 + H2O
( powder ) conc . Pale yellow gas
(ii) 2HClO3 + H2C2O4 60
C
2H2O + 2ClO2 + 2CO2
(iii) 2AgClO3 + Cl2 90 C
2AgCl + 2ClO2 + O2 [By this reaction pure ClO2 obtained]
ClO2 dissolves in water ClO2 ClO + O
producting dark green 2ClO + H2O HCl + HClO3
solution which decomposes

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in presence of light.
But in alkali gives a mixture of chlorite and chlorate.
2ClO2 + 2NaOH NaClO2 + NaClO3 + H2O
where 2ClO2 + 2NaOH + H2O2 2NaClO2 + O2 + 2H2O
used in bleaching
textles and paper.
* ClO2 does not dimerise because odd e' undergoes delocalisation (in its own vaccant 3d-orbital)
* Cl2O4 (Cl.ClO4) is not the dimer of ClO2. Actually it is Cl-perchlorate.
CsClO4 + ClOSO2F Cs(SO3)F + ClOClO3
Cl2O6 : Possible structures are:
ClO 2 ClO 4
liq dark red

Solid Yellow
Q. Prove that Cl2O6 is consisting of ClO 2 and ClO 4 .
0C
Prepn.: 2ClO2 + 2O3 Cl2O6 + 2O2
Cl2O6 l 2ClO3 (monomer is paramagnetic)
Reactions : Cl2O6 + H2O HClO3 + HClO4
Cl2O6 + NaOH NaClO3 + NaClO4 + H2O
Cl2O6 + HF ClO2F + HClO4
Cl2O6 + NO2 ClO2 + [NO2]+ [ClO4]
Cl2O7 (colourless solid): It is the anhydriide of HClO4 and prepared from it by the action of P2O5.
2HClO4 + P2O5 2HPO3 + Cl2O7
Structure :
INTER HALOGEN
Types : AX AX3 AX5 AX7
ClF ClF3 ClF5 IF7
BrF BrF3 BrF5
BrCl (ICl3)2 IF5
ICl IF3(unstable)
IBr
IF(unstable)
* 5IF IF5 + 2I2 [The overall system gains B.E. by 250 kJ/mol ]
* There are never more than two halogens in a molecule.
* Bonds are essentially covalent and b.p. increases as the E.N. difference increases.
* AX5 & AX7 type formed by large atoms like Br & I to accommodate more atoms around it.
* The interhalogens are generally more reactive than the halogens (except F2) due to weaker AX bonds
compared toXX bond.
Reactions : ICl + H2O HCl + HOI Oxohalide is always formedwith larger
halogen present during hydrolysis of
BrF5 3H 2O HBrO3 5HF
interhalogen compounds
IF5 3H 2O HIO3 5HF
IF H O IOF 2HF less
7 2 5
4 H 2 O HIO 4 7 HF
(i) ClF is highly reactive and as a fluorinating agent.
6ClF + 2Al 2AlF3 + 3Cl2
6ClF + U UF6 + 3Cl2
6ClF + S SF6 + 3Cl2

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ClF + SF4 SF5Cl
One pecularity with ICl :
In IInd case, the attacking species is I+ which has been supporetd by the formation of I+ in fused state
as follows : 3ICl [I2Cl]+ + [ICl2]
* ICl3 does not exist

but its dimer exist. 2ICl3 l I2Cl6
Structure is planar.
(Bright yellow solid)
I2Cl6 : liq. has appreciable electrical conductivity like other interhalogens.

I2Cl6 l [ICl2]+ + [ICl4]
BrF3 l [BrF2]+ + [BrF4]
IF5 l [IF4]+ + [IF6]
3ICl l [I2Cl]+ + [ICl2]
Polyhalides :
(i) KI + I2 KI3
(ii) ICl + KCl K+ [ICl2]
(iii) ICl3 + KCl K+[ICl4]
(iv) IF5 + CsF Cs+[IF6]
(v) ICl + KBr K+[BrICl]

Rb[ICl2] RbCl + ICl [not RbI + Cl2]
Here the products on heating depends on the lattice energy of the product halide. The lattice energy of alkali
halide with smaller halogen is highest since the interatomic distance is least.
Structure of I5 , I 7 , I82

in NCH 3 I7
4
in Cs2I8
** Only F3 not known [due to absence of d-orbital] [i.e. Cs2 I3 I2 I3]

I3 , Br3 , Cl 3 are known Cl 3 compounds are very less.
Stability order : I3 Br3 Cl 3 : depends upon the donating ability of X.
PSEUDO HALOGEN
There are univalent ion consisting of two or more atoms of which at least one is N, that have properties
similar to those of the halide ions. E.g.
(i) Na-salts are soluble in water but Ag-salts are insoluble in water.
(ii) H-compounds are acids like HX.

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(iii) Some anions can be oxidised to give molecules X2.

Anions : Acids Dimer
CN HCN (CN)2
SCN HSCN(thiocyanic acid) (SCN)2
SeCN (SeCN)2
OCN HOCN (cyanic acid)
2
NCN (Bivalent) H2NCN (cyanamide)
ONC HONC (Fulminic acid)
N 3 HN3 (Hydrazoic acid)
CN shows maximum similarites with Cl, Br, I

(i) froms HCN

(ii) forms(CN)2
(iii) AgCN, Pb(CN)2, are insoluble
(iv) Interpseudo halogen compounds ClCN, BrCN, ICN can be formed
(v) AgCN is insoluble in H2O but soluble in NH3
(vi) forms large no.of complex.e.g. [Cu(CN)4]3 & [CuCl4]3
[Co(CN)6]3 & [CoCl6]3
Group -18 Elements (Noble Gases)

* I.E. order : He > Ne > Ar > Kr > Xe > Rn
* M.P. order : He < Ne < Ar < Kr < Xe < Rn

* B.P. order : (269C) same
* Atomic radius order : Same
* Density order : Same
* Relative abundance : Ar is highest (Ne, Kr, He, Rn)
* "He" (helium) has the lowest b.p (269C) of any liquid (lowest of any substance)
(i) It is used in cryoscopy to obtain the very low temperature required for superconductor and
laser.
(ii) It is used in airships though H2 is cheaper and has lower density compared to He because H2
is highly inflammable.
(iii) He is used in preference to N2 to dil. O2 in the gas cylinders used by divers. This is because
N2 is quite soluble in blood, so a sudden change in pressure causes degassing and gives
bubbles of N2 in the blood. This causes the painful condition called bends.
He is slightly soluble so the risk of bends is reduced.
* Noble gases are all able to diffuse through glass, rubber, plastics and same metals.
* He liquid can exist in two forms. I-form when changes to II-form at -point temperature many
physical properties change abruptly.
e.g.
(i) Sp. heat changes by a factor of 10
(ii) Thermal conductivity increases by 106 and it becomes 800 times faster than Cu
(iii) It shows zero resistance
(iv) It can flow up the sides of the vessel
* Ar, Kr, Xe can form clathrate compounds but He, Ne cannot due to their smaller size.
What is noble gas hydrate?
eg. Xe 6H2O formed only when
Ar 6H2O water freezes at high
Kr 6H2O pressure together with noble gas
Xe COMPOUNDS
Xenon Fluorides:

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(1) Xe + F2
(2) H2 reduces Xe fluorides to Xe

XeF2 + H2 Xe + 2HF and so on
(3) Xe - fluorides oxidise Cl to Cl2 and I to I2
XeF2 + 2HCl 2HF + Xe + Cl2
XeF4 + 4KI 4KF + Xe + 2I2
(4) Hydrolysis
XeF2 reacts slowly with water
2XeF2 + 2H2O 2Xe + 4HF + O2
XeF4 and XeF6 react violently with water giving XeO3
3
3XeF4 + 6H2O 2Xe + XeO3 + 12HF + O2
2
XeF6 + 3H2O XeO3 + 6HF

(explosive, white hygroscopic solid)
(5) SiO2 also converts XeF6 into XeOF4

2XeF6 + SiO2 SiF4 + 2XeOF4
violet
Similarly, XeO3 + XeOF4 2XeO2F2 | XeO3 + 2XeF6 3XeOF4
(6) Xe-fluorides are also hydrolysed in alkaline medium
2XeF2 + 4OH 2Xe + 4F + 2H2O + O2
XeF6 + 7OH HXeO 4 + 3H2O + 6F
Xenate ion
2HXeO 4 + 2OH XeO64 + Xe + 2H2O + O2

(7) They are used as fluorinating agent
2SF4 + XeF4 2SF6 + Xe
Pt + XeF4 PtF4 + Xe
(8) Act as a fluoride donor
XeF2 + MF5 [XeF]+ [MF6] (M = As, Sb, P)
XeF6 + BF3 [XeF5]+ [BF4 ]
XeF6 + HF [XeF5]+ [HF2]
(9) Act as Fluoride acceptor also:
XeF6 + RbF/CsF Rb+/Cs+ [XeF7]

2Cs+[XeF7]
XeF6 + Cs2[XeF8]
50C
XeF4 + MF M+ + XeF5
(alkali metals fluoride)

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TRANSITION ELEMENTS
Definition: They one often called 'transition elements' because their position in the periodic table is between
s-block and p-block elements
Typically, the transition elements have an incompletely filled d-level. Since Zn group has d10 configuration
and are not considered as transition elements but they are d-block elements.
General Characteristics:
(i) Metallic character: They are all metal and good conductor of heat & electricity
(ii) Electronic configuration: (n1)d110ns12
Sc Ti V Cr Mn Fe Co Ni Cu Zn
others are
as usual 4s1
3d5
4s 1
3d10
(iii) M.P. Cr Maximum Zn lowest m.p.
Mo 6 no. of unpaired es Cd due to no unpaired e

W are involved in metallic bonding Hg for metallic bonding
(iv) Variation in atomic radius:
Sc Mn Fe Co Ni Cu Zn

decreases remains increases
same again
(v) Variable oxidation states possible
Sc Ti V Cr Mn Fe Co Ni Cu Zn
1 1
2 2 2 2 2 2 2 2 2
3 3 3 3 3 3 3 3
4 4 4 4 4 4 4
5 5 5
6 6 6
7
Colour: (aquated)
Sc3+ colourless
Ti4+ colourless
Ti3+ purple
V4+ blue
V3+ green
V2+ violet
Cr2+ blue
Cr3+ green
Mn3+ violet
Mn2+ light pink
Fe2+ light green
Fe3+ yellow
Co2+ pink
Ni2+ green
Cu2+ blue
Zn2+ colourless

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CHROMATE -DICHROMATE
Preparation: 4FeCr2O4 + 8Na2CO3 + 7O2 10001300C

8Na2CrO4 + 2Fe2O3 + 8CO2
red hot in presence of air
(chromite ore)
[Lime (CaO) added with Na2CO3 which keeps the mass porous so that air has access to all parts and
prevents fusion]
Then, 2Na2CrO4 + H2SO4 Na2SO4 + Na2Cr2O7 + H2O
conc. It's solubility Hence, suitable temp. is to be
upto 32C increases
and then decreases
}
employed to crystallise out
Na2SO4 first.
Then Na2Cr2O7 is crystallised out as Na2Cr2O72H2O on evaporation.
(red crystal)
How to get K2Cr2O7 : Na 2Cr2O7 + KCl double

K2Cr2O7 + 2NaCl
decomposit ion
hot conc.
NaCl crystallises out first and filtered off. Then K2Cr2O7 crystallised out on cooling
* Other props & test of CrO 24 & Cr2O 72 : Already discussed

* Similarities between hexavalent Cr & S-compounds:
(i) SO3 & CrO3 both acidic.
(ii) S SO 24 , S2O72 , Cr CrO 24 , Cr2O 72
(iii) CrO 42 & SO 24 are isomorphous

2 2
(iv) SO2Cl2 & CrO2Cl2 OH
SO 4 & CrO 4 respectively..
2 2
(v) SO3Cl & CrO3Cl OH
SO 4 & CrO 4
O O O
|| || ||
(vi) CrO3 & (SO3) has same structure Cr O Cr O Cr
|| || ||
O O O
Ques. In laboratory K2Cr2O7 is used mainly not Na2Cr2O7. Why?
Sol. Na2Cr2O7 is deliquescent enough and changes its concentration and can not be taken as primary standard
solution whereas K2Cr2O7 has no water of crystallisation and not deliquescent.
Ques. How to standardise Na2S2O3 solution in iodometry?

Sol. K2Cr2O7 is primary standard strength is known by weighing the salt in chemical balance and
dissolving in measured amount of water.
Then in acidic solution add. KI
Cr2O72 + 14H+ + 6I 2Cr3+ + 3I2 + 7H2O
This I2 is liberated can be estimated with S2O32.
MANGANATE & PERMANGANATE

Preparation of Manganate ( MnO 24 ):-

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MnO2 KOH
MnO 24 [2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O]
or NaOH ,
in presence of air green MnO + 2KOH + KNO K MnO + KNO + H O
2 3 2 4 2 2
melt
3MnO2 + 6KOH + KClO3 3K2MnO4 + KCl + 3H2O
In presence of KClO3 & KNO3 the above

reaction is more faster because these two on
decomposition provides O2 easily.
* Manganate is also obtained when KMnO4 is boiled with KOH.
4KMnO4 + 4KOH boiled
4K2MnO4 + 2H2O + O2
Props :The above green solution is quite stable in alkali, but in pure water and in presence of
acids, depositing MnO2 and giving a purple solution of permanganate.
3K2MnO4 + 2H2O l 2KMnO4 + MnO2 + 4KOH
purple drak brown
Prob. : E o = 2.26 V ; Eo = 0.56 V
MnO 24 / MnO 2 MnO 24 / MnO 4
Prove that MnO 24 will disproportionate in acidic medium.
Another Method of Prepn. : 3K2MnO4 + 2H2SO4 2KMnO4 + MnO2 + 2K2SO4 + 2H2O

or 3K2MnO4 + 2H2O + 4CO2 2KMnO4 + MnO2 + 4KHCO3
1
of Mn is lost as MnO2 but when oxidised either by Cl2or by O3
But in the above method
3
2K2MnO4 + Cl2 2KMnO4 + 2KCl [Unwanted MnO2 does not form]
OR
2K2MnO4 + O3 + H2O 2KMnO4 + 2KOH + O2
Oxidising Prop. of KMnO4 : (in acidic medium)

(i) MnO 4 + Fe+2 + H+ Fe+3 + Mn+2 + H2O
(ii) MnO 4 + I + H+ Mn+2 + I2 + H2O
(iii) MnO 4 + H2O2 + H+ Mn+2 + O2 + H2O

H
(iv) MnO 4 + SO2
Mn+2 + H2SO4
(v) MnO 4 + NO 2 + H+ Mn+2 + NO3 + H2O
(vi) MnO 4 + H2C2O4+ H+ Mn+2 +CO2+ H2O
(vii) MnO 4 + H2S Mn2+ + S + H2O
* (1) It is not a primary standard since it is difficult to get it in a high degree of purity and free from traces of
MnO2.
*(2) It is slowly reduced to MnO2 especially in presence of light or acid
4MnO 4 + 4H+ 4MnO2 + 2H2O + 3O2

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Hence it should be kept in dark bottles and standardise just before use.
(viii) 2KMnO4 + 16HCl 2KCl + 5Cl2 + 8H2O + 2MnCl2
Oxidising Prop. of KMnO4 in alk. medium :
2MnO 4 + 2OH 2MnO 24 +H2O + O. Then 2MnO 24 + 2H2O 2MnO2 + 4OH + 2O
(i) 2KMnO4 + H2O + KI 2MnO2 + 2KOH + KIO3
(ii) 2KMnO4 + 3HCO2K 2MnO2 + KHCO3 + 2K2CO3 + H2O
(iii) 2KMnO4 + 3H2O2 2KOH + 2MnO2 + 2H2O + 3O2
Oxidising Prop. in neutral or weakly acidic solution:
in presence Zn 2 or ZnO
(i) 2KMnO4 + 3MnSO4 + 2H2O 5MnO2 + K2SO4 + 2H2SO4
or MnO 4 + Mn+2 + 2H2O 5MnO2 + 4H+
In absence of Zn+2 ions, some of the Mn+2 ion may escape, oxidation through the formation of insoluble
MnII[MnIVO3] manganous permanganite.
(ii) 8KMnO4 + 3Na2S2O3 + H2O 8MnO2 + 3Na2SO4 + 3S + 2KOH
** Conversion of Mn+2 to MnO 4 :

(i) PbO2 (ii) Pb3O4 + HNO3 (iii) Pb2O3 + HNO3 (iv) NaBiO3 / H+
(v) (NH4)2S2O8 / H (vi) KIO4 / H+
+

Heating effect : 2KMnO4
K2MnO4 + MnO2 + O2
200C
green Black
at red
2K2MnO4 2K2MnO3 + O2
hot
SILVER AND ITS COMPOUND
(I) Metallic Ag
In the same way in presence of O2, Ag complexes with NaCN / KCN.

4Ag + 8KCN + 2H2O + O2 4K[Ag(CN)2] + 4KOH
AgNO3
Prepn.: already done.
Properties.: (i) It is called as lunar caustic because in contact with skin it produces burning sensation
like that of caustic soda with the formation of finely devided silver (black colour)
(ii) Thermal decomposition:
(iii) Props. of AgNO3 : [Already done in basic radical]
6AgNO3 + 3I2 + 3H2O 5AgI + AgIO3 + 6HNO3
(excess)

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(iv)
Ag2SO4 2Ag + SO2 + O2
B
(v) A(AgNO3) white ppt appears quickly
added
A
Explain
B(Na2S2O3)
It takes time to give white ppt.
added
(vi) Ag2S2O3 + H2O Ag2S + H2SO4

AgCl . AgBr. AgI (but not Ag2S) are soluble in Na2S2O3 forming
[Ag(S2O3)2]3 complexes
(vii) AgBr : AgNO3 KBr
AgBr + KNO3
Pale yellow
ppt.
Heating effect: 2AgNO3 212
C
2AgNO2 + O2
2AgNO2 500
C
2Ag + 2NO + O2
(viii)
Ag2O + H2O2 2Ag + H2O + O2

K2S2O8 + 2AgNO3 + 2H2O 2AgO + 2KHSO4 + 2HNO3
* AgO supposed to be paramagnetic due to d9 configuration. But actually it is diamagnetic and exists as AgI
[AgIIIO2]
* Reaction involved in developer :
K2FeII(C2O4)2 + AgBr KFeIII (C2O4)2 + Ag + KBr
ZINC COMPOUNDS
ZnO: It is called as phillospher's wool due to its wooly flock type appearance
Preparation: 1] 2Zn + O2 2ZnO

2] ZnCO3 ZnO + CO2

3] 2Zn(NO3)2 2ZnO + 4NO2 + O2

4] Zn(OH)2 ZnO + H2O
Purest ZnO : 4ZnSO4 + 4Na2CO3 + 3H2O ZnCO33Zn(OH)2 + 4Na2SO4 + 3CO2
white basic zinc
carbonate
4ZnO + 3H2O + CO2

pure
Properties: 1] ZnO(cold) ZnO(hot)

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white yellow
2] It is insoluble in water
3] It sublimes at 400C
4] It is amphoteric oxide
ZnO + 2HCl ZnCl2 + H2O
ZnO + H2SO4 ZnSO4 + H2O
ZnO + 2NaOH Na2ZnO2 + H2O
5] ZnO Zn by H2 & C
ZnO + H2 400C
Zn + H2O
ZnO + C Zn + CO
6] It forms Rinmann's green with Co(NO3)2
2Co(NO3)2 2CoO + 4NO2 + O2
CoO + ZnO CoZnO2 or CoOZnO
Rinmann's green
Uses: (1) As white pigment. It is superior than white lead because it does not turn into black
(2) Rinmann's green is used as green pigment
(3) It is used as zinc ointment in medicine
ZnCl2
Preparation: ZnO + 2HCl ZnCl2 + H2O
ZnCO3 + 2HCl ZnCl2 + H2O + CO2 It crystallis es as ZnCl 2 2 H 2O
Zn(OH)2 + 2HCl ZnCl2 + 2H2O
Anh. ZnCl2 cannot be made by heating ZnCl22H2O because

ZnCl22H2O Zn(OH)Cl + HCl + H2O

Zn(OH)Cl ZnO + HCl
To get anh. ZnCl2: Zn + Cl2 ZnCl2
Zn + 2HCl(dry) ZnCl2 + H2
or Zn + HgCl2 ZnCl2 + Hg
Properties: (i) It is deliquescent white solid (when anhydrous)
(ii) ZnCl2 + H2S ZnS
" + NaOH Zn(OH)2 excess
Na2[Zn(OH)4]
" + NH4OH Zn(OH)2 excess 2+
[Zn(NH3)4]
Uses: 1] Used for impregnating timber to prevent destruction by insects
2] As dehydrating agent when anhydrous
3] ZnOZnCl2 used in dental filling
ZnSO4:
Preparation:
Zn + dil H2SO4 ZnSO4 + H2
ZnO + dil H2SO4 ZnSO4 + H2O
ZnCO3 + dil H2SO4 ZnSO4 + H2O + CO2
ZnS 2O 2 ZnSO 4
3 parallel reaction
ZnS + O2 ZnO + SO2
2
ZnS + 4O3 ZnSO4 + 4O2
70C 280C
Props. 1] ZnSO47H2O 39
70C
ZnSO46H2O ZnSO4H2O ZnSO4

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1
O + SO2 + ZnO
2 2
Uses: 1] in eye lotion
2] Lithophone making (ZnS + BaSO4) as white pigment
COPPER COMPOUNDS
CuO:

Preparation: (i) CuCO3.Cu(OH)2 2CuO + H2O + CO2 (Commercial process )
Malachite Green
(native Cu-carbonate)
1
(ii) 2Cu + O2 2CuO & Cu2O + O 2CuO
2 2

(iii) Cu(OH)2 CuO + H2O
(iv) 2Cu(NO3)2 250
C
2CuO + 4NO2 + O2
Properties: (i) CuO is insoluble in water

(ii) Readily dissolves in dil. acids
CuO + H2SO4 CuSO4 + H2O
HCl CuCl2
HNO3 Cu(NO3)2
(iii) It decomposes when, heated above 1100C
4CuO 2Cu2O + O2
(iv) CuO is reduced to Cu by H2 or C under hot condition
CuO + C Cu + CO
CuO + H2 Cu + H2O
CuCl2 :
Preparation: CuO + 2HCl(conc.) CuCl2 + H2O
Cu(OH)2CuCO3 + 4HCl 2CuCl2 + 3H2O + CO2
Properties: (i) It is crystallised as CuCl22H2O of Emerald green colour

(ii) dil. solution in water is blue in colour due to formation of
[Cu(H2O)4]2+complex.
(iii) conc. HCl or KCl added to dil. solution of CuCl2 the colour changes
into yellow, owing to the formation of [CuCl4]2
(iv) The conc. aq. solution is green in colour having the two complex ions in
equilibrium 2[Cu(H2O)4]Cl2 l [Cu(H2O)4]2+ + [CuCl4]2 + 4H2O
(v) CuCl2 CuCl by no. of reagents

(a) CuCl2 + Cu-turnings 2CuCl
(b) 2CuCl2 + H2SO3 + H2O 2CuCl + 2HCl + 2H2SO4
(c) 2CuCl2 + Zn/HCl 2CuCl + ZnCl2
(d) CuCl2 + SnCl2 CuCl + SnCl4
** CuF22H2O light blue Anh. CuCl 2 is dark brown mass obtained

CuCl22H2O green by heating CuCl 22H 2O at 150C in prese nce
CuBr2 almost black of HCl vap.
150C
CuI2 does not exist CuCl22H2O CuCl2 + 2H2O
HCl gas
CuSO4:
Preparation: CuO + H2SO4(dil) CuSO4 + H2O

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Cu(OH)2 + H2SO4(dil) CuSO4 + 2H2O

Cu(OH)2CuCO3 + H2SO4 (dil) CuSO4 + 3H2O + CO2
1
Cu + H2SO4 + O CuSO4 + H2O [Commercial scale]
2 2
(Scrap)
Cu + dil. H2SO4 no reaction {Cu is a below H in electrochemical series}
Properties: (i) It is crystallised as CuSO45H2O
(ii) CuSO45H2O CuSO43H2O CuSO4H2O

Blue take places Pale blue Bluish white
CuSO4(anh.)
white
(iii) Revision with all others reagent

IRON COMPOUNDS
FeSO47H2O:
Preparation: (i) Scrap Fe + H2SO4 FeSO4 + H2
(dil.)
(ii) From Kipp's waste
FeS + H2SO4(dil) FeSO4 + H2S
7
(iii) FeS2 + 2H2O + O2 FeSO4 + H2SO4
2
Properties: (i) It undergoes aerial oxidation forming basic ferric sulphate
4FeSO4 + H2O + O2 4Fe(OH)SO4
FeSO 4 high
(ii) FeSO47H2O 300 C
anh. white Fe2O3+SO2+SO3
temp.
(iii) Aq. solution is acidic due to hydrolysis
FeSO4 + 2H2O l Fe(OH)2 + H2SO4
weak base
(iv) It is a reducing agent
(a) Fe2+ + MnO4 + H+ Fe3+ + Mn2+ + H2O
(b) Fe2+ + Cr2O72 + H+ Fe3+ + Cr3+ + H2O
(c) Au 3+ + Fe2+ Au + Fe3+
(d) Fe2+ + HgCl2 Hg2Cl2 + Fe3+
white ppt.
(v) It forms double salt. Example (NH4)2SO4FeSO46H2O
FeO(Black): Prepn : FeC2O4 FeO + CO + CO2

in absence of air
Props: It is stable at high temperature and on cooling slowly disproportionates
into Fe3O4 and iron
4FeO Fe3O4 + Fe
heated in
FeCl2: Prepn: Fe + 2HCl FeCl2 + H2
a current of HCl
OR

2FeCl3 + H2 2FeCl2 + 2HCl

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Props: (i) It is deliquescent in air like FeCl3

(ii) It is soluble in water, alcohol and ether also because it is
sufficiently covalent in nature
(iii) It volatilises at about 1000C and vapour density indicates the
presence of Fe2Cl4. Above 1300C density becomes normal
(iv) It oxidises on heating in air
12FeCl2 + 3O2 2Fe2O3 + 8FeCl3
(v) H2 evolves on heating in steam
3FeCl2 + 4H2O Fe3O4 + 6HCl + H2
(vi) It can exist as different hydrated form
FeCl22H2O colourless
FeCl24H2O pale green
FeCl26H2O green
FeCl3: Prepn: Anhydrous ferric chloride is prepared by heating metallic iron in a stream
of dry chlorine gas.
(i) FeCl3 solid is almost black. It sublimes at about 300C, giving

a dimeric gas.
(ii) FeCl3 dissolves in both ether and water, giving solvated
monomeric species.
(iii) Iron (III) chloride is usually obtained as yellow-brown lumps of
the hydrate FeCl36H2O.
(iv) This is very soluble in water and is used both as an oxidizing
agent, and as a mordant in dyeing.
(v) FeCl3 is also used in the manufacture of CCl4.

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COMMON NAME
S. Compound Common Name
No.
Group A: ALKANES
CH 3
|
1 CH 3 CH CH CH 3 Isopentane 2 CH 3 C CH 2 CH CH 3 Iso Octane
| | |
CH 3 CH 3 CH 3
CH 3 CH 3
| |
3 CH 3 C CH 3 Neo Pentane 4 CH 3 C CH CH 3 Triptane
| | |
CH 3 CH 3 CH 3
5 CH 3 CH 2 CH CH 2 Active Amyl Group

|
CH 3
Group B:ALKENES
6 CH3CH2CH=CH2 Butylene 7 CH3CH=CHCH3 Butylene
8 CH 3 C CH 2 Iso Butylene 9 CH2=C=CH2 Allene

|
CH 3
CH 3
|
10 CH 2 C CH CH 2 Isoprene
No.
Group C:ALKYNES
11 CHCH Purified Acetylene or Norcelyne 12 CH2=CHCCH Vinyl Acetylene
13 CH3CCH Allylene
Group D:ALKYL HALIDE

14 CH3CHCl2 Ethylidene Chloride
(A Jem dihalide)
15 CH 2 CH 2 Ethylene Dichloride
| | (A Vinyl dihlide)
Cl Cl
16 CH 2Cl CH 2Cl Mustard Gas

| | (Poisionous; used in war)
CH 2 S CH 2

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17 CH 2Cl Westron (Solvent)

|
CH 2Cl
18 ClCH=CCl2 Westrosol or
Triclean (Solvent)
19 Cl2C=CCl2 Tetraclean or Perclean

Cl
|
20 Cl C NO 2 Chloropicrin (tear gas)
|
Cl
CCl 3
|
21 CH 3 C CH 3 Chloretone
|
OH
Cl
22 | Chloroprene
CH 2 C CH CH 2
H C Cl
23 || Lewisite
H C AsCl 2

No.
Group E:ALCOHOL
24 CH 2 OH Glycol or Ethylene
|
CH 2 OH
25 CH 2 CH CH 2 Glycerol
| | |
OH OH OH
26 CHCCH2OH Propargyl Alcohol

27 CH2=CHCH2OH Allyl Alcohol
28 CH2=CHOH Vinyl Alcohol
CH 3
|
CH 3 C OH
29 | Pinacol
CH 3 C OH
|
CH 3

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Group F:ETHER
30 C6H5OCH3 Anesol
(Methyl Phenyl Ether)
31 C6H5OC2H5 Phenetol
(Ethyl Phenyl Ether)
32 CH3CH(OCH3)2 Methylal
33 Methylal
or
CH3CH(OCH3)2
Group G:ALDEHYDE
CHO
34 | Glyoxalic acid
COOH

No.
CH 3
|
35 CH 3 C CHO Pavaldehyde
|
CH 3
or
(CH3)3CCHO
36 CH3CH=CHCHO Crotonaldehyde
37 CH2=CHCHO Acraldehyde
or Acrolein
38 (CH3)2CHCHO Isobutyraldehyde
39 CH 3 C C CH 3 Dimethyl Glyoxal
|| ||
O O
40 H 2C CH CHO Glyceraldehyde
| |
OH OH
O
||
CH
41 | Glyoxal
CH
||
O

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42 CH 3 C C H Methyl Glyoxal or
|| || Pyruvic Aldehyde
O O
Group H:KETONE
43 CH3COCH3 Acetone
44 Phorone
45 Mesityl Oxide
46 H2C=C=O Ketene

No.
Group I:CARBOXYLIC ACID
47 CH3CH2CH2CH2COOH Valeric Acide

(nPentanoic acid)
48 CH3(CH2)4COOH Caproic Acid

(nHexanoic acid)
CH 2 COOH
49 | Malic Acid
CH (OH) COOH
OH
|
50 CH 2 C CH 2 Citric Acid
| | | (In lemon)
COOH COOH COOH
51 CH2=CHCOOH Acralic Acid

H
|
52 CH 3 C COOH Lactic Acid (In milk)
|
OH
53 HO C OH (H 2CO 3 ) Carbonic Acid

||
O
54 CH3COCOOH Pyruvic Acid
55 CH3CH=CHCOOH Crotonic Acid

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56 C 6H 5 CH COOH Mendalic Acid

|
OH
57 NH2CH2COOH Glycine
(Amino Acetic Acid)
58 NH2COOH Carbamic Acid

(Amino formic Acid)
59 COOH(CH2)4COOH Adipic Acid
60 C6H5CH=CHCOOH Cinnamic Acid

No.
CH 3
|
61 NH 2 C H Alanine
|
COOH
62 HO CH2 COOH Glycolic Acid
COOH
63 | Oxalic acid
COOH
64 Malonic acid
CH 2 COOH
65 | Succinic acid
CH 2 COOH
66 HO CH COOH Malic acid

|
CH 2 COOH
HO CH COOH
67 | Tarteric acid
HO CH COOH

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O
||
H C C OH
68 || Maleic acid
H C C OH
||
O
O
||
H C C OH
69 || Fumeric acid
HO C C H
||
O

No.
Group J:ACID DERIVATIVES
70 Cl C C Cl Oxalyl Chloride
|| ||
O O
71 NH2COONH4 Ammonium Carbamate
72 CH 3 C CH 2 C O C 2 H 5
|| ||
O O
Aceto Acetic Ester
or Ethyl Aceto Acetate
NH 2 C C NH 2
73 || || Oxanamide
O O
74 Cl C Cl Phosgene
||
O
75 H 2 N C NH 2 Urea
||
O
Group K:NDERIVATIVES
76 CH2=CHCN Vinyl Cyanide or

Acrelio Nitrile
77 HCN Forma Nitrile
78 CH3CN Aceto Nitrile
79 CH3NCO MIC

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Group L:AROMATIC COMPOUNDS
80 Anthracene
81 Indol

No.
82 Pyridine
83 Thiophene
84 Pyrol
85 Sulphanilic acid
86 Azulene
87 Napthelene
88
Orange II
89 Butter Yellow
90 Furfurel
91 Furan

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92 Conmarine
93 Michlers Ketone

No.
94 Phenolphthalein
95 Tropone
(Cycloheptatrienone)
96 Tropolone
(Cycloheptatrienolone)
97 oxylene
98 DDT
(Dichlorodiphenyltrichloroethane)
99 Nitrobenzene (oil of mirbane)
100 naphthol

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101 naphthol
102 Benzidine

No.
103 Hydrazobenzene
104 Orthanilic Acid
105 Catechol
106 Resorcinol
107 Quinol
108 Phloroglucinol
109 Wurster salts
110
Salicylaldehyde(o-hydroxybenzaldehyde)

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111C6H5CONH2 Benzamide
112(C6H5CO)2O Benzoic Anhydride

113(C6H5CO)2O2 Benzoyl Peroxide

No.
114C6H5CO2CH3 Perbenzoic acid
115 Toluic acids
116
Anthranilic acid (o-aminobenzoic acid)
117
Saccharin (o-sulphobenzoic imide)
118C6H5CH=CH2 Styrene
119C6H5CHO Benzaldehyde
120 C6H5COCOC6H5 Benzil
121 (C6H5)2C(OH)CO2H Benzilic acid
Group M: HETROCYCLIC COMPOUNDS
122 Pyrrolidine
123 Piperidine
124 Morpholine

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No.
125 Aziridine
126 Tatrahydrofuran
127
Hexa-methlyenetetramine or Urotropene
128 Oxirane or Ethylene Oxide or
Oxo Cyclo Propane

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HYDROCARBONS
REACTION CHART FOR ALKANES

GMP GR
H , Ni
(1) RC CH 2 (1) X , h or UV light or 400 C
2
RX
200300C
or
RCH=CH2 Sabatier senderens (2) Nitration
R-N
reaction
(2) RX Zn
Cu HCl
Sulphonation H S O
Re d P Hi, LiAlH 4 (3) 2
2
7 Alkyl Sulphonic acid
(3) RMgX
HOH or ROH

or NH3 or RNH 2 Reed reaction
(4) SO2 + Cl2 RSO2Cl
h
Na , dry ether
(4) RX
Wurtz reaction RH
AlCl / HCl
Zn or (5) 3 branched alkanes
(5) RX
Isomerisation
Frankland's reaction RR
or
R C Cl or ROH CnH2n+2 Pyrolysis
Re
d
(6) P / Hi Alkenes
|| (6) 500 700 C
+ CH4 or C2H6
O
or Cr or Mo or V oxide

R CR or RCHO (7) Al 2O3 500C Aromatic com-
|| pound
O
R CR CH N
22
Zn Hg / Conc. HCl (8) Higher alkane
(7) ||
step up reaction
O Clemension 's reduction
R C O O
2
| H N NH
2 2
(9)
CO2 + H2O
(8) Wolf / Kishner reduction

R Combustion
or
(RCH2CH2)3B H O
2
(9) RCOONa NaOH CaO

(10) RCOONa Kolbe's electrolytic synthesis


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184
REACTION CHART FOR ALKENES

GMP GR
conc . H SO H Ni
(1) RCH2CH2OH 24 (1) 2, RCH2CH3
H2O 200300 C
alc
. KOH
(2) X
2 RCHXCH2X
(2) RCH2CH2X
HX
HX
RCH=CH2 (3)
RCHXCH3
Zn
dust

or (4) HBr , Peroxide
(3) RCH2CH for higher alkene
CnH2n RCH2CH2Br
X2
(5) HOCl
RCH(OH)CH2Cl
R CH CH 2 dil. H SO
Zn
dust
2 4
(4) | |
(6) HO RCH2(OH)CH3
2
X X 1 / 2 O2
(7) Ag
300C
Ni, H
2
(5) RC CH
200300C
RCH COOK
(8)
CH 2 N 2

(6) | Kolbe's electrolytic synthesis

RCH COOK
(9) BH
3 (RCH2CH2)3B
CO H
R CH CH 3 R CH CH
(7) (C2H5)4N+OH 2 2 2

(10)
HCo ( CO ) 4
| + |
Pyrolysis CHO CHO
R C O CH 2 CH 2 R
(8) 2 O
||
O
(11) CO2 + H2O

(9) RH Pyrolysis R CH CH 2
(12) O
S O4
| |
(10) CH2=CHCl CuR OH OH
2
Bayer reagent R CH CH 2
(13)
1% alkalineKM nO | |
4
OH OH
(14) strong R C OH + CO + H O
oxidant
|| 2 2
O
Per acid
(15) Pr iles
chalev 's reaction
3 O H O
2

(16) Ozonolysis +
2O

(17) 200 Polyalkene
C high P
Cl
(18) 2 Substitution product

500 C
Al (SO )
2
(19) 200
4 3
Isomerisation
300 C
(20) acetic
anhydride
RCH2=CHCOCH3
Methyl alkenyl ketone
(21) Alkane
Higher alkane

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185
REACTION CHART FOR ALKYNES

GMP GR
(1) CH2BrCH2Br (1) 2

H
C2H4, C2H6
alc. KOH or NaNH Ni
2

(2) X
2 C2H2X4
(2) CH3CHBr2 alc. KOH , NaNH
2 HBr
(3) CH BrCH Br
3 2
Peroxide
(3) CHCl3 Ag
powder
C2H2
HBr

(4) No CH CHBr
(4) CHBr2CHBr2 Peroxide 3 2
Zn
dust

(5) HOCl
Cl2CHCHO

(6) HCN , Ba ( CN ) 2
2 CH2=CHCN
CHBr (7) CH 3COOH , Hg
CH3CH(OCOCH3)2
(5) || Zn

CHBr Hg 2 , 80C , dil. H SO
(8) 2 4 CH CHO
( Kucherov 's reaction ) 3
(6) CH2=CHCl
alc. KOH , NaNH (7) (9) Conc

. H 2SO 4
CH3CH(HSO4)2
2
AsCl
HC COONa Kolbe's electroly tic synthesis (10) Ca det 3 CHCl=CHAsCl2
|| & Bunsen reaction
HC COONa
C 2 H5OH / H 2O
H 2O (11)
HgSO
CH CHO
(8) CaC2
3
4
electric arc,1200C CO HOH

(9) 2C + H2

Berthelot 's process
(12) CH =CHCOOH
Ni( CO ) 2 4
(
(10) CH3CCH i ) Na ( ii ) R X CO EtOH
(13) CH =CHCOOEt
Ni ,160C 2
(10) CH3CCH (i ) CH MgI (ii ) R X
3 (14) NaNH
2 NaCCNa
AgNO3 NH 4OH
(15) ( AgCCAg
Tollen 's Re agent )
(16) Cu Cl NH OH
22 4 CuCCCu
(17) Combustion

O2
CO2 + H2O
CHO
(18) Bayer
Reagent
| HCOOH
CHO
3O

(19) Ozonolysis H O
2
HCOOH
Trimerisat ion
(20) benzene
(Re d hot iron tube)
(21) Trimerisat
ion C8H8or 1,3,5,7-cyclo octa tetraene
[ Ni( CN ) 2 ]
Dimerisati on
(22) butenyne
[ Cu ( NH 3 ) 2 ]
s
(23)

CH OH
(24) 3 methylal
( BF HgO )
3

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186
PRACTICAL ORGANIC CHEMISTRY

(A) FUNCTIONAL GROUP ANALYSIS
1. Unsaturation : Alkenes & alkynes:
(a) Bayers test : Cold dil alk. KMnO4 decolourisation test
Purple colour Colourless + MnO2 (Brown ppt)
(b) Br2 water decolourisation test
Violet colourless of Br2 Colourless
2. Terminal alkynes:
Confirmed by ppt of Acetylide ion with NaNH2 or AgNO3 or Cu2Cl2NH4OH
3. Alkyl halides:
(a) If they are capable of carbocation formation then they will give ppt with AgNO3.
(b) Beilsteins test : A green colour is imported to the flame if small amount of organic compound is
taken on
copper wire.
4. Alcohol:
(a) Cerric ammonium nitrate Give red colour
(b) Boil with acetic acid & conc. H2SO4 fruity smell

(c) 2-alkanol & ethanol also give Iodoform test Yellow ppt. of CH3I on reaction with I2+ OH
5. Aldehyde & Ketones:
2,4- Dinitrophenyl hydrazize (or) Braddys reagent give yellow, orange or red color with ald. & Ketones
(2,4-DNP)
6. Aldehydes:
(a) Tollens test Silver mirror
(b) Fehlings test {except benzaldehyde} Red colour
(c) Benedicts test Red colour
(d) Schiffs dye colour regeneration test Pink colour
(e) Gly ppt with HgCl2 .
7. Ketones:
(a) Methyl Ketones give haloform test
(b) -hydroxy Ketones give Tollens & Fehling tests too.
8. Carboxylic acids:
(a) Brisk effervescence with aq. NaHCO3 solution.
(b) HCOOH alone gives silver mirror test with Tollens reagent.
(c) Blue litmus red
(d) Give fruity smell on reaction with alcohols.
9. Phenols:
(a) Violet colouration with neural FeCl3
(b) Liebermann test
(c) White ppt with Br2 water
(d) Brisk effervescence with aq. NaHCO3 is observed in case of Nitrophenols.
10. Primary amines:
(a) Carbylamine reaction Isonitriles have very distinctive foul odors
(b) Hoffmann mustard oil reaction Oily liquid with mustard like smell.
11. Aromatic 1 amine diazo test
12. Amide boil with NaOH NH3
13. Nitrobenzene Mullikqn Baker test Treat it with ZnNH4Cl then boil with Tollens reagent Silver

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187
mirror will appear

14. Proteins:
(a) Biuret test : Also used for urea Alkaline solution of protein treated with a drop of aq CuSO4
when bluish violet colour is obtained
(b) Ninhydrin test : Protein treated with a puridine solution of ninhydrin give colour ranging from deep blue
to violet pink.
DIFFERENTATION TEST
D1. 1, 2 & 3 alcohols:
(a) Lucas test : Lucas reagent is conc. HCl + ZnCl2
(b) Victor Meyers test (RBC test)
(i) 1 Alcohol Blood red colour
(ii) 2 Alcohol Blue
(iii) 3 Alcohol Colourless
D2. 1, 2 & 3 amines:
(a) Hinsbergs reagent
(i) 1 Amine yield a clear solution from which upon acidification an insoluble material separated.
(ii) 2 Amine yield an insoluble compound which is unaffected by acid
(iii) 3 Amine yield insoluble compound
(b) Reaction with HNO2
QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS

The elements present inorganic compounds aer carbon and hydrogen. In addition to these, they may also
contain oxygen, nitrogen, sulphur,halogens and phosphorus.
1. Detection of Carbon and Hydrogen
Carbon and hydrogen are detected by heating the compound iwth copper (II) oxide. Carbon present in the
compound is oxidised to carbon dioxide (tested with lime-water, which develops turbidity) and hydrogen to
water (tested with anhydrous copper suphate, which turns blue).
C + 2CuO 2Cu + CO2

2H + CuO Cu + H2O

CO2 + Ca(OH)2 CaCO3 + H2O
5H2O + CuSO4 CuSO4 . 5H2O
White Blue
2. Detection of Other Elements
Nitrogen, sulphur, halogens and phosphorus present in an organic comopund are detected by Lassaignes
test . The elements present in the compound are converted from covalent form into the ionic form by
fusing the compound with sodium metal. Following reactions take place:
Na + + N NaCN

2Na + S Na2S

Na + X NaX

(X = Cl, Br or I)
C, N, S and X come from organic comopund.
Cyanide, sulphide and halide of sodium so formed on sodium fusion are extracted from the fused mass by
boiling it with distilled water. This extract is known as sodium fusion extract.
(A) Test of Nitrogen
The sodium fusion extract is boiled with iron(II) sulphate and then acidified with concentrated sulphuric
acid. The formation of Prussian blue colour confirms the presence of nitrogne. Sodium cyanide first reacts
with iron(II) sulphate and forms sodium hexacyanoferate(II). On heating with concentrated sulphuric acid
some iron(II) ions are oxidised to iron(III) ions which react with sodium hexacyanoferrate(II) to produce
iron(III) hexacyanoferrate(II) (ferriferrocyanide) which is Prussian blue in colour.

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188
6CN + Fe2+ [Fe(CN)6]4

3[Fe(CN)6]4 + 4Fe3+ xH
2O
Fe4[Fe(CN)6]3 . xH2O
Prussian blue
(B) Test for Sulphur
(a) The soldium fusion extract is acidified with acetic acid and lead acetate is added to it. A black precipitate
of lead sulphide indicates the presence of sulphur.
S2 + Pb2+ PbS
Black
(b) On treating sodium fusion extract with sodium nitroprusside, appearance of a violet colour further
indicates the presence of sulphur.
S2 + [Fe(CN)5NO]2 [Fe(CN)5NOS]4
Violet
In case, nitrogen and sulphur both are present in an organic compuond, sodium thiocyanate is formed. It
gives blood red colour and no Prussian blue since there are no free cyanide ions.
Na + C + N + S NaSCN
Fe3+ + SCN [Fe(SCN)]2+
Blood red
If sodium fusion is carried out with excess of sodium, the thiocyanate decomposes to yield cyanide and
sulphide. These ions give their usual tests.
NaSCN + 2Na NaCN + Na2S
(C) Test of Halogens
The sodium fustion extract is acidified with nitric acid and then treated with silver nitrate. A white precipi-
tate, soluble in ammonium hydroxide shows the presence of chlorine, a yellowish precipitate, sparingly
soluble in ammonium hydroxide shows the presence of bromine and a yellow precipitate, insolube in ammo-
nium hydroxide shows the presence of iodine.
X + Ag+ AgX
X represents a halogen Cl, Br or I.
If nitrogen or sulphur is also present in the compound, the sodium fusion extract is first boiled with concen-
trated nitric acid to decompose cyanide or sulphide of sodium formed during Lassaignes test. These ions
would otherwise interfere with silver nitrate test for halogens.
(D) Test for Phosphorus
The compound is heated with an oxidising agent (sodium peroxide). The phosphorus present in the com-
pound is oxidised to phophate. The solution is boiled with nitric acid and then treated with ammonium
molybdate. A yellow colouration or precipitate indicates the presence of phophorus.
Na3PO4 + 3HNO3 H3PO4 + 3NaNO3
H3PO4 + 12(NH4)2MoO4 + 21HNO3 (NH4)3PO4 . 12MoO3 + 21NH4NO3 + 12H2O
Ammonium molybdate Ammonium phophomolybdate

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190
POINTS TO REMEMBER
(1) List of Monomers & Polymers
Monomer(s) Structure of Polymer / Common uses
Name of Polymer
1. CH 2 C CH CH 2 CH 2 C C CH 2
n
| |
G G
Branched chain polymer
2. G = CH3
Natural rubber
CH 2 C C CH 2
n
CH 2 C CH CH 2 |
| CH 3
CH 3 Polyisoprene
( (Isoprene)
Synthetic rubber
3. G = Cl CH 2 C C CH 2
n
(Cloroprene) |
Cl
Polycloroprene or Neoprene
Houseware, containers, bottles,

4. CH2=CH2 (ethylene) CH 2 CH 2n
toys, polyethylene sheets, and
Polyethene films for packaging
5. CH2=CHPh (styrene) [ CH CH 2 ]n
| Houseware, toys, disposable,
Ph food containers, packaging
Polystyrene (styrofoam), cabinets for
electrical and electronic gadgets
6. CH2=CHCl(vinyl chloride) [CH CH ]n Tubes and pipes for electrical
| fitting, sanitary pipes, floor tiles,
Cl
insulation for cables, as a
Polyvinyl Chloride (PVC) substitute for leather
In sweaters, blankets, and
7. CH2=CHCN [CH 2 CH ]n clothing as a substitute for wool
(acrylonitrile) |
CN
Poly acrylonitrite (PAN) Orlon
Non-stick cooking utensils,
8. CF2 = CF2 [CF2 CF2]n gaskets, bearings, and insulating
Polytetrafluoro ethylene or Teflon fittings.
9. CH2=CHCH=CH2 +
[CH 2 CH CH 2 (CH 2 ) 2 CH
]n
PhCH=CH2 | Synthetic rubber
Ph
StyreneButadiene Rubber (BUNAS)
10. CH2=CHCH=CH2 + [CH 2 CH CH CH 2 CH CH

]n
|
CH CH 2 CN Synthetic rubber
| BUNAN
CN

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191
11. + Terylene or Dacron Fibre, Tyre, Belts
12. + as a binding
material for
mixed plastic
Glyptal
O
13. ||
[ NH (CH 2 )5 C ]n Fibre, rope, plastic
Caprolactum
Nylon6
14. NH2(CH2)6NH2 O O
|| ||
Hexa methyl diamine + [ NH (CH ) NH C (CH ) C ]n Fibre, parachutes
2 6 2 4
Adipic acid
Nylon66
COOH(CH2)4COOH
O
||
15. Urea + HCHO
[ NH C NH CH 2
]n Fibre, unbreakable
cups & plates
Urea formaldehyde resin
16. Plastic sheets
Melamine
+ Melamine formaldehyde resin
HCH
||
O
Insulating material
for electrical goods
17. + HCHO t h er mo s et t ing
Bakellite plastic
[ CH 2 CH ]n Synthetic carpets,
18. CH2=CHCH3 | automobile parts,
(Propylene) CH 3 packaging, toys,
Polypropylene and houseware.
[ CH 2 CH ]n Adhesives, as
19. CH2=CHOCOCH3 | binder for paints
(Vinyl acetate) OCOCH 3
Polyvinyl acetate
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192
20. CH2=CHCO2CH3 [ CH 2 CH
]n As a substitute of glass
Methyl methacrylate |
COOCH 3
Polymethyl methacrylate
(Plexiglass, Lucite)
21. CH2=CCl2 Cl Air and water proof packaging

|
[Vinylidine chloride] [ CH 2 C ]n films. Its copolymer with vinyl
(1,1-dichloroethene) | chloride is used for making
Cl conveyer belts and acid proof
Polyvinylidine chloride ropes.
(Saran)
CH 3
|
22. CH2=C(CH3)2 [ CH 2 C
]n As lining and insulators for cables.
(Isobutene) | Its copolymer with isoprene is
CH 3 used for manufacturing tyres.
Polyisobutene
23. Phenol and Bakelite Electrical switches, lamination,
formaldehyde etc.
24. Urea and formaldehyde Urea-formaldehyde resin Ion-exchange resin, adhesives,

electrical fittings, grease resisting
textile, foams, lamination.
25. Melamine and Melamine-formaldehyde resin Kictenware (melamine crockery),

formaldehyde furniture, laminates, electrical
insulators, adhesives, fabric and
paper treatment.
26. Adipic acid and Nylon 6,6 Synthetic fibre

Hexa-methylenediamine
27. Caprolactam *Nylon 6 Synthetic fibre
28. Terphthalic acid and Polyester (Terylene, Dacron) Synthetic fibre of high tensile
Ethylene glycol (or its strengt h with anti-wrinkle
ester) properties.
29. Bis-phenol A and Polycarbonate Used extensively in automobile

Carbonic acid indust ry, table cutlery, as
derivative protective covering, compact disc
(CD), as bullet proof sheets, safety
glasses, etc.
30. Diisocyanates and Diols Polyurethanes As adhesive, in shoe soles, tyres,

and foam surface coating in paints
and varnishes.

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193
(2) Reducing agents and their role

Group Product LAH in LiA lH(OCM e3)3 NaBH4 LiAH4 B2H6 H2+
ether in THF in EtOH +AlCl3 in THF catalyst
CHO CH2OH + + + + +
>C=O >CHOH + + + + +
CO2H CH2OH + + + +
CO2R CH2OH + + + +
COCl CH2OH + +* + + +
CONH2 CH2NH2 + + + +
(RCO)2O RCH2OH + + + +
CN CH2NH2 + + + +
>C=NOH CH2NH 2 + + +
RNO2 RNH2 + + +
>C=C< >CHCH< + +
CC CH=CH + + +
1 RX RH + + +
* Product is RCHO

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1

IDEAL 21ST CENTURY COMPETITIONS

APPLICATION OF MOLE CONCEPT

1. LAWS OF CHEMICAL COMBINATION

"Wonder these laws are useful?"

2.2 Methods of Calculations of mole :

Gases do not have volume. What is meant by "Volume of gas"?

Do not use this expression (PV = nRT) for solids/liquids.

How would I calculate moles if volume of a solid is given?

IDEAL 21ST CENTURY COMPETITIONS

Be clear in the difference between 1 amu and 1 gm.

Average atomic weight wt of X B

Try working out of such a shortcut for XA, XB, XC

3. EMPIRICAL FORMULA, MOLECULAR FORMULA :

3.2 Relation between the two : Molecular formula = Empirical formula n

3.3 Vapour density :

Can you prove the above expression?

Is the above parameter temperature dependent?

4. STOICHIOMETRY : Stoichiometry pronounced (stoy key om e tree) is the calculations of the

IDEAL 21ST CENTURY COMPETITIONS

(a) Mole Method Balance reaction required

5. CONCEPT OF LIMITING REAGENT.

5.2 Calculation of Limiting Reagent :

7. SOME EXPERIMENTAL METHODS :

IDEAL 21ST CENTURY COMPETITIONS

(b) Silver salt method : (for organic acids)

(1) Which of these are temperature dependent.

1.2 For solutions (homogeneous mixture) :

What is solute and solvent in a solution.

IDEAL 21ST CENTURY COMPETITIONS

If the mixture is not homogeneous, then none of them is applicable.

for gases % by volume is same as mole %

Mass of solute 6 Mass of solute

Get yourselves very much confortable in their interconversion. It is very handy.

1.3 Some typical concentration terms :

Work out a relationship between M and volume H2O2 and remember it

IDEAL 21ST CENTURY COMPETITIONS

EUDIOMETRY : [For reactions involving gaseous reactants and products]

IDEAL 21ST CENTURY COMPETITIONS

(c) Rn = R1 (A)1/3 , R1 = 1.33 1013 cm A = mass number

IDEAL 21ST CENTURY COMPETITIONS

(b) For First line of a series n2 = n1 + 1

(c) Limiting spectral line (series limit) means n2 =

(e) Similarly H line means n2 = n1+ 2

IDEAL 21ST CENTURY COMPETITIONS

6. De-broglie, Heisenberg & Schrodinger equations

7. Terms associated with elements

Cosmic -rays X-rays Vaccum UV Visible Near Far Micro Radio

IDEAL 21ST CENTURY COMPETITIONS

(i) Forces of attraction

Are volume of solids & liquid totally independent of pressure??

Parameter associated with the gas : P ,V ,T , n

INSTRUMENTS FOR PRESSURE CALCULATIONS :

IDEAL 21ST CENTURY COMPETITIONS

Manometer : Pgas = Patm + hdg

EQUATION & GRAPHS OF EXTENSIVE UTILITY IN GASEOUS STATE :

Two Parameters 'y' & 'x' if are related as

Plot the different curves for difference values of n & V to compare.

Plot graphs of V vs Tc & V vs TF

IDEAL 21ST CENTURY COMPETITIONS

PM = dRT = 8.314 joule / kelvin = 2cal kelvin1 mol1

Dalton's law of partial pressure :

PA , PB are partial pressures . ; PA = mole fractionA Total pressure