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STOICHIOMETRY - 1 Page # 3
LAWS OF CHEMICAL COMBINATION
(a) Law of conservation of mass [Lavoisier]

In a chemical change total mass remains conserved i.e. mass before the reaction is always equal to
mass after the reaction.
H2 + 1/2 O2 → H2O ()
(g) (g)
1 mole 1/2 mole 1 mole
mass before the reaction = 1 × 2 + 1/2 × 32 = 18 gm
mass after the reaction = 1 × 18 = 18 gm
(b) Law of constant composition [Proust]

All chemical compounds are found to have constant composition irrespective of their method of prepration
or sources.
⇒ In H2O, Hydrogen & oxygen combine in 2 : 1 molar ratio, this ratio remains constant whether it is Tap
water, river water or seawater or produced by any chemical reaction.
(c) Law of multiple proportions [Dalton]

When one element combines with the other element to form two or more different compounds, the
mass of one element, which combines with a constant mass of the other bear a simple ratio to one
another.
⇒ Carbon is found to form two oxides which contain 42.9% & 27.3% of carbon respectively show that
these figures shows the law of multiple proportion.
First oxide Second oxide
Carbon 42.9 % 27.3 %
Oxygen 57.1 % 72.7% Given
In th first oxide, 57.1 parts by mass of oxygen combine with 42.9 parts of carbon.
42.9
1 part of oxygen will combine with part of carbon = 0.751
57.1
Similarly in 2nd oxide
27.3
1 part of oxygen will combine with part of carbon = 0.376
72.7
The ratio of carbon that combine with the same mass of oxygen = 0.751 : 0.376 = 2 : 1
This is a simple whole no ratio this means above data shows the law of multiple proportion.
(d) Law of reciprocal proportions [Richter]

When two elements combine seperately with definite mass of a third element, then the ratio of their
masses in which they do so is either the same or some whole number multiple of the ratio in which they
combine with each other.
This law can be understood easily with the help of the following examples.
At. Mass 1 At. Mass 32

H2S
H S
H
2O
2
SO
At. Mass 16
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Page # 4 STOICHIOMETRY - 1
⇒ Let us consider three elements – hydrogen, sulphur and oxygen. Hydrogen combines with oxygen to
form H2O whereas sulphur combines with it to form SO2. Hydrogen and sulphur can also combine
together to form H2S. The formation of these compounds is shown in fig.
In H2O, the ratio of masses of H and O is 2 : 16.
In SO2, the ratio of masses of S and O is 32 : 32. Therefore, the ratio of masses of H and S which
combines with a fixed mass of oxygen (say 32 parts) will be
4 : 32 i.e. 1 : 8 ...(1)
When H and S combine together, they form H2S in which the ratio of masses of H and S is
2 : 32 i.e., 1 : 16 ...(ii)
The two ratios (i) and (ii) are related to each other as
1 1
: or 2 :1
8 16
i.e., they are whole number multiples of each other.
Thus, the ratio masses of H and S which combines with a fixed mass of oxygen is a whole number
multiple of the ratio in which H and S combine together.
(e) Gay Lussac law of combining volumes :

When two or more gases react with one another, their volumes bear simple whole number ratio with
one another and to the volume of products (if they are also gases) provided all volumes are measured
under identical conditions of temperature and pressure.
⇒ When gaseous hydrogen and gaseous chlorine react together to form gaseous hydrogen chloride
according to the following equation.
H (g) + Cl 2 (g) →2HCl( g)
2
one volume one volume two volumes
It has been observed experimentally that in this reaction, one volume of hydrogen always reacts with
one volume of chlorine to form two volumes of gaseous hydrogen chloride. all reactants and products
are in gaseous state and their volumes bear a ratio of 1 : 1 : 2. This ratio is a simple whole number
ratio.
“These are no longer useful in chemical calculations now but gives an idea of earlier methods of
analysing and relating compounds by mass.”
MOLE CONCEPT
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.
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, then 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 (0°C & 1 bar) occupies 22.7 litre.
1 mole of any gas at STP (0°C & 1 atm) occupies 22.4 litre.
Atom : Atom is smallest particle which can not be divided into its constituents.
Atomic weight : It is the weight of an atom relative to one twelvth of weight of 1 atom of C-12
RELATIONSHIP BETWEEN GRAM AND AMU

1
1 amu = wt of one C - 12 atom.
12
for C 1 mole C = 12 gm = 6.023 × 1023 atoms
wt of 6.023 × 1023 atoms = 12 gm
12
wt of 1 atom of C = N gm (NA → Avogadro’s number = 6.23 × 1023)
A
1
1 amu = wt of one C - 12 atom
12
1 12
= 12 × N gm
A
1
1 amu = N gm
A
ELEMENTAL ANALYSIS
For n mole of a compound (C3H7O2)
Moles of C = 3n
Moles of H = 7n
Moles of O = 2n
Ex.1 Find the wt of water present in 1.61 g of Na2SO4. 10H2O
wt. in gram 1.61
Sol. Moles of Na2SO4. 10H2O = = = 0.005 moles
molecular wt 322
Moles of water = 10 × moles of Na2SO4. 10H2O
= 10 × 0.05 = 0.05
wt of water = 0.5 × 18 = 0.9 gm Ans.
Ex.2 Calculate the following for 49 gm of H2SO4

(a) moles (b) Molecules (c) Total H atoms (d) Total O atoms (e) Total electrons
Sol. Molecular wt of H2SO4 = 98
wt in gm 49 1
(a) moles = = = mole
molecular wt 98 2
(b) Since 1 mole = 6.023 × 1023 molecules.

1 1
mole = 6.023 × 1023 × molecules
2 2
23
= 3.011 × 10 molecules
(c) 1 molecule of H2SO4 Contains 2 H atom
3.011 × 1023 of H2SO4 contain 2 × 3.011 × 1023 atoms
= 6.023 × 1023 atoms
(d) 1 molecules of H2SO4 contains 4 O atoms
3.011 × 1023 molecular of H2SO4 contains = 4 × 3.011 × 1023 = 12.044 × 1023
(e) 1 molecule of H2SO4 contains
2H atoms + 1 S atom + 4 O atom
this means 1 molecule of H2SO4 Contains (2 + 16 + 4 × 8) e–
So 3.011 × 1023 molecules have 3.011 × 1023 × 50 electrons
1.5055 × 1025 e–
Ex.3 Calculate the total ions & charge present in 4.2 gm of N–3
wt in gm 4.2
Sol. mole = = = 0.3
Ionic wt 14
total no of ions = 0.3 × NA ions
total charge = 0.3 NA × 3 × 1.6 × 10–19
= 0.3 × 6.023 × 1023 × 3 × 1.6 × 10–19
= 8.67 × 104 C Ans.
Ex.4 Find the total number of iron atom present in 224 amu iron.
Sol. Since 56 amu = 1 atom
1
therefore 224 amu = × 224 = 4 atom Ans.
56
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%)
MOLECULAR WEIGHT
It is the sum of the atomic weight of all the constituent atom.
∑n M i i
(a) Average molecular weight =
∑n i
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 wei ght – wt of XB
%of X A = × 100
difference in weight of X A & XB
Try working out of such a shortcut for XA, XB, XC
EMPIRICAL FORMULA, MOLECULAR FORMULA
Empirical formula : Formula depicting constituent atom in their simplest ratio.

Molecular formula : Formula depicting actual number of atoms in one molecule of the compound.
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.
Ex.5 A molecule of a compound have 13 carbon atoms, 12 hydrogen atom, 3 oxygen atoms and 3.02
× 10–23 gm of other element. Find the molecular wt. of compound.
12 1 16
Sol. wt. of the 1 molecule of a compound = 13 × N + 12 × N + 3 × N + 3.02 × 10–23
A A A
156 + 12 + 48 + 3.02 + 10 –23 NA

= = 234.18 / NA = 234 amu. Ans.
NA
Ex.6 A compound containing Ca, C, N and S was subjected to quantitative analysis and formula
mass determination. A 0.25 g of this compound was mixed with Na2CO3 to convert all Ca into
0.16 g CaCO3. A 0.115 gm sample of compound was carried through a series of reactions until
all its S was changed into SO42– and precipitated as 0.344 g of BaSO4. A 0.712 g sample was
processed to liberated all of its N as NH3 and 0.155 g NH3 was obtained. The formula mass was
found to be 156. Determine the empirical and molecular formula of the compound.
0.16
Sol. Moles of CaCO3 = = Moles of Ca
100
0.16
Wt of Ca = × 40
100
0.16 100
Mass % of Ca = × 40 × = 25.6
100 0.25
0.344 32 × 100
Similarly Mass % of S= × = 41
233 0.115
0.155 14
Similarly Mass % of N= × × 100 = 17.9
17 0.712
⇒ Mass % of C = 15.48
Now :
Elements Ca S N C
Mass % 25.6 41 17.9 15.48
Mol ratio 0.64 1.28 1.28 1.29
Simple ratio 1 2 2 2
Empirical formula = CaC2N2S2,
Molecular formula wt = 156
n × 156 = 156 ⇒ n = 1
Hence, molecular formula = CaC2N2S2
• Density :
(a) Absolute density
(b) Relative density
Mass
Absolute density =
volume
density of subs tan ce

Relative density =
density of s tan dard subs tan ce
density of subs tan ce

Specific gravity = density of H O at 4° C
2
Vapour density : It is defined only for gas.

It is a density of gas with respect to H2 gas at same temp & press
dgas PMgas / RT Mgas M

V.D = dH = PM / RT = M =
2 H2 H2 2
M
V.D =
2
Molecular wt of gas
V.D = Molecular wt of H gas
2
• density of Cl2 gas with respect to O2 gas
Molecular wt of Cl2 gas

= Molecular wt of O gas
2
• STOICHIOMETRY : Stoichiometry is the calculations of the quantities of reactants and products

involved in a chemical reaction. Following methods can be used for solving problems.
(a) Mole Method (For Balance reaction)
(b) POAC method } Balancing not required but common sense ------- use it with slight care.
(c) Equivalent concept
• CONCEPT OF LIMITING REAGENT.

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.
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.]
• PERCENTAGE YIELD :
actual yield
The percentage yield of product = × 100
the theoretical maximum yield
• 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.)
Ex.7 A compound which contains one atom of X and two atoms of y for each three atoms of z is made
of mixing 5 gm of x, 1.15 × 1023 atoms of Y and 0.03 mole of Z atoms. Given that only 4.40 gm
of compound results. Calculate the atomic weight of Y if atomic weight of X and Z are 60 and 80
respectively.
5 1
Sol. Moles of x = = = 0.083
60 12
. × 10 23
115
moles of y = = 0.19
6.023 × 10 23
moles of z = 0.03
x + 2y + 3z → xy2z3
for limiting reagent, 0.083/1 = 0.083
0.19 0.03
= 0.095 , = 0.01
2 3
Hence z is limiting reagent
wt of xy2z3 = 4.4 gm = moles × molecular wt.
1
moles of xy2z3 = × 0.03 = 0.01
3
300 + 2 m = 440 ⇒ 2m = 440 – 300 ⇒ m = 70 Ans.
Ex.8 A polystyrne having formula Br3C6H3(C3H8)n found to contain 10.46% of bromine by weight.
Find the value of n. (At. wt. Br = 80)
Sol. Let the wt of compound is 100 gm & molecular wt is M
100
Then moles of compound =
M
100
Moles of Br = ×3
M
100
wt of Br = × 3 × 80 = 10.46
M
M = 2294.45 = 240 + 75 + 44 n
Hence n = 45 Ans.
Ex.9 A sample of clay was partially dried and then analysed to 50% silica and 7% water. The original
clay contained 12% water. Find the percentage of silica in the original sample.
Sol. In the partially dried clay the total percentage of silica + water = 57%. The rest of 43% must be some
50
impurity. Therefore the ratio of wts. of silica to impurity = . This would be true in the original sample
43
of silica.
The total percentage of silica + impurity in the original sample is 88. If x is the percentage of silica,
x 50
= ; x = 47.3% Ans.
88 – x 43
Ex.10 A mixture of CuSO4.5H2O and MgSO4. 7H2O was heated until all the water was driven-off. if 5.0
g of mixture gave 3 g of anhydrous salts, what was the percentage by mass of CuSO4.5H2O in
the original mixture ?
Sol. Let the mixture contain x g CuSO4.5H2O
x 5–x
⇒ × 159.5 + × 120 = 3 ⇒ x = 3.56
249.5 246
3.56
⇒ Mass percentage of CuSO4. 5H2O = × 100 = 71.25 % Ans.
5
P O A C Rule : P O A C is the simple mass conservation.
KClO3 → KCl + O2
Apply the POAC on K.
moles of K in KClO3 = moles of K in KCl
1 × moles of KClO3 = 1 × moles of KCl
moles of KClO3 = moles of KCl
Apply POAC on O
moles O in KClO3 = moles of O in O2
3 × moles of kClO3 = 2 × moles of O2
Ex.11 In the gravimetric determination of phosphorous, an aqueous solution of dihydrogen phosphate

ion (H2PO4–) is treated with a mix of ammonium & magnesium ions to precipitate magnesium
a mmon iu m ph os ph ate
MgNH4 PO4.6H2O. This is heated and decomposed to magnesium Pyrophosphate, Mg2P2O7 which
is weighted. A solution of H2PO4– yielded 1.054 gm of Mg2P2O7 what weight of NaH2 PO4 was
present originally.
NaH2PO4 → Mg2P2O7
apply POAC on P
Let wt of NaH2PO4 = w gm
moles of P in NaH2PO4 = moles of P in Mg2P2O7
w 1.054
×1 = ×2
120 232
120
w = 1.054 × × 2 = 1.09 gm Ans.
232
Ex .12 367.5 gm KClO3 (M = 122.5) when heated, How many litre of oxygen gas is proudced at S.T.P.
Sol. KClO3 → KCl + O2
Applying POAC on O
moles of O in KClO3 = moles of O in O2
3 × moles of KClO3 = 2 × moles of O2
367.5
3× =2×n
122.5
3 367.5
n= ×
2 122.5
Volume of O2 gas at S.T.P = moles × 22.4
3 367.5
= × × 22.4 = 9 × 11.2 = 100.8 lit Ans.
2 122.5
SOME EXPERIMENTAL METHODS
FOR DETERMINATION OF ATOMIC MASS

Dulong’s and Petit’s Law :
Atomic weight × specific heat (cal/gm°C) ∝ ≅ 6.4
Gives approximate atomic weight and is applicable for metals only. Take care of units of specific heat.
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′
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 replacible H+ atoms in an acid (H bonded to more electronegative atom is
acidic)
Procedure : Some known amount of silver salt (w1 gm) is heated to obtain w2 gm of white shining
residue of silver. Then if the basicity of acid is n, molecular weight of acid would be
AgnA → nAg+ + A–n
Agn A is the salt
 w 2 1
 ×  × Msalt = w 1 and molecular weight of acid = M – n(108)
 108 n  salt
This is one good practicle 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
 w 2 1 Msalt – n( 410)
‘n’ then  ×  × M = w and M =
195 n  salt 1 base
2
• For % determination of elements in organic compounds :

• All these methods are applications of POAC
• Do not remember the formulas, derive them using the concept, its easy.
(a) Liebig’s method : (Carbon and hydrogen)
∆
(w) Organic Compound  → (w1) CO2 + H2O (w2)
CuO
w 1 12
% of C = × × 100
44 w
w2 2
% of H = × × 100
18 w
where w1 = wt. of CO2 produced, w2 = wt. of H2O produced,
w = wt, of organic compound taken
(b) Duma’s method : (for nitrogen)

∆
(w) Organic Compound CuO
→ N → (P, V, T given)
2
use PV = nRT to calculate moles of N2, n.

n × 28
∴ % of N = × 100
w
w = wt of organic compound taken
(c) Kjeldahl’s method : (for nitrogen)

(w) O.C. + H2SO4 → (NH4)2SO4 NaOH
→ NH3 + H2SO4 → (molarity M and volume (V1) consumed given)
MV1 × 2 × 14
⇒ % of N = × 100
w
where M = molarity of H2SO4.
• Some N containing compounds do not give the above set of reaction as in Kjeldahl’s method.
(d) Sulphur :
(w) O.C. + HNO3 → H2SO4 + BaCl2 → (w1) BaSO4
w1 32
⇒ % of S = ×1× × 100
233 w
where w1 = wt. of Ba SO4, w = wt. of organic compound
(e) Phosphorus :
∆
O.C+ HNO3 → H3PO4 + [NH3 + magnesia mixture ammonium molybdate] → MgNH4 PO4  → Mg2P2O7
w 1 2 × 31
% of P = × × 100
222 w
(f) Carius method : (Halogens)
O.C. + HNO3 + AgNO3 → AgX
If X is Cl then colour = white
If X is Br then colour = dull yellow
If X is I then colour = bright yellow
• Flourine can’t be estimated by this
w1 1 × ( At. wt of X )
% of X = × × 100
(M. weight of AgX ) w
Ex.13 0.607 g of a silver salt of a tribasic organic acid was quantitatively reduced to 0.370 g of pure
silver. Calculate the molecular weight of the acid (Ag = 108)
Sol. Suppose the tribasic acid is H3A.
H3A → Ag3A → Ag
acid salt
0.607 g 0.37 g
Since Ag atoms are conserved, applying POAC for Ag atoms,

moles of Ag atoms in Ag3A = moles of Ag atoms in the prduct
3 × moles of Ag3A = moles of Ag in the product
0.607 0.37
3× = (Ag = 108)
mol. wt. of Ag3 A 108
mol. wt. of Ag3A = 531.
∴ mol. weight of tribasic acid (H3A)
= mol wt. of the salt (Ag3A) – 3 × at. wt. of Ag
+ 3 × at. wt. of H
= 531 – 324 + 3 = 210 Ans.
Ex.14 0.532 g of the chloroplatinate of a diacid base on ignition left 0.195 g of residue of Pt. Calculate
molecular weight of the base (Pt = 195)
Sol. Suppose the diacid base is B.
B + H2PtCl6\ → BH2PtCl6 → Pt
diacid acid chloroplatinate
base 0.532 g 0.195 g
Since Pt atoms are conserved, applying POAC for Pt atoms,
moles of Pt atoms in BH2PtCl6 = moles of Pt atoms in the product
1 × moles of BH2PtCl6 = moles of Pt in the product
0.532 0.195
=
mol. wt. of BH2PtCl6 195
∴ mol. wt. of BH2PtCl6 = 532
From the formula BH2PtCl6, we get
mol. wt. of B = mol. wt. of BH2PtCl6 – mol. wt. of H2PtCl6
= 532 – 410 = 122. Ans.
EUDIOMETRY
[For reactions involving gaseous reactants and products]
• The stoichiometric coefficient of a balanced chemical reactions also gives that ratio of volumes in
which gasesous 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
Ammon Cu2Cl2 CO
Turpentine oil O3
Alkaline pyrogallol O2
water NH3, HCl
CuSO4/CaCl2 H2O
Assumption : On cooling the volume of water is negligible
Ex.15 7.5 mL of a hydrocarbon gas was exploded with excess of oxygen. On cooling, it was found to
have undergone a contraction of 15 mL. If the vapour density of the hydrocarbon is 14, determine
its molecular formula. (C = 12, H = 1)
y y
Sol. CxHy + (x + ) O2 → X CO2 + HO
4 2 2
7.5 ml 15
on cooling the volume contraction = 15 ml
i.e. The volume of H2O (g) = 15 ml
V.D. of hydrocarbon = 14
Molecular wt. of CxHy = 28
12x + y = 28 ...(1)
From reaction
y
7.5 = 15 ⇒ y=4
2
12 x + 4 = 28
12x = 24
x=2
Hence Hydrocalbon is C2H4.
Ex.16 10 mL of a gaseous organic compound containing. C, H and O only was mixed with 100 mL of
oxygen and exploded under conditions which allowed the water formed to condense. The volume
of the gas after explosion was 90 mL. On treatment with potash solution, a further contraction
of 20 mL in volume was observed. Given that the vapour density of the compound is 23, deduce
the molecular formula. All volume measurements were carried out under the same conditions.
 y z y
Sol. CxHyOz +  x + –  O2 → xCO2 + H2O
4 2 2
10 ml
after explosion volume of gas = 90 ml
90 = volume of CO2 gas + volume of unreacted O2
on treatment with KOH solution volume reduces by 20 ml. This means the volume of CO2 = 20 ml
the volume of unreacted O2 = 70 ml
volume of reacted O2 = 30 ml
V.D of compoud = 23
molecular wt 12x + y + 16z = 46 ...(1)
from equation we can write
 y z
10 x + –  = 30
 4 2
y z
x+ – =3
4 2
4x + y – 2z = 12 ...(11)
& 10x = 20 ⇒ x=2
from eq. (1) & (2)
z=1 &y=6 Hence C2H6O Ans.
Ex.17 A sample of coal gas contained H2, CH4 and CO. 20 mL of this mixture was exploded with 80 mL
of oxygen. On cooling, the volume of gases was 68 mL. There was a contraction of 10 mL. When
treated with KOH. Find the composition of the original mixture.
Sol. H2 + CH4 + CO
at H2 = x ml
CH4 = y ml
CO = (20 – x – y) ml
H2 + CH4 + CO + O2 → CO2 + H2O
x y 20 – x – y
on cooling the volume of gases = 68 ml
68 = volume of CO2 + unreacted O2
volume contraction due to KOH = 10 ml
this means volume of CO2 = 10 ml
volume of unreacted O2 = 58 ml
volume of reacted O2 = 80 – 58 = 22 ml
Applying POAC on C
y + 20 – x – y = volume of CO2
20 – x = 10 ⇒ x = 10
Applying POAC on H
2x + 4y = 2x moles of H2O
moles of H2O = x + 2y
Applying POAC on O
1 × moles of CO + 2 × moles of O2
= 2 × moles of CO2 + 1 × moles of H2O
1 × 20 – x – y + 2 × 22 = 2 × 10 + x + 2y
20 – x – y + 44 = 20 + x + 2y
2x + 3y = 44
3y = 44 – 20 = 24
y = 8 ml
x = 10 ml
volume of CO = 20 – x – y ⇒ = 2 ml Ans.
CONCENTRATION OF SOLUTION
Concentration of solution can be expressed in any of the following ways.
(a) % by wt ⇒ amount of solute dissolved in 100 gm of solution
4.9% H2SO4 by wt.
⇒ 100 gm of solution contains 4.9 gm of H2SO4
(b) % by volume ⇒ volume of solute dissolved in 100 ml of solution
x% H2SO4 by volume
⇒ 100 ml of solution contains x ml H2SO4
(c) % wt by volume ⇒ wt. of solute present in 100 ml of solution
(d) % volume by wt. ⇒ volume of solute present in 100 gm of solution.
CONCENTRATION TERMS
• Molarity (M) : No. of moles of solute present in 1000 ml of solution.
moles of solute
molarity (M) =
volume of solution (lit)
m.moles of solute
M=
volume of solution(ml)
MOLALITY (m)
No. of moles of solute present in 1000 gm of solvent
moles of solute m.moles of solute
m= m=
wt.of solvent in kg wt.of solvent in gm
NORMALITY (N)
No of gm equivalents of solute present in 1000 ml of solution
gm equivalents of solute m. equivalent of solute
N= =
volume of solution(lit) volume of solution in (ml)
FORMALITY (f)
The formality is the no. of gm -formula weights of the ionic solute present in 1000 ml of solution.
wt in gm
f=
formula wt × volume of solution (lit)
MOLE FRACTION
The mole fraction of a perticular component in a solution is defined as the number of moles of that
component per mole of solution.
If a solution has nA mole A & nB mole of B.
nA
mole fraction of A (XA) = n + n
A B
nB
mole fraction of B (XB) = n + n
A B
XA + XB = 1
Mass of solute Mass of solute

• Parts per million (ppm) : =
Mass of solvent
× 106 ≅
Mass of solution
× 10 6
VOLUME STRENGTH OF H2O2

Strength of H2O2 is represented as 10V, 20V, 30V etc.
20V H2O2 means one litre of this sample of H2O2 on decomposition gives 20 It of O2 gas at S.T.P.
Decomposition of H2O2 is given as
1
H2O2 → H2O + O2
2
1
1 mole × 22.4 It O2 at S.T.P..
2
= 34 g = 11.2 It O2 at S.T.P.
• To obtain 11.2 litre O2 at S.T.P. at lest 34 gm H2O2 must be decomposed
34
• for 20 It O2, we should decompose atleast × 20 gm H2O2
112
.
34
∴ 1 It solution of H2O2 contains × 20 gm H2O2
112
.
34 20 M 34
∴ 1 It solution of H2O2 contains × equivalents of H2O2 (EH2O 2 = = = 17)
112
. 17 2 2
34 20 20
• Normality of H2O2 = × =
112
. 17 5.6
Volume, strength of H2 O 2
Normality of H2O2(N) =
5.6
NH2O 2 NH2O 2
∴ MH2O 2 = =
v. f 2
IInd Method :
1
H2O2 → H2O + O2
2
From law of equivalence
gm eq. of O2 = gm eq. of H2O2
20 20
gm eq. of O2 = moles × n factor of O2, = ×4 =
22.4 5.6
20
gm. eq. of H2O2 =
5.6
and the volume of H2O2 is 1 lit.
20
this means 1 lit of H2O2 have gm eq.
5.6
i.e. Normality
20
N=
5.6
NORMALITY OF H2O2
volume strength of H2 O 2
=
5.6
Volume, strength of H2O 2

• Molarity of H2O2(M) =
11.2
Strength (in g/) : Denoted by S
Strength = molarity × mol. wt.
= molarity × 34
strength = Normality × Eq. weight.
= Normality × 17
Ex.18 A bottole labeled with “12V H2O2” contain 700 ml solution. If a sdudent mix 300 ml water in it
what is the g/litre strenth & normality and volume strength o final solution.
12
Sol. N=
5.6
12
meq. of H2O2 = × 700
5.6
let the normality of H2O2 on dilution is N
meq. before dilution = meq. after dilution
12 12 7 15
.
N × 1000 = × 700 N= × = 1.5 M=
5.6 5.6 10 2
15
.
strength gm/lit = × 34 = 25.5
2
84
volume strength = N × 5.6 = = 8.4 V Ans.
10
Strength of Oleum
Oleum is SO3 dissolved in 100% H2SO4. Sometimes, oleum is reported as more then 100% by weight,
say y% (where y > 100). This means that (y – 100) grams of water, when added to 100 g of given
oleum sample, will combine with all the free SO3 in the oleum to give 100% sulphuric acid.
80( y – 100)
Hence weight % of free SO3 in oleum =
18
Ex.19 Calculate the percentage of free SO3 in an oleum (considered as a solution of SO3 in H2SO4) that
is labelled '109% H2SO4'.
Sol. '109% H2SO4' refers to the total mass of pure H2SO4, i.e., 109 g that will be formed when 100 g of oleum
is diluted by 9 g of H2O which (H2O) combines with all the free SO3 present in oleum to form H2SO4
H2O + SO3 → H2SO4
1 mole of H2O combines with 1 mole of SO3
or 18 g of H2O combines with 80 g of SO3
or 9 g of H2O combines with 40 g of SO3.
Thus, 100 g of oleum contains 40 g of SO3 or oleum contains 40% of free SO3.
Ex.20 A 62% by mass of an aqueous solution of acid has specific gravity 1.8. This solution is diluted
such that the specific gravity of solutin became 1.2. Find the % by wt of acid in new solutiuon.
mass
Sol. density =
volume
100 100
1.8 = ⇒ volume of solution =
volume of soln 18
.
Let x gm water is added in soluion
mass
then d=
volume
100 + x
12
. =
100
+x
18
.
100
12
. × × 12
. x = 100 + x
18
.
200
+ 12
. x = 100 + x
3
200 100
0.2 x = 100 – =
3 3
100 1000 500

x= = = = 166.67
3 × 0.2 6 3
mass of new solution = 100 + 166.67 = 266.67
266.67 gm solution contains 62 gm of acid
62
% by mass = × 100 = 23.24 %
266.67
RELATION SHIP BETWEEN MOLARITY, MOLALITY & DENSITY OF SOLUTION
Let the molarity of solution be 'M', molality be 'm' and the density of solution be d gm/m.
Molarity implies that there are M moles of solute in 1000 ml of solution wt of solution = density ×
volume
= 1000 d gm
wt of solute = MM1
where M1 is the molecular wt of solute
wt of solvent = (1000d – MM1) gm
(1000d – MM1) gm of solvent contains M moles of solute
M
1000 gm of solvent have = × 1000 mole = Molality
1000 d – MM1
1000 × M
no. of moles of solute present in 1000 gm of solvent = 1000d – MM = Molality
1
1 M1 
on simplyfying d = M  + 
 m 1000 
RELATION SHIP BETWEEN MOLALITY & MOLE FRACTION

consider a binary solution consisting of two components A (Solute) and B (Solvent).
Let xA & xB are the mole fraction of A & B respectively.
nA nB
xA = n + n , xb = n + n
A B A B
If molality of solution be m then
nA nA
m= × 1000 = × 1000
mass of solvent nB × MB
where MB is the molecular wt of the solvent B
x A 1000
m= ×
xB MB
mole fraction of A 1000

molality = mole fraction of B × M
B
mole fraction of solute 1000

m= ×
mole fraction of solvent molecular wt. of solvent
Ex.21 An aqueous solution is 1.33 molal in methanol. Determine the mole fraction of methanol & H2O
mole fraction of solute
Sol. molality = × 1000
mole fraction of solvent × mol.wt of solvent
xA
1.33 = × 1000
x B × MB
1.33 × 18 x A
=
1000 xB
23.94 x A
=
1000 xB
⇒ xA = 0.02394 xB
xA + xB = 1
⇒ 1.02394 xB = 1
1
xB = = 0.98
102394
.
xA = 0.02 Ans.
Second Method : Let wt of solvent = 1000 gm molality = 1.33

= moles of solute
moles of solute
mole fraction of solute =
moles of solute + moles of solvent
m 1.33
= =
1000 1.33 + 1000 / 18
m+
18
mole fraction of solute = 0.02
mole fraction of solvent = 1 – 0.02 = 0.98
Ex.22 The density of 3 M solution of sodium thiosulphate (Na2S2O3) is 1.25 g/mL. Calculate
(i) amount of sodium thiosulphate
(ii) mole fraction of sodium thiosulphate
(iii) molality of Na+ and S2O32– ions
Sol. (i) Let us consider one litre of sodium thiosulphate solution.
∴ wt. of the solution = density × volume (mL)
= 1.25 × 1000 = 1250 g.
wt. of Na2S2O3 present in 1 L of the solution
= molarity × mol. wt.
= 3 × 158 = 474 g. Ans.
474
wt. % of Na2S2O3 = × 100 = 37.92%
1250
(ii) Wt. of solute (Na2S2O3) = 474 g.
474
Moles of solute = = 3 Ans.
158
Wt. of solvent (H2O) = 1250 – 474 = 776 g
776
Moles of solvent = = 43.11
18
3
∴ mole fraction of Na2S2O3 = = 0.063
3 + 43.11
moles of Na2 S2 O 3 3
(iii) Molality of Na2S2O3 = × 1000 = × 1000 = 3.865
wt. of solvent in grams 776
∴ 1 mole of Na2S2O3 contains 2 moles of Na+ ions and 1 mole of S2O32– ions.
∴ molality of Na+ = 2 × 3.865 = 7.73 m
Molality of S2O32– = 3.865 m. Ans.
STOICHIOMETRY - II Page # 3
OXIDATION & REDUCTION

Oxidation Number :
It is the charge (real or imaginary) which an atom appears to have when it is in combination. It may be
a whole no. or fractional. An element may have different values of oxidation number depending. It
depends on nature of compound in which it is present. There are some operational rules to determine
oxidation number.
Oxidation :
Addition of oxygen, removal of hydrogen, addition of electro-negative element, removal of electroposi-
tive element, loss of electrons, increase in oxidation number (de – electronation).
Reduction :
Removal of oxygen, addition of hydrogen, removal of electronegative element, addition of electro +ve
element, gain of electrons, decrease in oxid. no. (electronation).
Redox Reactions :
A reaction in which oxidation & reduction occur simultaneously.
Oxidising Agents :
(oxidants, oxidisors). They oxidise others, themselves are reduced & gain electrons. eg. O2, O3, HNO3,
MnO2, H2O2, halogens, KMnO4, K2Cr2O7, KIO3, Cl(SO4)3, FeCl3, NaOCl, hydrogen ions.
[Atoms present in their higher oxidation state.]
Reducing Agents :
H2, molecular form is weak reducing agent but Nascent hydrogen is powerful. C, CO, H2S, SO2, SnCl2,
sodium thio Sulphate, Al, Na, CaH2, NaBH4, LiAlH4 . They reduce others, themselves get oxidised & lose
electrons. Also called reductants or reducers.
[Atoms present in their lower oxidation state.]
Both oxidising & Reducing Agents :

SO2, H2O2, O3, NO2, etc.
Balancing of Equations :
(i) Ion - electron method
(ii) Oxidation number method
[Concept involved that in any chemical reaction e– cannot be produced so no. of e– s in O.H. & R.H.
should be same]
Note : To predict the product of reaction remember :
(a) Free halogen on reduction gives halide ion (F2  F–)
(b) Alkali metals on oxidation give metallic ion with +1 oxidation state.
(c) In alkaline medium it is reduced to K2MnO4 but in strong alkaline or neutral medium it reduces of Mn+4
(d) In acid solution KMnO4 is reduced to Mn2+
(e) H2O2 on reduction gives water and on oxidation gives oxygen.
(f) Dichromate ion in acid solution is reduced to Cr3+.
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Page # 4 STOICHIOMETRY - II
Nature of Oxides Based on Oxidation Number :

Lowest oxidation state  Basic (MnO)
Intermediate oxidation state  Amphoteric (Mn3O4, MnO2)
Highest oxidation state  Acidic (Mn2O7)
Rules For Assigning Oxidation Number :
(i) Oxidation number of free elements or atoms is zero.
(ii) Oxidation number of allotropes is zero.
(iii) Oxidation number of atoms in homo-nuclear molecules is zero.
(iv) Oxidation number of mono-atomic ions is equal to the algebric charge on them.
(v) Oxidation number of F in compounds is –1
(vi) Oxidation number of H in its compounds is +1, except in metalhydrides where it is –1
(vii) Oxidation number of O is –2 in its compounds, but in F2 O it is +2 and in peroxides it is –1 and
–0.5 in KO2
(viii) Oxidation number of alkali metals in their compounds +1.
(ix) Oxidation number of alkaline earth metals in their compounds is +2.
(x) The sum of oxidation number of all the atoms in a molecule should be zero and in an ion equal to
its charge.
Average Oxidation Number : Find Oxidation Number of Fe in Fe3O4.

Fe3O4 is FeO. Fe2O3
O.N. of Fe in FeO is +2 ; O.N. of Fe in Fe2O3 is +3.
2  2 x( 3 ) 8
Therefore average O.N. of three Fe atoms = =+
3 3
EQUIVALENT CONCEPT
(A) Volumetric analysis :

This mainly involve titrations based chemistry. If can be divided into two major category.
(I) Non-redox system (II) Redox system
(I) Non-redox system

This involve following kind of titrations :
1. Acid-Base titrations 2. Back titration
3. Precipitation titration 4. Double indicator acid base titration
Titrimetric Method of Analysis :

A titrimetric method of analysis is based on chemical reaction such as.
aA + tT  Product.
Where 'a' molecules of "analysis", A reacts with t molecules of reagent T.
T is called Titrant normally taken in buret in form of solution of known concentration. The solution of
titrant is called "standard solution".
The addition of titrant is added till the amount of T, chemically equivalent to that of 'A' has been
added. It is said equivalent point of titration has been reached. In order to know when to stop addition
of titrant, a chemical substance is used called indicator, which respond to appearance of excess of
titrant by changing colour precisely at the equivalence point. The point in the titration where the
indicator changes colour is termed the 'end point'. It is possible that end point be as close as possible
to the equivalence point. The term titration refer's to process of measuring the volume of titrant
required to reach the end point.
Law of Chemical equivalence :

It states that in any chemical reaction the equivalents of all the reactants and products must be
same.
2A + 3B  4C
Eg. of A = Equivalents of 'B' = Equivalents of 'C'
Weight of ' A'

Equivalents of 'A' =
Equivalent weight of ' A'
or Equivalents of 'A' = no. of moles of 'A' × n-factor
A + B + C  product
If A & B do not react with each other but C react with both A & B then
gm eq. of A + gm eq. of B = gm eq. of C
or
meq. of A + meq. of B = meq. of C
n - factor calculation
n factor here we mean a conversion factor by which we divide molar mass of substance to get
equivalent mass and it depends on nature of substance which vary from one condition to another
condition. We can divide n-factor calculations in two category.
(1) In case of non-redox reaction.
(a) n factor of acid = basicity of the acid
Basicity : Number of replacible H+ ion.
Ex.1 n factor of HCl = 1
n factor of CH3COOH = 1
n factor of H2SO4 = 2
(b) n factor of base = acidity of the base
Acidity : Number of replaceble OH– ion.
Ex.2 n factor of NaOH = 1
n factor of Ca(OH)2 = 2
n factor of Al(OH)3 = 3
n factor of B(OH)3 = 1 (because it is a mono basic acid)
(c) n factor Salt : Total number of positive or negative charge.
Ex.3 n factor of NaCl = 1
n factor of Na2SO4 = 2
n factor of K2SO4.Al2(SO4)3.24H2O = 8
Ex.4 Find the n factor of H3PO4 in the following reaction.
H3PO4 + Ca(OH)2  CaHPO4 + 2H2O
Sol. Basicity of H3PO4 in the above reaction is 2
 the n factor of H3PO4 is 2
(2) In case of redox reaction.

(a) From oxidation number
n factor of oxidising or redusing agent = change in oxidation number per molecule.
 consider a salt AxBy in which the O.S. of A is +c. It changes to a compound AdE in which the O.S.
of A is +f. Here we are assuming that B does not undergo any change in O.S.
Ax+c By  Ad+f E (obviously AxBy must have reacted with some other substance to produce the product
AdE. That means other substance has the atom E in it.)
The 'n' factor is = |xc – xf |.
Ex.5 Find the n factor of KMnO4 in different medium.

Sol. (i) In acidic mediam
KMnO4  Mn+2
Change in oxidation number of Mn = +7 – 2 = 5
 the n factor of KMnO4 = 5 Ans.
(ii) basic medium
KMnO4  K2MnO4
n factor of KMnO4 = +7 – 6 = 1 Ans.
(iii) neutral medium
KMnO4  MnO2
n factor of KMnO4 = +7 – 4 = 3 Ans.
Ex.6 Find the n factor of Na2S2O3 in the following reactions.

(a) Na2S2O3 + I2  NaI + Na2S4O6
sodium thio sodium tetra
sulphate thionate
(b) Na2S2O3 + I2  NaI + Na2SO4
Sol. (a) Change in oxidation number of sulphur = |+2 – 2.5| = 0.5
Change in oxidation number per molecule = 0.5 × 2
 n factor of Na2S2O3 = 1
(b) Change in oxidation number of sulphur = |2 – 6| = 4
Change in oxidation number per molecule = 4 × 2
 n factor of Na2S2O3 = 8
 Consider the salt AxBy to undergo a reaction so that the element A undergoes a change in O.S. but
is present in more than one product with the same O.S. i.e. A x cBy  A a f B y  A g f H (the superscripts
denote the oxidation state of the respective elements).
 n = |xc – xf|
 Salts that react in such a way that more than one type of atom in the salt undergoes O.S. change.
A x cBy  A a f E  JxB –1
In this case both A and B are changing their O.S.'s and both of them are either getting oxidised or
reduced. In such a case n factor of the compound is the sum of the individual n factors of A and B. i.e.
|xc – xf | + | –xC – (–yi)|. Then n factor of A can be undersood which is |xc – xf|. The n factor of B is
|–xc – (–yi)|
Disproportionation Reactions :
A redox reaction in which a same element present in a particular compound in a definite oxidation state
is oxidized as well as reduced simultaneously is a disporportionation reactions.
n factor = 2 = n2
0 1 –1
Cl2 (g)  2OH – (aq)  C l O – (aq)  C l – (aq)  H2O( )
Ex.7
n factor = 2 = n1
n factor of overall reaction = n1 × n2 / n1 + n2
(b) From ion electron method :

n factor = total number of electrons transfered per mole of the reactant
Ex.8 MnO4– + 8H+ + 5e  Mn+2 + 4 H2O
n factor of KMnO4 = 5
Acid-Base titration.
To find out strength or concentration of unknown acid or base it is titrated against base or acid of
known strength. At the equivalence point we can know amount of acid or base used and then with the
help of law of equivalents we can find strength of unknown.
Meq of acid at equivalence point = Meq of base at equivalence point
Ex.9 One litre solution of alkali (NaOH) is prepared by dissolving impure solid of alkali which contain 5%
Na2CO3 and 8% CaCO3 and 10% NaCl. A 10 ml portion of this solution required 9.8 mL of a 0.5 M H2SO4
solution for neutralization. Calculate weight of alkali dissolved initially.
gm eq. of Na2CO3 + gm eq. of CaCO3 + gm eq. of NaOH = gm eq. of H2SO4
5x 1 8x 1 77 x 1
Sol.       0.98 x = 45 g Ans.
100 53 100 50 100 40
Back titration
Back titration is used in volumetric analysis to find out excess of reagent added by titrating it with
suitable reagent. it is also used to find out percentage purity of sample. For example in acid-base
titration suppose we have added excess base in acid mixture. To find excess base we can titrate the
solution with another acid of known strength.
Ex.10 20 g. of a sample of Ba(OH)2 is dissolved in 50 ml. Of 0.1 N HCl solution. The excess of HCl was titrated
with 0.1 N NaOH. The volume of NaOH used was 20 cc. Calculate the percentage of Ba(OH)2 in the
sample.
Sol. Milli eq. of HCl initially = 50 × 0.1 = 5
Milli eq. of NaOH consumed = Milli eq. of HCl in excess = 20 × 0.1 = 2
Milli eq. of HCl consumed = Milli eq. of Ba(OH)2 = 5 – 2 = 3
 eq. of Ba(OH)2 = 3/1000 = 3 × 10–3
Mass of Ba(OH)2 = 3 × 10–3 × (171/2) = 0.2565 g.
% Ba(OH)2 = (0.2565/20) × 100 = 1.28 % Ans.
Ex.11 4.0 g of monobasic, saturated carboxylic acid is dissolved in 100 mL water and its 10 mL portion
required 8.0 mL 0.27 M NaOH to reach the equivalence point. In an another experiment, 5.0 g of the
same acid is burnt completely and CO2 produced is absorbed completely in 500 mL of a 2.0 N NaOH
solution. A 10 mL portion of the resulting solution is treated with excess of BaCl2 to precipitate all
carbonate and finally titrated with 0.5 N H2SO4 solution. Determine the volume of the acid solution that
would be required to make this solution neutral.
Sol. meq. of NaOH = 8 × 0.27 = meq. of acid for 10 ml of acid solution
8  0.27  100 4
meq. of acid for 100 ml of solution = =  10 3
10 M
4
M (acid) = × 1000 = 185.2
8  0.27  10
Formula of acid. = CnH2nO2
 M = 14n + 32 = 185.2
 n = 11
5 55
Now 5g acid will produce × 11 = mol CO2 after complete combustion.
185 .2 185 .2
2NaOH + CO2  Na2CO3 + H2O
Total mass of NaOH available = 500 × 2 × 10–3 = 1.0 mole
2  55 76
Moles of NaOH left unreacted = 1 – = in 500 mL
185 .2 185 .2
 Molarity of NaOH after precipitation of Na2CO3 = 0.812
Therefore, 0.812 × 10 = 0.5 × V
 V = 16.24 mL Ans.
Precipitation titration :
In ionic reaction we can know strength of unknown solution of salt by titrating it against a reagent
with which it can form precipitate. For example NaCl strength can be known by titrating it against
AgNO3 solution with which it form white ppt. of AgCl.
So meq. of NaCl at equivalence point = meq. of AgNO3 used = meq. of AgCl formed
Ex.12 A complex of cobalt with ammonia is analyzed for determining its formula, by titrating it against a
standardized acid as follows :
Co(NH3)x Cl3(aq) + HCl  NH4+ (aq) + Co3+ (aq) + Cl–(aq)
A 1.58 g complex required 23.63 mL 1.5 M HCl to reach the equivalence point. Determine formula. If the
reaction mixture at equivalence point is trated with excess of AgNO3 solution, what mass of AgCl will
precipitate out ?
Sol. The balanced chemical reaction is :
Co(NH3)xCl3 + xHCl  xNH4+ + Co3+ + (x + 3) Cl–
158
. 158
. x 158
. ( x  3)
165.5  17 x 165.5  17 x 165.5  17 x
158
. x 23.63  15
.
  = moles of HCl
165.5  17 x 1000
 x=6
(x + 3)  1.58
moles of Cl = moles of AgCl =
165.5 + 17x
(x + 3)  1.58
wt. of AgCl =  143.5  7.62
165.5 + 17x
m(AgCl) = 0.053 × 143.5 = 7.62 g Ans.
CALCULATION OF AVAILABLE CHLORINE FROM A SAMPLE OF BLEACHING POWDER

The weight % of available Cl2 from the given sample of balaching powder on reaction with dil acids or
CO2 is called available chlorine.
CaOCl2 + H2SO4  CaSO4 + H2O + Cl2
CaOCl2 + 2HCl  CaCl2 + H2O + Cl2
CaOCl2 + 2CH3COOH Ca(CH3COO)2 + H2O + Cl2
CaOCl2 + CO2  CaCO3 + Cl2
Method of determination :
starch
Bleaching powder + CH3COOH + KI end point
Hypo
meq. of I2 = meq. of Cl2 = meq. of Hypo solution
3.55  x  V(mL)
% of Cl2 =
W (g)
where x = molarity of hypo solution

v = mL. of hypo solution used in titration.
Ex.13 10 gm sample of bleaching powder was dissolved into water to make the solution on litre. To this
solution 35 mL of 1.0 M Mohr salt solution was added containing enough H2SO4. After the reaction was
complete, the excess Mohr salt required 30 mL of 0.1 M KMnO4 for oxidation. The % of available Cl2
approximately is (mol wt = 71)
Sol.14 meq. of Mohr's salt = 35 × 1 × 1 = 35
meq. of KMnO4 = meq. of excess mohr salt = 30 × 0.1 × 5 = 15
meq. of Mohr salt reacted with bleaching powder = 35 – 15 = 20
meq. of Cl2 = 20
71
wt. of Cl2 = 20 × 10–3 × = 0.71 gm
2
0.71
% of Cl2 =  100 = 7.1 % Ans.
2
Double indicator acid-base titration :

In the acid-base titration the equivalence point is known with the help of indicator which changes its
colour at the end point. In the titration of polyacidic base or polybasic acid there are more than one
end point. One indicator is not able to give colour change at every end point. So to find out each end
point we have to use more than one indicator. For example in the titration of Na2CO3 against HCl there
are two end points.
Na2CO3 + HCl  NaHCO3 + NaCl

NaHCO3 + HCl  H2CO3 + NaCl
When we use phenolphthalein in the above titration it changes its colour at first end point when
NaHCO3 is formed and with it we can not know second end point. Similarly with methyl orange it
changes its colour at second end point only and we can not know first end point. it is because all
indicator changes colour on the basis of pH of medium. So in titration of NaHCO3, KHCO3 against acid
phenolphthalein can not be used.
Titration Indicator pH Range n factor
Na2CO3 Phenolphthalein 8.3 – 10 1

against acid
Na2CO3 Methyl orange 3.1 – 4.4 2
A sample contains NaOH, Na2CO3 & NaHCO3. This solution is titrated with HCl or H2SO4
(i) When Phenolphthalein (HPh) is used as indicator the reaction are given below.
Na2CO3 + HCl  NaHCO3 + NaCl
This is the Half neutralisation of Na2CO3
NaHCO3 + HCl  X
NaOH + HCl  NaCl + H2O
Hence
1
Meq. of HCl = meq of NaOH + meq. of Na2CO3
2
(ii) when methyl orange (MeOH) is used as indicator
Na2CO3 + 2HCl  2 NaCl + H2O + CO2
This is the complete neutralisation
NaHCO3 + HCl  NaCl + H2O + CO2
NaOH + HCl  NaCl + H2O
in this case
meq. of HCl = meq of NaOH + meq. of Na2CO3 + meq. of NaHCO3
(iii) If MeOH is added after the first end point obtained from HPh
NaHCO3 + NaHCO3 + HCl  NaCl + H2O + CO2
Produced original
meq. of HCl = meq. of NaHCO3 (produced) + meq. of NaHCO3 (original)
Note :
When we carry out dilution of solution, meq eq. milli mole or mole of substance does not change
because they represent amount of substance, however molar concentration may change.
Ex.15 A solution contains a mixture of Na2CO3 and NaOH. Using phenolphthalein as indicator 25 ml. of mixture
required 19.5 ml of 0.995 N HCl for the end point. With methyl orange. 25 ml of solution required 25 ml.
of the same. HCl for the end point. Calculate grams per litre of each substance in the mixture.
Sol. Let a & b are the meq. of Na2CO3 and NaOH respectively
when phenolphthale in is used as indicator
1
meq. of Na2CO3 + meq. of NaOH = meq of HCl
2
a
 b = 19.5 × 0.995
2
a
 b = 19.4 ...(1)
2
when MeOH is used as indicator
meq. of Na2CO3 + Meq. of NaOH = meq. of HCl
a + b = 25 × 0.995
a + b = 24.875 ...(2)
from (1) & (2)
a
= 5.475  a = 10.95
2
b = 24.875 – 10.95 = 13.925
10.95 106
wt of Na2CO3 /lit =  10 –3   1000 = 23.2 gm/lit
25 2
wt of NaOH/lit = b × 10–3 × 84/25 × 1000 = 22.28 gm/lit Ans.
Ex.16 2.5 g of a mixture containing CaCO3, Ca(HCO3)2 and NaCl was dissolved in 100 mL water and its 10 mL
portion required 10 mL 0.05 M H2SO4 solution to reach the phenolphthalein end point. An another 10 mL
portion of the same stock solution required 32.35 mL of the same acid solution to reach the methyl
orange end point. Determine mass percentage of CaCO3 and Ca(HCO3)2 in the original mixture.
Sol. Let a and b are the meq. of CaCO3 and Ca(HCO3)2 respectively.
When HPh is used is indicater then only CaCO3 will react with H2SO4
meq. of H2SO4 = 1/2 meq. of CaCO3
10  0.05  100  2
meq. of H2SO4 = = 10
10
meq. of CaCO3 = 20
When MeOH is used as indicator
then meq. of CaCO3 + meq. of Ca(HCO3)2 = meq. of H2SO4
32.35  0.05  2
a+b=  100
10
a + b = 32.35
b = 12.5
wt. of CaCO3 = a × 10–3 × 100/2
= 1 gm
wt. of Ca(HCO3)2 = b × 10–3 × 162/2 = 1 gm
1
% of CaCO3 =  100 = 40%
2.5
1
% of Ca(HCO3)2 =  100 = 40%
2.5
Ex.17 6.4 g of a pure monobasic organic acid is burnt completely in excess of oxygen and CO2 evolved is
absorbed completely in one litre of an aqueous solution of NaOH. A 10 mL portion of this solution
required 14.5 mL of a normal HCl solution to reach the phenolphthalein end point. An another 10 mL
portion of the same solution required 18 mL of the same HCl solution to reach the methyl organe end
point. If the organic acid contains 25% oxygen by weight, deduce the empirical formula of this acid and
strength of original NaOH solution.
Sol. CxHyO2 + O2  xCO2 2NaOH

   xNa2CO3
6.4 6.4 x 6.4 x

M M M
Let 100 ml of solution contains a meq. of NaOH & b meq. of Na2CO3

when HPh is used as indicator then
meq. of NaOH + 1/2 meq. of Na2CO3 = Meq. of HCl
14.5  1
=  1000 = 40%
10
a + b/2 = 14.5 × 100

a + b/2 = 14.5 × 100 = 1450 ...(1)
when MeOH is used as indicator
meq. of NaOH + meq. of Na2CO3 = Meq. of HCl
1
a + b = 18 × 1 × × 100 = 1800 ...(2)
10
from (1) & (2)

b = 700
a = 100
b  10 –3 6.4
moles of Na2CO3 = = x
2 M
700  10 –3 x
 = 6.4 ...(1)
2 M
wt % of = 25
25
M  32  M = 128
100
700  10 –3 x
from (1) = 6.4 ×
2 128
700  10 –3 128
× =x=7
2 6.4
formula C7H12O2
1800
Molarity of NaOH = = 1.8 M Ans.
1000
Ex.18 A solution contains Na2CO3 and NaHCO3. 10 mL of the solution requires 2.5 mL of 0.1 M H2SO4 for
neutralisation using phenolphthalein as an indicator. Methyl organge is added when a further 2.5 mL of
0.2 M H2SO4 was required. Calculate the amount of Na2CO3 and NaHCO3 in one litre of the solution.
Sol. Na2CO3 NaHCO3
Let a meq. b meq.
when HPh is used as indicator
1
then meq. of Na2Cl3 = meq. of H2SO4
2
a
= 2.5 × 0.1 × 2  a=1
2
MeOH is added after the forst eard point the solution

Contains NaHCO3 original & NaHCO3 produced.
meq. of H2SO4 = meq. of NaHCO3 original + meq. of NaHCO3 produced
2.5 × 0.2 × 2 = b + 1/2 meq. of Na2CO3
= b + a/2
b + a/2 = 1
b = 1 – 0.5 = 0.5
106 1
wt of Na2CO3/lit = a × 10–3 × × × 1000
2 10
53
=1× = 5.3 gm
10
1
wt of NaHCO3/lit = b × 10–3 ×84 × × 1000 = 4.2 gm Ans.
10
THE ATLAS
STOICHIOMETRY
1. Mole-definition and meaning

2. Gram - atomic mass
3. Gram - molecular weight
4. Relative atomic mass
5. Isotopic abundance
6. Average atomic mass
CHEMICAL CALCULATION USING

MOLE CONCEPT BASED ON
BALANCED CHEMICAL REACTION
THEORETICAL EXPERIMENTAL
STOICHIOMETRY STOICHIOMETRY
ANALYSIS
1. Stoichiometric proportion
2. Non stoichiometric proportion
3. Concept of limiting reagent Titrimetric
Gravimetric Method Gas Analysis
Reaction in Reaction
aqueous solution involving
1. Acid Base gaseous
2. Redox reactants and
3. Precipitation products
4. Complex titrimetric
GLOSSARY
Aliquot . A portion of the whole, usually a simple fraction. A portion of a sample withdraw from a
volumetric flask with a pipet is called as aliquot.
Analytical concentration, The total number of moles per litre of a solute regardless of any reactions
that might occur when the solute dissolves. Used synonymously with formality.
Equivalent. The amount of a substance which furnishes or reacts with 1 mole of H+ (acid-base), 1 mol
of electrons (redox), or 1 mol of a univalent cation (precipitation and complex formation).
Equivalent weight. The weight in grams of one equivalent of a substance.
Equivalence point. The point in a titration where the number of equivalents of titrant is the same as
the number of equivalents of analyte.
End point. The point in a titration where an indicator changes color.
Formula weight. The number of formula weights of all the atoms in the chemical formula of a sub-
stance.
Formality. The number formula weights of solute per litre of solution; synonymous with analytical
concentration.
Indicator. A chemical substance which exhibits different colors in the presence of excess analyte or
titrant.
Normality. The number of equivalents of solute per litre of solution.
Primary standard. A substance available in a pure form or state of known purity which is used in
standardizing a solution.
Standardization. The process by which the concentration of a solution is accurately ascertained.
Standard solution. A solution whose concentration has been accurately determined.
Titrant. The reagent (a standard solution) which is added from a buret to react with the analyte.
Page # 22 ATOMIC STRUCTURE
The Uncertainty Principle
The position and momentum of a particle cannot be simultaneously measured with arbitrarily high
precision. There is a minimum for the product of the uncertainties of these two measurements. There
is likewise a minimum for the product of the uncertainties of the energy and time.
h
∆x∆p ≥
4π
h
∆E∆t ≥
4π
The uncertainty principle contains implications about the energy that would be required to contain a
particle within a given volume. The energy required to contain particles comes from the fundamental
forces, and in particular the electromagnetic force provides the attraction necessary to contain
electrons within the atom, and the strong nuclear force provides the attraction necessary to contain
particles within the nucleus. But Planck's constant, appearing in the uncertainty principle, determines
the size of the confinement that can be produced by these forces. Another way of saying it is that the
strengths of the nuclear and electromagnetic forces along with the constraint embodied in the value of
Planck's constant determine the scales of the atom and the nucleus.
Q. Does uncertainty principle violates energy conservation principle?
(6) Wave mechanical model of Atom

Schordinger equation :
The Schrodinger equation plays the role of Newton's laws and conservation of energy in classical
mechanics - i.e., it predicts the future behavior of a dynamic system. It is a wave equation in terms of
the wave function which predicts analytically and precisely the probability of events or outcome. The
detailed outcome is not strictly determined, but given a large number of events, the Schrodinger
equation will predict the distribution of results.
Hψ = EΨ
The kinetic and potential energies are transformed into the Hamiltonian which acts upon the wave
function to generate the evolution of the wave function in time and space. The Schrodinger equation
gives the quantized energies of the system and gives the form of the wave function so that other
properties may be calculated.
8π2m
∇2 ψ + (E − U)ψ = 0
h2
ATOMIC STRUCTURE Page # 23
Where , E = total energy of electron
U = potential energy of electron
∂2 ∂2 ∂2
∇ =
2 Laplacian operator = + +
∂x2 ∂y2 ∂z2
and ψ = wave function of electron = amplitude of matter wave.

Schordinger equation can be solved completely for hydrogen atom and hydrogen-like species like He+,
Li2+.
The Schordinger equation can also be written in terms of spherical polar coordinates (r, θ, φ) in addition
to Cartesian coordinate x, y, z.
Since, H-atom posses spherical symmetry, ∴ it is easier to solve schordinger equation if it is represented
in polar coordinate.
z
z = r cos θ
r cos θ
x = r sin θ . cos φ
y = r sin θ sin φ
θ r
y
φ r si
nθ
x
x 2 + y 2 + z 2 = R2
When schordinger equation in polar coordinate is solved for H-atom then the solution obtained can be
expressed as
ψ = ψr .ψ θ.φ
ψ r represents radial wave function which depends on n, .
ψ θ . φ → Angular wave function which depends on m, .
ψ (Psi) : [Wave function or Amplitude of Electron Wave]
It is also known as atomic orbitals. It is a mathematical function whose value depends on coordinates
of electron in an atom. It may be +ve or –ve depending upon value of coordinates and it has no
physical significance.
ψ 2 [Probability Density] :
According to electromagnetic wave theory, intensity of light is proportional to square of amplitude. In
the same way ψ 2 gives an idea of intensity of electron wave i.e. probability of finding electron at that
point.
Q. What is the significance of ψ 2 (x).dx ?
Q. What is the significance of ψ 2 .dV ?
ORBITALS
Orbitals are defined as that region or zone in the space where probability of finding electrons is
possible (more than 90%). In an atom large no. of permissible orbitals are present.
These orbitals are designated by a set of 3 quantum number (n, , m) which arise as a natural
consequence in the solution of Schordinger equation i.e. the values of 3 quantum numbers are restricted
by the solution of Schordinger equation.
The Postulates of Quantum Mechanics

1. Associated with any particle moving in a conservative field of force is a wave function which
determines everything that can be known about the system.
2. With every physical observable q there is associated an operator Q, which when operating upon the
wave function associated with a definite value of that observable will yield that value times the wave
function.
3. Any operator Q associated with a physically measurable property q will be Hermitian.
4. The set of eigen functions of operator Q will form a complete set of linearly independent functions.
5. For a system described by a given wave function, the expectation value of any property q can be
found by performing the expectation value integral with respect to that wave function.
6. The time evolution of the wave function is given by the time dependent Schrodinger equation.
The Wave function Postulate
It is one of the postulates of quantum mechanics that for a physical system consisting of a particle
there is an associated wave function. This wave function determines everything that can be known
about the system. The wave function is assumed here to be a single-valued function of position and
time, since that is sufficient to guarantee an unambiguous value of probability of finding the particle at
a particular position and time. The wave function may be a complex function, since it is its product
with its complex conjugate which specifies the real physical probability of finding the particle in a
particular state.
ψ(x, t) = single-valued probability amplitude at (x, t)
ψ * (x, t)ψ(x, t) = probability of finding particle at x at time t provided the wave function is normalized.
Q. How can a continuous description such as wave lead to discrete energy levels ?
Constraints on Wave function
In order to represent a physically observable system, the wave function must satisfy certain constraints:
1. Must be a solution of the Schrodinger equation.
2. Must be normalizable. This implies that the wave function approaches zero as x approaches infinity.
3. Must be a continuous function of x.
4. The slope of the function in x must be continuous.
∂ψ(x)
Specifically must be continuous.
∂x
These constraints are applied to the boundary conditions on the solutions, and in the process help
determine the energy eigenvalues.
Few Radial Functions Rn,

3 /2
 1 
n = 1, = 0 R10(r) = 2   e −r / a0
 a0 
3 /2
1  1   r  −r / 2a0
n = 2, = 0 R20(r) =   2 − e
   a0 
8  a0  
3/2
1  1  r −r / 2a0
n = 2, = 1 R10(r) =   e
 
24  a0  a0
3 /2 2
 1 2    − r / 3a
n = 3, = 0 R10(r) =    27 − 18 r + 2 r e 0
   a20 
81 3  a0   a0 
3 /2
2  1   r
6 r 2  − r / 3a0
n = 3, = 1 R10(r) =  
  − 2 2 e
9 6  a0   a0 a0 

3 /2
 1  4 r2
n = 3, = 2 R10(r) =  
  e −r / 3a0
81 30  a0  a20
Ψ (r, θ , φ) for Hydrogen Atom
3 /2
1  1 
n = 1, = 0, m = 0 ψ100 (r) =  
  e −r / a0
π  a0 
3 /2
 1 
1  r  − r / 2a0
n = 2, = 0, m = 0 ψ 200 (r) =   2 − e
   
4 2π  a0   a 0 
3 /2
1  1  r −r / 2a0
n = 2, = 1, m = 0 ψ 210 (r, θ, φ) =   e cos θ
 
4 2π  a0  a0
3 /2
1  1  r −r / 2a0
n = 2, = 1, m = ±1 ψ 21 ±1 (r, θ, φ) =  
  e sin θ e ± iφ
8 π  a0  a0
3 /2 2 
 1
1  
n = 3, = 0, m = 0 ψ 300 (r) =    27 − 18 r + 2 r e −r / 3a0
   a20 
81 3π  a0   a0
1/2 3/2
1 2  1   r
6 r 2  − r / 3a0
n = 3, = 1, m = 0 ψ 310 (r, θ, φ) =     e cos θ
81  π  a   a a20 
 0   0
3 /2
 1
1   r r 2  −r / 3a0
n = 3, = 1, m = ±1 ψ 31 ±1(r, θ, φ) = 



6 + e sin θe ± iφ
81 π  a0  a0 a2 
  0 
3 /2
r2
n = 3, = 2, m = 0 ψ 320 (r, θ, φ) =
1  1 
 
  a20
(
e −r / 3a0 3 cos2 θ − 1 )
81 6π  a0 
3 /2
 1 
1 r2
n = 3, = 2, m = ±1 ψ 32 ±1(r, θ, φ) =  
  e − r / 3a0 sin θ cos θ e ± iφ
81 π  a0  a20
3 /2
1 1  r2
n = 3, = 2, m = ±2 ψ 32 ± 2 (r, θ, φ) =  
  e − r / 3a0 sin2 θ e ± 2iφ
162 π  a0  a20
Real Wave Functions For Hydrogen Atom
3 /2
1  1  r −r / 2a0
ψ 2p x (r, θ, φ) =   e sin θ cos φ
 
4 2π  a0  a0
3/2
1  1  r −r / 2a0
ψ 2p y (r, θ, φ) =   e sin θ sin φ
 
4 2π  a0  a0
3 /2
 1 
1 r − r / 2a0
ψ 2pz (r, θ, φ) =   e cos θ
 
4 2π  a0  a0
3 /2
2  1   r
6 r 2  −r / 3a0
ψ 3px (r, θ, φ) =  
a  − 2 e sin θ cos φ
81 π  a a0 
 0  0
3/2
2  1   r
6 r 2  − r / 3a0
ψ 3py (r, θ, φ) =  
a  − 2 e sin θ sin φ
81 π  a a0 
 0  0
3 /2
2  1   r
6 r 2  − r / 3a0
ψ 3pz (r, θ, φ) =  
a  − 2 e cos θ
81 π  a a0 
 0  0
3/2
ψ 3d 2 (r, θ, φ) =
z
1  1 
 
 
81 6π  a0 
r2
a20
(
e −r / 3a0 3 cos2 θ − 1 )
3 /2
2  1  r2
ψ 3dxz (r, θ, φ) =  
  e −r / 3a0 sin θ cos θ cos φ
81 π  a0  a20
3 /2
2  1  r2
ψ 3dyz (r, θ, φ) =  
  e − r / 3a0 sin θ cos θ sin φ
81 π  a0  a20
3/2
2  1  r2
ψ 3d 2 (r, θ, φ) =   e −r / 3a0 sin2 θ cos 2φ
x −y 2
81 2π a0  a02
3/2
1  1  r2
ψ 3dxy (r, θ, φ) =   e − r / 3a0 sin2 θ sin 2φ
81 2π  a0  a20
QUANTUM NUMBERS
In the solution to the Schrodinger equation for the hydrogen atom, three quantum numbers arise
from the space geometry of the solution and a fourth arises from electron spin. No two electrons
can have an identical set of quantum numbers according to the Pauli exclusion principle , so the
quantum numbers set limits on the number of electrons which can occupy a given state and there-
fore give insight into the building up of the periodic table of the elements.
(1) Principal Quantum No. (n) :

The principal quantum number or total quantum number n arises from the solution of the radial part of
the Schrodinger equation for the hydrogen atom. The bound state energies of the electron in the
hydrogen atom are given by
−13.6eV
En =
n2
(i) Permissible values of n : all integers from 1 to ∞ (infinity)

(ii) This no. identifies shell in an atom.
(iii) It gives an idea of average distance ‘R’ [size of any orbital from the nucleus higher the value of, n,
higher will be the average distance and hence greater will be the size].
(iv) It gives idea of energy of electron upto some extent. Higher the value of n, higher will be the
energy (if ‘’ is constant).
for example order of energy 4s > 3s > 2s > 1s
(v) It gives value of total no. of orbitals present in any shell and that is equal to n2.
(vi) It gives value of total no. of electrons which may he present in the given shell = 2n2.
nh
(vii) It gives value of angular momentum of electron i.e.
2π
(viii) It give variation of radial probability distribution.
(2) Azimuthal Quantum No. or Angular momentum Quantum no. () :

Permissible values of l is 0 to (n -1). i.e. value of is restricted by n.
n = 1, =0
n = 2, = 0, 1. ; i.e. 2 values of .
n = 3, = 0, 1, 2. i.e. 3 values of .
No. of values of ‘’ is equal to ‘n’ principal quantum number
It identify sub shell in an atom

The value of ‘’ gives name of sub-shell and shape of orbital.
Notation Name Shape

o s Sharp Spherical
1 p Principal dumbell shaped
2 d diffuse double dumbell
3 f fundamental complex
(3) magnetic quantum number (m)
The direct implication of this quantum number is that the z-component of angular momentum is
quantized according to L z = mlh / 2π
It is called the magnetic quantum number because the application of an external magnetic field causes
a splitting of spectral lines called the Zeeman effect. The different orientations of orbital angular
momentum represented by the magnetic quantum number can be visualized in terms of a vector model.
(4) Spin quantum number (s)

An electron, besides charge and mass, has also spin angular momentum commonly called spin. The
spin angular momentum of the electron is constant and cannot be changed.
An electron spin s = 1/2 is an intrinsic property of electrons. Electrons have intrinsic angular momen-
tum characterized by quantum number 1/2. In the pattern of other quantized angular momenta, this
gives total angular momentum
The resulting fine structure which is observed corresponds to two possibilities for the z-component
of the angular momentum.
This causes an energy splitting because of the magnetic moment of the electron
Orbitals diagram
Filling of Orbitals in atoms :

The filling of electrons into the orbitals of different atoms take place on the basic of 3 principles :
AUFBAU's PRINCIPLE
The electrons are added progressively to Various orbitals in the order of increasing energy, starting
with the orbital of lowest energy, generally.
ENERGY OF ORBITALS
(i) Hydrogen atom : In case of hydrogen atom, energy of
orbital is mainly determined by principle quantum number.
∴ n↑, E ↑
For H atom
1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p
(ii) Multielectronic atoms : In case of multielectronic atoms,

energy of orbitals depends upon both n and and hence
energy of orbitals is compared on the basis of (n + ) rules 1s
generally 2s 2p
⇒ n + rule : 3s 3p 3d
(iii) As the value (n + ) increases the total energy of orbitals 4s 4p 4d 4f
also increases. 5s 5p 5d 5f
(iv) If value of (n + ) is same or different orbital then orbital 6s 6p 6d 6f
with lower value of n, have lower energy. 7s 7p
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s
PAULI'S EXCLUSIONS PRINCIPLE

The principle states that no two electrons in an atom can have same set of all 4 quantum no.
Therefore spin quantum No. have only two values therefore it can also be commented that orbital can
have maximum two electrons with opposite spin.
HUND'S RULE OF MAXIMUM MULTIPLICITY

While filing the orbitals of same energy (i.e. orbitals of same subshell) pairing of electron start only
when each orbital have got 1 electron that too with same spin or parallel spin.
Multiplicity is expressed as 2|s| + 1 where s represent total spin.
1 1 1 1
s=+ – + =+ 2|s| + 1 = 2
2 2 2 2
1 1 1 1
s=+ + – =+ , 2|s| + 1 = 2
2 2 2 2
1 1 1 3 3
s=+ + + =+ ,2 + 1 = 4 (It has maximum multiplicity)
2 2 2 2 2
Q. Total spin resulting from d7 configuration ?
ELECTRONIC CONFIGURATION OF ATOM

The distribution of electrons of an atom in its various shell, sub shells and orbitals is known as electron
configuration.
Valence shell or outer most shell → nth shell
Penultimate shell-Inner to outermost shell → (n –1) shell
Anti Penultimate shell → (n – 2) shell
Electronic configuration can be expressed in the following ways :
( i ) O r b i t a l n o t a t i o n m e t h o d : n x
Li → 3 → 1s2 2s1
(ii) Orbital diagram method :
Li → 3 →
1s 2s
(iii) Condensed form :

[He] 2s1
H → 1 → 1s1 →
1s
He → 2 → 1s 2 →
1s
Li → 3 → 1s 2 2s1 →
1s 2s
Be → 4 → 1s 2 2s 2 →
1s 2s
B → 5 → 1s 2 2s 2 2 p1 →
1s 2s 2p
C → 6 → 1s 2 2s 2 2 p 2 →
1s 2s 2p
N → 7 → 1s 2 2s 2 2 p 3 →
1s 2s 2p
• Electronic Configuration of ions :

Al [Ne]3s2 3p1,
A +1 → [Ne ]3s2 ,
A 3+ → [ Ne ]
Similarly in case of transition elements electrons are removed from nth shell for e.g. 4th shell in case of
3d series.
Sc → [Ar] 4s2 3d1 ,
Sc +2 → [Ar]3d1 4s0
Cl : [Ne]3s2.3p5
Cl– : [Ne]3s2.3p6
Exceptional configuration
Expected confi. Cr − 24 → [Ar] 4s2 3d4
Observed confi. Cr − 24 → [Ar] 4s1 3d5
Expected confi. Cu − 29 → [Ar] 4s2 3d9
Observed confi. Cu − 29 → [Ar] 4s1 3d10

Above exceptional configuration can be explained on the basis of following factor.
(i) Symmetrical Electronic Configuration :
It is well known fact that symmetry leads to stability, ∴ orbitals of a sub shell having half-filled or full-
filled configuration (i.e. symmetrical distribution of electrons) are relatively more stable. This effect is
dominating in d and f subshell.
∴ d5, d10, f7, f14 configurations are relatively more stable.
(ii) Exchange Energy :

It is assumed that electrons in de-generate orbitals, do not remain confined to a particular orbital
rather it keep on exchanging its position with electron having same spin and same energy (electrons
present in orbitals having same energy). Energy is released in this process known as exchange energy
which imparts stability to the atom. More the number of exchanges, more will be the energy released,
more the energy released stability will be more.
Cr → 24
n(n − 1)
[ Ar ] 4S 2 3d4 →3+2+1=6
2
[ Ar ] 4S1 3d5 when n represents no. of
electron having same spin.
The relative value of exchange energy + depairing energy and transger energy
( energy relased [ 4S → 3 d]
during depairing)
decides the final configuration. For example, if magnitude of

Dep. energy + Ex. energy > transfer. energy as in cases of Cu and Cr then configuration is
Cr − 24 → [ Ar ] 4 s1 3d5
Cu − 29 → [ Ar ] 4 s1 3d10 respectively
In case of carbon magnitude of transfer energy > dep. energy + exch. energy and
∴ configuration of carbon is
1s 2 2s 2 2p 2
µ) : It is the measure of the magnetic nature of substance

Magnetic moment (µ
µ = n (n + 2) B.M. where n is no. of unpaired electrons.
When µ = 0, then there is no unpaired electron in the species and it is known as diamagnetic specie.
These species are repelled by magnetic field.
When µ ≠ 0 , for paramagnetic species. These species have unpaired electrons and are weakly attracted
by the magnetic field.
Calculate magnetic moment of these species
(i) Cr (ii) N (iii) Cl (iv) Ar
(i) Cr : No. of unpaired electrons = 6.
= 6( 6 + 2) = 48 BM
Generally species having unpaired electrons are coloured or impart colour to the flame. Species having
unpaired electrons can be easily excited by the wavelengths corresponding to visible lights and hence
they emit radiations having characteristic colour.
(A) Radial wave function (R)

In all cases R approaches zero as r approaches infinity. One finds that there is a node in the 2s radial
function. In general, it has been found that ns-orbitals have (n–1) nodes, np-orbitals have (n–2)
nodes etc.
The importance of these plots lies in the fact that they give information about how the radial wave
function changes with distance r and about the presence of nodes where the change of sign of R
occurs.
1s 2s 2p
R
R
R
r r r
(B) Radial Probability density (R2)

The square of the radial wave function R2 for an orbital gives the radial density. The radial density gives
the probability density of finding the electron at a point along a particular radius line. To get such a
variation, the simplest procedure is to plot R2 against r. These plots give useful information about
probability density or relative electron density at a point as a function of radius. It may be noted that
while for s-orbitals the maximum electron density is at the nucleus. all other orbitals have zero electron
density at the nucleus.
1s 2s 2p
r r r
(C) Radial probability functions 4πr2R2

The radial density R2 for an orbital, as discussed above, gives the probability density of finding the
electron at a point at a distance r from the nucleus. Since the atoms have spherical symmetry, it is
more useful to discuss the probability of finding the electron in a spherical shell between the spheres of
radius (r + dr) and r. The volume of the shell is equal to 4/3π(r + dr)3–4/3πr3 = 4πr2dr.
This probability which is independent of direction is called radial probability and is equal to 4πr2drR2.
Radial probability function (4πr2drR2) gives the probability of finding the electron at a distance
r from the nucleus regardless of direction.
1s 2s 2p
r r r
The radial probability distribution curves obtained by plotting radial probability functions versus distance
r from the nucleus for 1s, 2s and 2p orbitals are shown in fig.
Hydrogen 1s Radial Probability
Hydrogen 3s Radial Probability
Hydrogen 2p Radial Probability
Hydrogen 3p Radial Probability
Hydrogen 3d Radial Probability
Angular wave Function ΘΦ.

The angular wave function ' Θ Φ ' depends only on the quantum number and ml and is independent of
the principal quantum number n for a given type of orbital. It therefore means that all s orbitals will
have same angular wave function.
(A) Angular Wave Function, ' Θ Φ '

For an s-orbital, the angular part is independent or angle and is, therefore, of constant value. Hence
this graph is circular or, more properly, in three dimensions i.e., spherical. For the pz orbital, we get two
tangent spheres. The px and py orbitals are identical in shape but are oriented along the x and y axes
respectively. The angular, wave function plots for d and f-orbitals are four lobed and six-lobed respectively.
It is necessary to keep in mind that in the angular wave function plots, the distance from the center is
proportional to the numerical values of ' Θ Φ ' in that direction and is not the distance from the center
of the nucleus.
(B) Angular Wave Function, | Θ Φ |2

The angular probability density plots can be obtained by squaring the angular function plots shown in
fig. On squaring, different orbitals change in different ways. For an s orbital, the squaring causes no
change in shape since the function everywhere is the same: thus another sphere is obtained.
Plots of Total probability density: Shapes of Atomic Orbitals.
The problems associated with the representations of the variations of |Ψ|2 in space have been
circumvented by the following two approaches.
(a) Charge cloud diagrams
(b) Boundary surface diagrams
(A) Charge cloud diagrams
In this approach, the probability density |Ψ|2 is shown as a collection of dots such that the density of
dots in any region represents the electron probability density in that region. Fig. shows such plots for
some orbitals. These give some ideal about the shapes of the orbitals.
1s 3s
(B) Boundary surface digrams
In these diagrams, the shape of an orbital is defined as a surface of constant probability density that
encloses some large fraction (say 90 %) of the probability of finding the electron. The probability
density is |Ψ|2 . When |Ψ|2 is constant, so is |Ψ|. Hence |Ψ| is constant on the surface for an s orbital
(l = 0) has the shape of a spherical shell centered on the nucleus, fig. For each value of n, there is one
s orbital. As n increases, there are (n-1) concentric spherical shells like the successive layers in an
onion.
Fig. Boundary surface digrams for the 1 s orbital.
SHAPES OF ATOMIC ORBITALS
The spherical Polar Coordinates S
pX py pz
d z2 d dxy
x 2 − y2
dxz dyz f z3
fxyz f f
x ( y 2 −z 2 )
z( x 2 − y2 )
f f f
y( z2 − x 2 ) x3 y3
CHEMICAL BONDING Page # 3
CHEMICAL BONDING
KEY CONCEPTS
INTRODUCTION
A molecule will be formed if it is more stable and has a lower energy than the individual atom. Normally
only electrons in the outermost shell of an atom are involved in forming bonds, and in this process each
atom attains a stable electronic configuration of an inert gas.
Types of Bonds :
Atoms involved Bonding
(I) Metal + Nonmetal Ionic
(II) Nonmetal + Nonmetal Covalent
(III)Metal + Metal Metallic
(IV) Electron deficient molecule or ion (Lewis acid) and Coordinate
electron rich molecule or ion (Lewis base)
(V) H and electronegative elements (N, O, F some times with Cl) Hydrogen
Ionic, Covalent and coordinate bonding

Ionic bonding
An ionic bond is formed when a metal atom transfers one or more electrons to a non-metal atom.
–
e
1 + –
Na + F Na F
2 2
The oppositely charged ions get attracted through electrostatic force of attraction.
Properties of ionic compounds :
 In the solid state, each cation surrounds itself with anions and each anion with cations. These
very large number of ions are arranged in an ordinary network called ionic crystals.
 They are good conductors of electricity in fused state or aqueous solution.
 They are generally soluble in polar solvents and insoluble in non-polar solvents.
 Have high melting point and boiling point than covalent compounds.
 Have strong force of attraction between cation and anion (Coulombic force)
Z1Z2e2
F=
Dr 2
Where Z1 and Z2 are charge on the ions, D is dielectric constant of the medium and r the inner-ionic
distance (i.e., bond length).
Born-Haber cycle It is an indirect method to calculate the lattice energy of an ionic compound. For
example, the lattice energy of sodium chloride can be calculated as follows.
1
Na(s) + Cl2(g) NaCl(s)
2
S +D/2
Na(g) + Cl(g)
+ – –U
Na (g) + Cl (g)
Page # 4 CHEMICAL BONDING
Now, according to Hess’s law,

Hformation = S + IE1 + D/2 – EA1 – U
Where S is the enthalpy of sublimation of metal (Na), IE1 is the first ionisation energy of sodium, D is
the bond dissociation energy of Cl1 molecule, EA1 is the first electron affinity of Cl, U is the lattice
energy of NaCl(s) and Hformation is the enthalpy of formation of NaCl.
Covalent Bonding :
Whenever Chemical bond is formed by sharing of electrons then it is named as covalent bond.
Coordinate Bonding or Dative Bond :
Whenever covalent bond is formed by unequal sharing of a pair of electrons between a Lewis base and
Lewis acid is called coordinate bond.
(I) It is represented as () and considered as  bond.
(II) Atom/ion/molecule donating electron pair is called donor or Lewis base.
(III) Atom/ion/molecule accepting electron pair is called acceptor or Lewis acid.
Formation of NH4+ :
NH3 has three (N – H) bonds and one lone pair. In NH4+ formation. This lone pair is donated to H+ ion.
: NH3 + H +  NH4+
H H
| +
|
H — N: H or H—N H
| |
H H
Note : In a multiple bond (  ) sign is treated as a pi-covalent bond (Bock bond).
Valence Bond (V.B) theory :

According to this theory, a covalent bond is formed by the overlapping of atomic orbitals. Important
points of this theory are summarised below.
(I) Orbitals undergoing overlapping should be half-filled.
(II) Half-filled orbitals should contain the electron with opposite spin.
(III)Strength of a covalent bond depends upon the extent of overlapping, for example, axial or lateral
overlapping.
(IV) If the atomic orbitals overlap axially, then the bond formed is called a sigma () bond.
(V) A sigma bond is always stronger than a pi-bond.
(VI) Covalent bonds formed by the overlap of s-s and s-p orbitals are always sigma.
(VII) By the overlap of p-p orbitals, one sigma and two pi bonds are formed.
(VIII) Increasing strength of  covalent bonds is in the order s – s < s - p < p — p (when
internuclear distance is constant)
(IX) A single covalent bond is always a sigma bond. In a double covalent bond, one is sigma and the
other is pi-bond. In a triple covalent bond, one is sigma and two are pi-bonds.
Hybridisation :
It is defined as the concept of intermixing of orbitals of same energy or of slightly different energy to
produce entirely new orbitals of equivalent energy, identical shapes and which are symmetrically
disposed is plane.
Important features of hybridisation are given below.
(I) Only the orbitals generated are equal in number to that of pure atomic orbitals which are
intermixed.
(II) The hybrid orbitals generated are equal in number to that of pure atomic orbitals which are
intermixed.
(III) A hybrid orbital, like an atomic orbital, can have two electrons of opposite spins.
(IV) Hybrid orbitals usually form sigma bonds. If there are pi-bonds, equal number of atomic
orbitals must be left unhybridised for pi-bonding.
Valence shell electron pair repulsion (VSEPR) Theory (Gillespie theory) :

(I) The shape of a molecule is determined by repulsion between the electron pairs (p and bp) present
in the valence shell of the central atom.
(II) The order of repulsion is (p-p) > (p-bp) > (bp-bp)
Determination of the Type of Hybridisation :
The number of electron pairs = Bond Pairs + lone pairs
( Bond)
Table Shapes of molecules on the basis of VSEPR theory and hybridisation
Total Bond Lone Type of Geometry due to Bond angle Example

electron pairs pairs hybridization repulsion
pairs
2 2 0 sp Linear 180º BeCl 2
2
3 3 0 sp Trigonal Planar 120º BF 3
2
3 2 1 sp Angular <120º SO2
3 2
4 4 0 sp or dsp Tetrahedral 109º28’ CH 4
3 2
4 3 1 sp or dsp Pyramidal <109º28’ NH 3
3 2
4 2 2 sp or sp Bent <109º28’ H2O
3
5 5 0 sp d Trigonal bipyramidal 120º & 90º PCl 5
3
5 4 1 sp d See Saw <120 º & <90º SF 4
5 3 2 sp3d Bent T-shaped <90º ClF3
3 –
5 2 3 sp d Linear 180º I3
3 2
6 6 0 sp d Octahedral 90º SF 6
3 2
6 5 1 sp d Square pyramidal <90º BrF5
3 2
6 4 2 sp d Square planar 90º XeF4
3 3
7 7 0 sp d Pentagonal bipyramidal 90º & 72º IF 7
7 6 1 sp3d3 Pentagonal pyramidal <90º & <72º
3 3
7 5 2 sp d Pentagonal planar 72º XeF5–
Molecular Orbitals (M.O.) Theory :

(I) There is Linear combination of Atomic Orbitals (LCAO) to form molecular orbitals (M.O.)
Page # 6 CHEMICAL BONDING
(II) The number of molecular orbitals produced is equal to the number of atomic orbitals that are
combined.
(III)Two types of molecular orbitals are formed.
(a) Bonding molecular orbitals at a lower energy than the combining atomic orbitals which favour bond
formation.
(b) Anti - bonding molecular orbitals at a higher energy than the combining atomic orbitals which
opposes the bond formation.
Following molecular orbitals are formed when atomic orbitals overlap.
Atomic orbitals Bonding M. O. Anti-bonding M.O.
1s + 1s  1s * 1s
2s + 2s  2s * 2s
2px + 2px  2px * 2px
2py + 2py  2py * 2py
2pz + 2pz  2pz * 2pz
Electrons are filled in the increasing order of energy of the molecular orbitals which is in order of Aufbau
rule
(a) When total electrons in the molecule or ions are more than 14(simple order of energy level
of M. O.).
(b) When total number of electrons in the molecule are ions are 14 (modified order of energy
level of M.O.).
(I) The electrons are filled in molecular orbitals in the same way as in atomic orbitals, that is, as per
the Hund’s Rule, Pauli exclusion principle and Aufbau rule.
(II) Number of covalent bonds between two atoms is called Bond order and is given by
 NB  NA 
Bond order (B.O.) =  
 2 
Where, NB = number of electrons in bonding molecular orbital and NA = number of electrons in anti
bonding molecular orbitals.
(III)For a stable molecule/ion, NB > NA
(IV) A given molecule or ion is paramagnetic if it has unpaired electrons in the molecular orbital.
Otherwise it is diamagnetic
(V) Greater the bond order, shorter the bond length and greater the bond energy. Thus for O2, O2 + ,
O2—,O22–
+ – 2–
O2 O2 O2 O2
Increasing bond length
Increasing bond order
Fajan’s Rule :
This rule is used to decide relative ionic & covalent character in a molecule. A molecule is predomi-
nantly covalent if
(I) Smaller the size of cation.
(II) larger the size of anion.
(III)greater the charge on cation and anion.
(IV) ion does not have inert gas configuration but it possesses pseudo inert gas configuration (18
electrons in the ultimate shell).
LiCl > NaCl > KCl > RbCl > CsCl
(I) decreasing covalent character due to increase in the size of cation
NaF > NaCl > NaBr > NaI

(II) decreasing ionic character because of increase in anionic size
NaF > Na2O > Na3N

(III) increasing covalent nature due to increase of charge on anion and increase in size of anion
(IV) CuCl and NaCl

[Cu+] = [Ar]3d10 ; [Ne+] = [Ne]
Cations with 18-electron shells (pseudo inert gas configuration) has grater polarising power than 8-
electron shell (inert gas configuration) ion with the same charge and size. Thus, CuCl is more covalent
than NaCl.
Hydrogen Bonding :
(I) The concept of H-bonding was introduced by Latimer and Rodebush.
(II) H-bonding is said to be formed when slightly acidic hydrogen attached to a strongly electronega-
tive atom such as F, O and N is held with weak electrostatic forces by the non- bonded pair of electron
of another atom. That is , it is a dipole-dipole interaction.
(III)Of all the electronegative donor atoms, only F, O. and N enter into stable H-bond formation.
(IV) The weak electrostatic interaction leading to the H-bond formation is shown by dashed(.....) lines.
(V) Greater the electronegativity difference, stronger is the H-bond. For example,
F ........ H > O ........ H > N ........ H
Intramolecular H-bonding ;
This type of H-bonding occurs when polar H and electronegative atom are present in the same
molecule.
(a) o-hydroxy benzaldehyde (b) o-nitrophenol
O
H
CH O
O
H N
O
O
Intermolecular H-bonding
This type of H-bonding takes place between hydrogen and electronegative element (like F,O,N) present
between molecules of the same substance (H2O and H2O) or different substances (H2O and NH3).
CHEMICAL EQUILIBRIUM
THEORY AND EXERCISE BOOKLET
CONTENTS
S.NO. TOPIC PAGE NO.
¨ Theory (Include Examples) ............................................... 2 – 13
¨ Solved Examples ............................................................ 14 – 19
¨ Exercise - I (One option is correct) ................................... 20 – 36
¨ Exercise - II (Multiple choice Problems) .............................. 37 – 40
¨ Exercise - III (Subjective level - I) .................................... 41 – 55
¨ Exercise - IV (JEE PROBLEMS) .......................................... 56 – 58
¨ Answer key ................................................................... 59 – 60
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Page # 2 CHEMICAL EQUILIBRIUM
CHEMICAL EQUILIBRIUM
1. The state at which concentrations of reactants or products do not change with time.
2. It is attained when rate of forward reaction becomes equal to rate of backward reaction.
3. A dynamic equilibrium, attained from either side.
IRREVERSIBLE AND REVERSIBLE REACTIONS
Irreversible reactions Reversible reactions

1. Unidirectional 1. Both directional
2. Go for completion 2. Never go for completion
3. No equilibrium is attained 3. Attains equilibrium
4. A reaction is said to be irreversible 4. Otherwise the reaction is reversible e.g.,
when either of the product is settled CaCO3 CaO + CO2
down as solid or escapes out as gas,
e.g.,
BaCl2 + Na2SO4  BaSO4 (insoluble) in closed container
+ 2NaCl
CaCO3  CaO + CO2 
HOMOGENEOUS SYSTEM
The system in which all the reactant and product have same physical state.
N2(g) + 3H2(g) 2NH 3(g)
2SO2(g) + O2(g) 2SO 3(g)

CH3COOC2H5(aq) + H2O(aq) CH3COOH (aq) + C2H5OH (aq)
HETEROGENEOUS SYSTEM
The system in which atleast one reactant or product have different physical states from others. eg.
CaCO3(s) CaO(s) + CO2(g)
 This is three phase system
Salt + H2O(aq)  Salt (aq)
 Three phase system.
RATE OF REACTION
The change in concentration per unit time of reactant or product is called rate of reaction
1. Average Rate
2. Instantaneous Rate
A  B
t=0 a 0
t=t a–x x
– A B
Rate = 
t t
A a – x – a – x
 
t t t
B x – 0 x
 
t t t
2A  B
t=0 a 0
t=t a – 2x x
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CHEMICAL EQUILIBRIUM Page # 3
A a – 2 x – a 2x
 –
t 4t t
B x 1  A B
  – 
t t 2 Δt t
Instantaneous Rate :
– A – dA
lim  (inst. Rate)
t  0 t dt
3A + 2B  5C + 7D
t=0 a b 0 0
a – 3x b – 2x 5x 7x
A 3x B 2x
– ; –
t t t t
C 5 x D 7 x
 ; 
t t t t
1 A 1 B 1 C 1  D
 – – = 
3 t 2 t 5 t 7 t
LAW OF MASS ACTION

A  B
Ex.1 Is this a one step reaction or more than one step reaction ?
Sol. By merely seeing the reaction we can not predict the step of the reaction.
The above reaction can also be written as
A  C
C  D
D  B
Adding A  B
Law of mass action is only valid for elementary reaction.

According "The rate of a chemical reaction is directly proportional to active mass of the reactants"
A  Product
rate  Active mass of A
where Active mass = Activity coefficient × molar concentration
when active coefficient = 1
Active mass = Molar concentration
ACTIVITY COEFFICIENT
The fraction of molecules taking part in effective collision is called activity coefficient. It is always less than 1.
Rate  [A]
Rate = k [A]
k = Rate constant
A product (complex Reaction)
Rate = K [A]x where x = order of Reaction w.r.t. A
• 2A  product
Rate = K [A]2 [for elementory Reaction]
Rate = k [A]x [for complex Reaction]
"If there are more than one reactant then the rate of reaction is directly proportional to product of
Active masses of substances."
Rate  Active mass of A × Active mass of B
Rate = k [A] [B]
and if any reaction is of the type
aA + bB  product
Rate = k[A]a [B]b
aA + bB cC + dD
Rate of forward Reaction (Rf) = kf [A]a [B]b
Rate of backward Reation (Rb) = kb[C]c [D]d
At equilibrium
Rf = Rb
kf [C] c [D] d
kf[A]a [B]b = kb[C]c [D]d  
k b [ A ] a [B]b
kf
kc = k
b
Kc  equilibrium constant in terms of concentration
p c  p Dd
K p  ac (Kp = eq. constant in terms of partial pressure)
p A  p Bb
• Consider the reaction
N2(g) + 3 H2(g) 2NH3(g)
[NH3 ] 2
then KC 
[N 2 ][H2 ] 3
2
pNH3
Kp 
pN2  pH32
RELATION BETWEEN KP AND KC

PV = nRT
n
P= RT
V
P = CRT
PA = [A] RT ...(1)
PB = [B] RT ...(2)
Pc = [C] RT ...(3)
PD = [D] RT ...(4)
We know that for a reaction of the type
aA + bB cC + dD
p cC  p Dd
kp 
p aA  p Bb
[C] c [D] d (RT )C  d

kp  (from eq. (1), (2), (3) & (4))
[ A ] a [B] b (RT )a  b
kp  kc ( RT )n
where n = (c + d) – (a + b)
n = no. of moles of gaseous Reactants – no. of moles of gaseous products
if n = 0
 Kp = Kc
EQUILIBRIUM CONSTANT IN TERMS OF MOLE FRACTION
x cC  x Dd
kx 
x Bb  x aA
Partial pressure = mole fraction × total pressure
Ex.2 Find the relation between Kp and Kx for the reaction
N2(g) + 3 H2(g) 2 NH3(g)
2
pNH 3
( x NH3  p) 2 x NH3 p2 kx
Sol. kp  = ( x  p )  ( x  p )3 = x  ( x ) 3 p 4  k p  2
pN2  pH3 2 N2 H2 N2 H2 p
Ex.3 What is the relation between kc and kx for the same reaction ?
kx k xR 2 T 2
Sol. kc(RT)–2 =  k c 
p2 p2
CHEMICAL EQUILIBRIUM WITH GRAPH

rf
N 2O 4(g) 2NO 2(g)
rb
rf rf
rate rate
rb rb
(a) (b)
time time
equilibrium as rf = rb equilibrium as rf = rb
rf rf
rate rate
rb
(c) (d) rb
time time
Not equilibrium as rf  rb Not equilibrium as rf  rb
rf
rate
rb
(e) Same reason as below.
time
rf
rate
(f) rb (not equilibrium rate of forward reaction and backward
reaction can not increase together)
time
If we consider concentration and time for the above plot then only e and f will not show the state of equilibrium.
EXPRESSION FOR KP AND KC FOR A GIVEN REACTION
N2(g)+ 3H2(g) 2NH3(g)

t=0 a b 0
a–x b – 3x 2x
At eq.
v v v
2
 2x 
2  
[NH 3 ]  v 
kc  
[N 2 ] [H 2 ] 3  a – x   b – 3 x  3
  
 v  v 
2
4x 2 pNH 3
kc   kp 
(a – x )(b – 3 x )3 v 2 pN2  pH3 2
2
 2x 
  p
 a  b – 2x  4 x 2 (a  b – 2 x ) 2
 kp   kp 
 a–x   b – 3x 
3
(a – x )(b – 3 x )3 p 2
  p    p
 a  b – 2x   a  b – 2x 
DEGREE OF DISSOCIATION
2NH3(g) N2(g) + 3 H2(g)

a – 2x x 3x
It is the no. of moles dissociated from 1 mole of reactant.
OR
Fraction of moles dissociated from one mole of reactant.
 a moles NH3 gives 2x mole
2x
 1 mole NH3 
a
2x
degree of dissociation () =
a
2NH 3 N 2 + 3H 2
a 3a 
a(1–)
2 2
DEGREE OF DISSOCIATION FROM VAPOUR DENSITY
Ex.4 The V.D. of mixture of PCl5, PCl3 and Cl2 is 92. Find the degree of dissociation of PCl5.
Sol. PCl5 PCl3 + Cl2
1 0 0
1–x x x
If initial concentration is not given in the question then we suppose initial mole = 1 mole
molecular wt. of mixture. = 2 × 92 = 184
total moles of mix = 1 – x + x + x = 1 + x
wt. of the mixture = (1 + x) × 184
wt. of initial mixture = 1 × 208.5
 1 × 208.5 = (1 + x) × 184 (according to law of mass conservation)
 208.5 = 184 + 184 x  x = 0.13
% dissociation = 13 %
Ex.5 nA An
V.D. of A = d
V.D. of mix = D
find the degree of polymerisation.
Sol. nA An
1 0
x
1–x
n
x
moles of mix = 1 – x +
n
x
wt. of mix = (1 – x  )  2D
n
x
1 × 2d = (1 – x + ) × 2D (According to law of mass conservation)
n
d 1  d 1  (d – D)n (D – d)n
 1  x – 1   1  x – 1  x  x
D n  D n  D(1 – n) D(n – 1)
CHARACTERISTICS OF EQUILIBRIUM CONSTANT
k1
1. A + B C + D
[C][D]
k1 
[ A ][B]
After reversing the reaction
k2
C + D A + B
[ A ][B] 1
k2  
[C][D] k 1
After reversing the reaction the equilibrium constant get reversed.
k2 k1
2. E + F G and A + B C + D
k3
After adding the reaction  A + B + E + F C+D+G
[C][D] [G]
k3 
[ A ][B] [E] [F]  K3 = K1 × K2
when the two reaction are added there equilibrium constant get multiplied.
k1
3. A + B C + D
[C][D]
k1 
[ A ][B]
After multiplying by n
k2
nA + nB nC + nD
[C]n [D] n n
k2   k1  k  k n
[ A ]n [B]n 2 1
When the reaction is multiplied by any number then eq. constant gets the same number in its power.
HETEROGENEOUS EQUILIBRIUM
CaCO 3 (s) CaO(s) + CO2(g)

The density of the solid at constant temp. remains constant.
m
d=
V
d m 1 n
   Here m = mass of solid
M v M V
n
constant = M = molecular weight of solid
v
 concentration = constant n = moles of solid.
[CaO(s)][CO 2 (g)] [CaCO3 (s)]
k  k  [CO 2 (g)]
[CaCO 3 (s)] [CaO(s)]
 Kc = [CO2(g)]
PREDICTION OF THE DIRECTION OF THE REACTION

Kc = 10
2A + B C + D
conc. at t time 2 mol 3 mol 5 mol 4 mol [volume of container = 1 litre]
[C] [D]
kC   All concentration at eq.
[ A ] 2 [B]
[C] [D]
Reaction quotient Q C  Here concentration is at any time 't'
[ A ] 2 [B]
54 5
QC  
43 3
If QC > Kc  backward Reaction
QC < KC  forward Reaction
QC = KC  Equilibrium condition
LE CHATELIER'S PRINCIPLE
When the equilibrium is disturbed by changing pressure, temp, volume and concentration of the reactants or
products then reaction proceeds in that direction where the applied change is nullified"
1. Effect of Temperature :
(i) Endothermic Reaction
A + B product H > 0
or A + B + heat product
In case of endothermic reaction on increasing the temp, reaction proceeds in the forward direction and vice
versa.
On increasing temp, the value of eq. constant increasing.
k2 H  1 1
log   – 
k 1 2.303R  T1 T2 
If temp is increased
T1 < T2
for endothermic reaction, H > 0 i.e. +ve
1 1
Also –
T1 T2 = +ve
k k
 log 2  0  log 2  log1
k1 k1
k2
 1  K > K
k1 2 1
if T1 > T2
k2 k2
 log k < 0  log k  log1  k2 < k1
1 1
Thus it can be conclude that

H > 0 T k
(endothermic) T  k
H < 0 T k
(exothermic reaction) T  k
(ii) Exothermic Reaction(H < 0)

On increasing temperature, the reaction proceeds in backward direction.
2. Effect of Pressure :
PCl5 PCl3 + Cl2
At eq. n1 n2 n3
 n2  n3 
  P     P
 n1  n 2  n 3   n1  n 2  n 3 
kp 
n1
P
n1  n 2  n 3
n 2n 3  P
 kp 
n1(n1  n 2  n3 )
On increasing P, eq. will be disturbed  kp will not defined at that pressure Hence Qp will be defined
n 2n3
Qp   p1
n1(n 2  n1  n 3 )
 value of Qp > value of kp

 backward reaction
 On increasing Pressure the reaction shift in direction where the number of moles are less.
 If no. of moles at reactant side and product side are equal then there will be no effect of changing pressure
at equilibrium.
3. Effect of volume :
If the concentration of reactant increases or that of concentration product decreases then reaction proceeds
in forward direction.
3. Addition of Inert Gas

(1) At constant volume
(2) At constant pressure
(i) At constant volume.

PCl5 PCl3 + Cl2
n1 n2 n3
At eq.
v v v
n 2 n3

kc  v v n 2 n3
n1 = nv
1
v
PV = nRT
P  n (V, T constant)
After the Adding of inert gas
n 2n3
Qc   Qc = Kc
n1v
 there is no effect of adding inert gas on the state of equilibrium at constant volume.
 n2  n 3p 
  p   
PPCl3  PCl2 n1  n 2  n 3 n 1  n2  n3 n 2 n3 p
kp    

PPCl5  n1  n1 (n1  n 2  n3 )
  P 
n
 1  n 2  n 3 
If we n4 moles of inert gas is added
n 2 n3 p' P
Qp  (n  n  n  n )  = constant
1 2 3 4 n
 QP = Kp
 there will be no effect of adding inert gas on equilibrium at constant volume.
(ii) At constant pressure

PV = nRT
Vn
PCl 5 PCl3 + Cl2
n1 n2 n3
At eq.
v v v
n 2n3
 kc 
n1v
After the Adding of inert gas
n 2n3
Qc 
n1( v  v )
 Qc < KC  forward direction

• On Adding of inert gas At constant pressure, the reaction proceeds in that direction where the sum of
stoichiometric coefficient is greater.
SIMULTANEOUS EQUILIBRIUM
A(s) B(g) + C(g)

D(s) B(g) + E(g)
Applicable only when at least one of the product is common in both the reaction.
Ex.6 The pressure at equilibrium over solid A is 50 atm and over solid D is 68 atm if both solid A and D are
heated simultaneously then find the total pressure over the solids.
Sol. At 1st equilibrium
k p1  (25) 2 ; k p 2  (34 ) 2
At IInd equilibrium
A(s) B (g) + C(g)
x+y x
D (s) B(g) + E (g)
x+y y
K p1  (x  y)  x ...(i)
K p2  ( x  y)  y ...(ii)
total pressure = pB + pC + pE = x + y + x + y = 2 (x + y)
Also k p1  k p 2  ( x  y )2
 x  y  k p1  k p 2
 Total pressure = 2 (x + y) = 2 k p1  k p2
(i) In the above question find the mole ratio of C and B
(ii) mole fraction of C
Sol. At constant temp and volume
Pn
 pressure Ratio will their mole ratio
by eq. (i)/(ii)
k p1 x

k p2 y
(iii) Mole fraction of C
x
C
2( x  y )
k p1 x
As we know k  y
p2
y k p2 x  y k p 2  k p1
   
x k p1 x k p1
2 ( x  y ) 2(k p 2  k p1 ) x k p1
   
x k p1 2 ( x  y ) 2(k p 2  k p1 )
k p1
 mole fraction of C = 2(k  k )
p2 p1
Ex.7 A(s) H2S(g) + B(g) At eq., pressure = 18 atm

C(s) H2S(g) + D(g) At eq., pressure = 36 atm
Calculation
(i) total pressure at new equilibrium when both the solids are heated simultaneously.
(ii) mole ratio of B and D
(iii) mole fraction of B in the mixture.
Sol. kp1 = (9)2 = 81
kp2 = (18)2 = 324
After
A(s) H2S(g) + B(g)
x+y x
C(s) H2S(g) + D(g)
x+y y
total pressure = x + y + x + y = 2 (x + y)
kp1 = x(x + y)
kp2 = y(x + y)
 kp1  kp 2 = (x+ y)2  x + y = kp1  kp 2
 total pressure = 2 (x + y) = 2 kp1  kp 2
= 2 81  324  2 405 atm
x 81 9 1
(ii) mole ratio of B & D = y =  =
324 108 12
x kp1
(iii) mole fraction of B in mixture = 2( x  y ) = 2(kp  kp )
1 2
PHYSICAL EQUILIBRIUM
Let us consider the following physical equilibrium

H2O() H2O(g)
1. Effect of temperature
Since it is an endothermic reaction therefore reaction will proceed in forward direction on increasing temp.
(Le Chatelier's principle)
2. Effect of pressure :
dP H

dT TV
for the above equilibrium H > 0
V ie Vg – V = +ve
dP
   ve
dT
 on increasing P, T increases
But As reaction is to complete at the initial temp, therefore temperature must be lowered. This will make the
reaction go to direction as suggested by Le-chatelior (endothermic reaction)
Ex.8 A(s) (d = 1.14 gm/cc)

B(s) (d = 1.5 gm/cc)
A(s) B(s) + Heat
If mass of A and B are equal, on increasing the pressure, will for formation of B  or  ?
Sol. A(s) B(s)
As density of solid B > solid A
 VB < VA  VB – VA = – ve
since reaction is exothermic
 H = – ve
dP H
 =
dT TV
dP
 = +ve
dT
 on  ing P, T also es
To achieve initial temp. i.e., reaction temp. The temp. must lowered and lowering.
the temp. in an exothermic reaction clearly indicates forward reaction.
 On increasing pressure, the rate of formation of B will be enhanced.
IONIC EQUILIBRIUM Page # 3
IONIC EQUILIBRIUM
An ionic Equilibrium exists between the unionised electroyte molecules and the ions that result from
ionisation
A + B A+ + B–
 Types of keq

Self ionization Acid dissociation Base dissociation Salt Sparingly
of water constant constant hydrolysis soluble salt
H2O H++OH + –
H A H+ +A– BOH B++ OH– – +
A B +H2O HA+BOH AgCl Ag++Cl–
 Concept of electrolyte

Strong electrolyte Weak electrolyte
A  B–  A   B– AB A+ + B–
a 0 0 a 0 0
0 a a a (1 – ) a a
 100% disssociation ( = 1) <1
 no equilibrium equilibrium
 it is irreversible it is reversible process.
 Self ionization of water
1000 / 18
Concentration of H2O ([H2O]) =  55.5 M
1
Water is very weak electrolyte
H2O H+ + OH–
55.5
55.5 – 10–7 10–7 10–7 (at 25oC)
[H ] [OH– ]
 k eq 
[H2 O]
Constant
 Kw = keq [H2O] = [H+] [OH–]
 Kw = [H+] [OH–], at 25oC, [H+] = [OH–] = 10–7

o –14
Kw (25 C) = 10

Self ionization constant of water
let, Kw1 at temperature T1 , Kw2 at temperature T2
Kw 2 H  1 1 
 log   –  T   Kw 
K w1 2.303 R  T1 T2  ,
Page # 4 IONIC EQUILIBRIUM
 For calculation of  :
+ –
H2O H + OH
c 0 0
c (1 – ) cc
Kw = c × c
kw
   c = 5 5.56 M    1.8  10 –2 Kw
c
pH (pH scale is given by Sorension)
 potent Hydrogen ion


strength
at 25°C
+
 pH = – log [H ] pH scale
p OH = – log [OH–]
p Kw = – log Kw Neutral
at any temperature :
[H+] = [OH–] O Acidic basic
[H+] [OH–] = Kw 7 14
 – log [H+] – log [OH–] = – log [Kw]
 pH + pOH = p Kw
at 25oC at 80oC
Kw = 10–14 Kw = 10–12
pH + pOH = 14 pH + pOH = 12
25oC 90oC
pH + pOH = 14 pH + pOH = 12
Some concept regarding pH calculation

 Concept 1 :  Concept 2:
5L 1L 3L 2L 5L
pH = 3  pH = ? pH = 3 + pH = 3  pH = ?
 Concept 3:  Concept 4:
2L 8L 10 L 2L 8L 10 L
pH = 3 + H2O = pH = ? pH = 13 + water = pH = ?
Ca lcula te pH (i) Ca lcula te pOH

 Note : 7
pH (ii) pH = 14- pOH
 Concept 5:
pH = 3 + pH = 4 = pH = ?
2 : 1
 Note : The final pH of solution after mixing two solution is in between the previous solution pH.
 Concept 6:  Concept 7:
10 M HCl
–8
V V 2V
pH = 3 + pH = 11  pH = ? pH = ?
 Note :
When [H+] > 10–5  [H+]water neglected
When [H+] < 10–5  [H+]water considered
H2O H+ + OH–
55.56 10–8
55.56 – x 10–8 + x x
 x (10–8 + x) = 10–14  x = .94 × 10–7
 [H+] = 10–8 + .94 × 10–7 = 1.04 × 10–7
 pH = 7 – log (1.04)
 Concept 8:
2
10 M HCl
pH = ?
 Dissociation of weak acid :
H+ A– H+ + A–
c
c (1– ) c c
c 2
Ka  for weak acid < < 1 Ka = c2
1– 

Kw
[H+] = c = c Ka , pH = – log c Ka , for bases [H+] = c  Kb
 Note :
(a) HA1 c Ka 1
||
[H  ]1 Ka 1
HA2 c Ka 2 
 
[H ] 2 Ka 2
 So HA2 is stronger acid than HA1

(b) HA1 c1 Ka 1
[H ]1 c1 ka1
HA2 c2 Ka 2 
[H ]2 c 2 Ka2
 The acidic strength of two weak acid can be compared by Ka value only in the case when their
concentration are same. Otherwise the procedure of case (b) should be followed .

pH of mixture of two acids
 Case (I) (Strong acid + weak acid)
Question : HCl (0.1 M) + CH3COOH (0.2 M)


Ka = 10–5
CH3COOH CH3COO– + H+
t=0 0.2 0 0. 1
t = teq 0.2 – x x 0.1 + x (x is very small)
  
0.2 x 0.1
x  0.1
 pH = – log (0.1) = 1  [CH3COO–] = ?  10 – 5   [CH3 COO– ]  2  10 – 5
0.2
 Case (II-A) (weak acid + weak acid ) (kas are incomparable)
Question : HA1 (0.1 M, Ka 1 = 10–5)
HA2 (0.2 M, Ka 2 = 10–9)
HA1 H+ + A1 – HA2 H+ + A2–

0.1 0 0 0.2 0 0
0.1 – x x+y x 0.2 – y x+y y ( Ka 1 >> Ka 2
       x > > y)
0.1 x x 0.2 x y
x and y are also very less
x. x
10 –5  [H+] = x = 10–3 ,  pH = 3 [A1– ] = [A2–] =
10 –1
 Case (II-B) (weak acid + weak acid ) (kas are comparable)
Question : HA 1
(0.1) Ka 1 = 10–5
HA2 (0.2) Ka 2 = 10–6

HA1 H+ + A1 – HA2 H+ + A2–
0.1 0 0 0.2 0 0
0.1 – x x+y x 0.2 – y x+y y
0.1 x+y x 0.2 x+y y
x (x  y)
 now K a1 
0.1
x (x  y) (x  y) y
 Ka 1  , Ka 2 
c1 c2
 [H  ]  x  y  c 1 Ka1  c 2 Ka 2
 weak polyprotic acids or bases

(H2S, H3PO4, NH2 – NH2, H2CO3)
(a) H2S H+ + HS– Ka 1 HS– H+ + S2– Ka 2

 
(b) NH2 – NH2 + H+ NH2 – NH3+ Kb 1 NH2 – NH3+ + H+ NH3 – NH3 Kb 2
Cases
 Case I : H2S (0.1 M Ka 1 = 10–4 , Ka 2 = 10–9)
 H2S H+ + H S– H S– H+ + S2–
0.1 0 0 x x 0
0.1 – x x+y x–y x–y x+y y
     
0.1 x x x x y
Ka 1 > > Ka 2 x >> y
x2 x y
10 – 4   x 10 –5  10 –9
0.1 x
[H+] = x = [HS–] = x = [S2–] = y =
 Case II : HCl H+ + Cl–

0.2 0 0
0 0.2 0.2
 H2S H+ + HS– H S– H+ + S2–
0.1 0.2 0 x 0.2 + x 0
0.1 – x 0.2 + x + y x x–y 0.2 + x + y y
     
0.1 0.2 x x 0.2 y
[H+] = 0.2  pH = – log (0.2)
 Note : Strong acid controls the pH.

 Now , [H+] = 0.2
 Case III : H3PO4 (0.1 M) Ka 1 = 10–5 , Ka 2 = 10–8 , Ka 3 = 10–11
 H3PO4 H+ + H2PO4– H2PO4– H+ + HPO42–

0.1 0 0 x x
0.1 – x x+y+z x–y x–y x+y y
     
0.1 x x x x y
 HPO42– H+ + PO43–
y y+x
y–z x+y+z z
  
x2
y x z   10 – 5  x  10 – 3  pH = 3
0. 1
 Buffer
 Any solution which resist the change in pH is called Buffer solution.
 Requirement of Buffer
(1) Must have acidic and basic components so that it can consume H+, OH– added to the buffer.
(2) Acidic and basic components should not react with each other.
CH3COOH CH3COO– + H+
acid conjugate base
 
acidic component basic component
do not react with each other.

(3) Buffers can be prepared by following two ways
 Buffer
CH3COOH / CH3COONa NH4OH / NH4Cl

W. A / Canjugate Base W. B / Conjugate acid
 acidic buffer  basic buffer
 0 < pH < 14  0 < pH < 14
 Acidic buffer Basic buffer
Ka c1 c2 Kb c1 c2
CH3COOH CH3COO– + H+ NH4OH NH4+ + OH–
c1 c2 0 c1 c2 0
c1 – x c2 + x x c1 – x c2 + x x
     
c1 c2 x c1 c2 x
in presence of CH3COO– dissociation
c2 .x
of CH3COOH is supressed. Kb 
c1
c1
So x is very small x  Kb
c2
c2 x [salt]
Ka  pOH = pKb + log
c1 [base ]
Ka c 1 c2 [salt]
 x= pH  pK a  log pH  pK a  log
c2 c1 [acid]
 Buffer action
 Acidic Basic
c1 c2 c1 c2
c2 [c 2 ]
pH = pKa + log c pOH = pKb + log [c ]
1 1
 (a) NaOH is added (x M) (a) HCl is added (x M)

– –
CH3COOH + OH CH3COO + H2O NH4OH + H+ NH4+ + H2O
c1 x c2 c1 x c2
c1 – x 0 c2 + x c1 – x 0 c2 + x
c2  x c2  x
pH  pKa  log pOH  pKb  log
c1 – x c1 – x
 (b) HCl is added (x M) (b) NaOH is added (x M)
–
CH3COOH CH3COO + HCl NH4OH NH4+ + OH–
c1 c2 x c1 c2 x
c1 + x c2 – x 0 c1 + x c2 – x 0
c2 – x c2 – x
c1  x c1  x
 How to prepare buffer
Acidic buffer Basic buffer

 (a) CH3COOH / CH3COONa (a) NH4OH / NH4Cl
c1 c2 c1 c2
c2 c2
c1 c1
 (b) CH3COOH + NaOH CH3COONa + H2O (b) NH4OH + HCl NH4Cl + H2O
a x a x 0
a–x 0 x a–x 0 x
x x
a–x a–x
 (c) CH3COONa + HCl CH3COOH + NaCl (b) NH4Cl + NaOH NH4OH + NaCl
a x 0 a x
a–x 0 x a–x 0 x
a–x a–x
x x
 Parameters of buffer
 Buffer range Requirement of good buffer

The range of pH a buffer can work nicely (1) pH = pKa
is called buffer range resist both OH– and H+ in equal amount
salt c2
pH = pKa + log (2) pH = pKa + log c
acid 1
 [salt] 
after buffer action max. ratio   = 10
 [acid ] 
c2 – x
pH = pKa + log c  x  pH = pKa + 1
1
 [salt] 
min. ratio   = 0.1 both will be approximately same when
 [acid ] 
pH = pKa – 1 c1 and c2 are very large
c1 , c2 > > x
c2
pKa – 1 pKa pKa + 1  pH  pK a  log
c1
 Buffer capacity
number of mol of H added/L of solution
 Buffer Capacity 
Change in pH of buffer
 Buffer of polyprotic acid
H2CO3 / NaHCO3
c1 c2
H2CO3 HCO 3– + H+ Ka 1 HCO 3– H+ + CO 23– Ka 2
c1 c2 0 c2 + x x 0
c1 – x c2 + x – y x+y c2 + x – y y+x y
     
c1 c2 x c2 x y
c2 y
pH  pK a1  log pH  pK a 2  log
c1 c2
 Salt Hydrolysis
Acid + Base  Salt + H2O neutralization
Salt + H2O  Acid + Base  reverse of neutralization  Salt hydrolysis
since salt hydrolysis is an endothermic reaction hence on increasing the temperature, the extent
of hydrolysis increases.
 Types of salt
Case I Case II Case III Case IV

W. A + S. B S. A. + W. B. W. A + W. B. S. A. + S. B.
e.g. CH3COONa e.g. NH4Cl e.g. CH3COONH4 e.g. NaCl
Case : (I) Hydrolysis of WA + SB :

+
CH3COONa  CH3COO– + Na  spectator ion
 
Very strong Very weak
Conjugate base Conjugate acid
H – OH
CH3COOH NaOH
CH3COO– + H+ Na+ + OH–

CH3COONa CH3COO– + Na+
–
CH3COO + H2O CH3COOH + OH–
__________________________________________
CH3COONa + H2O CH3COOH + Na+ + OH–
__________________________________________________________________________
Note : (1) Only weaker part of salt undergoes hydrolysis. (2) This solution becomes basic.
Case : (II) S.A. + W.B. (NH4Cl) :
NH4+ + H2O NH4OH + H+, This solution becomes acidic
Case : (III) W.A. + W.B. (CH3COONH4) :
–
CH3COO + H2O CH3COOH + OH–
a x
a–x
NH4+ + H2O NH4OH + H+
a y
a–y
Can be acidic, basic or neutral
 Ka  Kb  acidic Ka  Kb  neutral Ka  Kb  basic
Case : (IV) S. A + S. B (NaCl) :
 No hydrolysis  Solution will be neutral
 Relationship between Ka, Kb, and Kh
Case (I) : W. A. + S.B. (CH3COONa)
CH3COO– + H2O CH3COOH + OH–
[CH3 COOH] [OH– ] [CH3 COOH] [OH– ]  [H ] wK
 Keq  –  Kh  Keq [H2 O]  –   Kh  K
[H2O] [CH3 COO ] [CH3 COO ]  [H ] a
Case (II) : S. A. + W. B. (NH4OH)

+
NH 4
+ H2O NH4OH + H+
[NH4 OH][H ] [NH4 OH][H ]  [OH– ] wK
 Kh    Kh   –  Kh  K
[NH4 ] [NH4 ]  [OH ] b
Case (III) W. A. + W. B. (CH3COO NH4)

CH3COO– + H2O CH3COOH + OH–
+
NH4 + H2O NH4OH + H+
_______________________________________________________
CH3COO– + NH4+ + 2 H2O NH4OH + CH3COOH + H+ + O H–
_______________________________________________________
[NH4 OH] [CH3 COOH] [NH4 OH] [CH3 COOH] [OH– ] [H ] w K
 Kh  –
[CH3 COO ] [NH4 ]   Kh   –   Kh  K . K
[NH4 ] [OH ] –
[CH3 COO ] [H ] a b
 pH calculation
Case (I) : W. A. + S. B. (CH3COONa  c, Ka) , h  degree of hydrolysis.
– –
CH3COO + H2O CH3COOH + OH
c 0 0
c (1 – h) ch ch
(ch) 2 ch 2 Kh
Kh   h<<1 Kh = ch2 h

c (1– h) 1 – h
  c
Kw 1 1
 pOH  [pKw – pKa – log c]  pH  [pKw  pKa  log c]
–
 [OH ]  c  h  c. Kh  c.
Ka 2 2
Case (II) :S. A. + W. B. (NH Cl 4  c, Kb)

+
NH 4
+ H2O NH4OH + H+
c 0 0
c (1 – h) ch ch
ch 2 Kh
 Kh  h<<1  Kh = ch2  h 
1– h c
Kw 1 1 kw
 [H ]  c.h  c  Kh  c   pH  [pKw – pKb – log c]  pOH = p  pk b  log c
 
Kb 2 2
Case (III) W. A. + W. B. (CH3COONH4  Ka, Kb , c)

– +
CH3 COO + NH + H2O 4
NH4OH + CH3COOH
c c
c (1 – h) c (1 – h) ch ch
c 2h 2 h2
 Kh  2 2
  K h = h2 1– h  1  h  Kh
c (1– h) (1 – h)2
Kw
 h - - - - - (1)
Ka Kb
[H ] [CH3 COO – ]  [CH3 COOH]

 CH3COOH CH3COO– + H+  Ka  [CH3 COOH]  [H ]  Ka [CH COO – ]
3
ch Kw
  Ka  (h < < 1)  [H+] = Ka . h  [H ]  Ka . (from 1)
c (1– h) Ka . Kb
Ka 1
 [H ]  Kw .  pH  [pKw  pKa – pKb ]
Kb 2
 If , Ka > Kb  pKa < pKb  acidic, Ka = Kb  neutral, Ka < Kb  basic
 Summary of hydrolysis
Kw 1
1. W. A. + S. B. Kh  K pH 
2
[pK w  pK a  log c]
a
Kw 1
2. W. B. + S. A. Kh  K pH 
2
[pK w – pKb – log c]
b
Kw 1
3. W. A. + W. B. K h  K . K pH 
2
[pK w  pK a – pK b ]
a b
 Hydrolysis of salt of polyprotic acid / base (Na2 CO3)

Kw
 CO 23– + H2O HCO3– + OH– Kh1 (CO3 – – ) 
Ka 2
a
a–x x–y x+y
 
x x
– Kw
 HCO3– + H2O H2CO3 + OH– Kh2 (HCO3 )  K
a1
x–y y x+y
  
x y x
Ka1   Ka 2  Kh1   Kh2  Mainly hydrolysis is governed by CO 23– .
– c  Kw c  Kw Kw x y Kw
[HCO3– ]  [OH– ]  [H2CO 3 ] 
  [OH ]  c  Kh1 
Ka 2 ,   Ka 1 ,   Ka 
x  Ka1
1
 Solubility of sparingly soluble salt
Solubility
AgCl (s)   AgCl (aq.) Ag  (aq)  Cl– (aq)
 In ionic equilibrium all the components of equilibrium should be in same phase.
 In case of solubility equilibrium of sparingly soluble salt equilibrium is a heterogeneous equilibrium.
Example (1) : Solubility of AgCl
AgCl (s) Ag+(aq) + Cl–(aq)
[Ag  ] [Cl – ]
Keq 
[AgCl]
 Ksp = Keq . [AgCl] = [Ag+] [Cl–]
 It is a endothermic reaction on increasing temperature T   solubility 
Ksp2 H 1 1
 log   – 
Ksp1 2.303 R  T1 T2 
Example (2) : Solubility of Ag2 CO3 Ag2 CO3(s) 2 Ag+ + CO 23–
 Ksp  [Ag ]2 [CO 32 – ] ,  In general , if salt is Mx Ny type, Mx Ny x My+ + y Nx–
 Ksp  [M y  ]x [Nx– ]y
let , Q = [My+]x [Nx–]y Q = ionic product
If , Q = Ksp  Equilibrium (Saturated solution) Q > Ksp  PPt (Super saturated)
Q < Ksp  Unsaturated solution.
 Various case in solubility
 Case (1) : Ag2SO4 (S = 10–3 mol/L)
Ag2SO4 2 Ag+ + SO 24 –
S 0 0
0 2S S Ksp = [Ag+]2 [SO4- - ] = (2 S)2 (S) = 4 S3
= 4 × (10–3)3
 Case (2) : S (moL / L)  S (gm / L)

10–3
SAg2SO4 (gm/L) = 10–3 × (108 × 2 + 96)
 Case (3) : Ksp given , Solubility = ?
Ag2 SO4 2 Ag +
+ SO24–
S 0 0
0 2S S
S  3 Ksp
 4 S3 = Ksp  mol/L
4
 Case (4) : 70% of the dissolved salt ionizes .
Ag2SO4 2Ag+ + SO24–
S 0 0
S – 0.7S 2 × 0.7S 0.7S
S  3 K sp
 Ksp = (1.4S)2 (0.7S) 
0.98
 Case (5) : Solubility of Ag2SO4 in 0.1 M AgNO3
AgNO3  Ag+ + NO3–
0.1 0 0
0 0.1 0.1
Ag2SO4 (solid) Ag2 SO4 (aq) 2 Ag+ + SO4–
S 0.1
0 0.1 + 2S S
K sp
 KSp = (0.1 + 2S)2 (S)  Ksp  (0.1)2  S  S 
0.01
 Case (6) : Solubility of Ag2SO4 in 0.1M Na2 SO4
Na2SO4 2 Na+ + SO24–
0.1 0 0
0 0.2 0.1
Ag2SO4 (S) Ag2 SO4 (aq) 2 Ag+ (aq) + SO24– (aq.)
S 0 0.1
0 2S 0.1 + S
K sp
 KSp = (2 S)2 (S + 0.1)   4 S2  0.1  S
0.4
 Case (7) : 100 ml 0.01 M AgNO3 + 400 ml 0.02 M Na2SO4, Ksp (Ag2 SO4) = 4 × 10–9
(a) Will any ppt or not ?
 8 
Q = [Ag+]2 [SO24– ] Q = (1/500)2   = 6.4 × 10–8 Q > Ksp  ppt
 500 
(b) After ppt [Ag+] = ? ; [SO42–] = ?
at equilibrium
4S3 = 4 × 10–9 S = 10–3
Number of moles of (Ag2SO4) = 500 × 10–3 = 0.5 m mole
2 Ag+ + SO24– Ag2SO4
1 8
1 – 2x 8–x x
2
 y   7.5  –9
     Ksp  4  10
y 7.5 0.5  500   500  y =?
THERMOCHEMISTRY Page # 3
THERMOCHEMISTRY
Thermochemistry is the branch of physical chemistry which deals with the thermal or heat changes
caused by chemical reactions.
SPECIFIC HEAT (S)
Amount of energy required to raise the temp by 1º C of 1 gm of a substance.
Unit  Energy/gmºC
HEAT CAPACITY
The amount of heat required to raise the temperature by 1ºC or 1K of a given amount of a substance.
C=m×s
Unit  Energy/ºC
Total heat given to increase the temperature by t.
q = mst
MOLAR HEAT CAPACITY
The amount of heat required to raise the temp by 1º of 1 mole of a substance.
CLASSIFICATION OF MOLAR HEAT CAPACITY

(A) Molar heat capacity at constant pressure (Cp)
(B) Molar heat capacity at constant volume (Cv)
Relation between Cp and Cv
Cp – Cv = R (Mayor's formula)
Cp
= (Poison' Ratio)
Cv
RULES FOR THERMOCHEMICAL EQUATION
(1) It is necessary to mention physical state of all reactants and products.
(2) A  B
H = HB – HA
if H > 0 (Endothermic reaction)
H < 0  (Exothermic reaction)
If A  B + x kJ/mole
 H = –x kJ/mole
If A + x kJ/mole  B
or A B – x kJ/mole
 H = x kJ/mole
(3) After reversing a thermochemical eqn then sign of enthalpy also get changed.
e.g. A(g) + B(g)  C(g) + D(g)
H = x kJ
C(g) + D(g)  A(g) + B(g)
H = – x kJ
(4) When two reactions are added their enthalpies are also get added with their sigh.
e.g.
A(g) + B(g)  C(g) + D(g) H = x1 kJ
C(g) + E(g)  F(g) H = – x2 kJ
________________________________________
A(g) + B(g) + E(g)  D(g) + F(g)
H = x1– x2
Page # 4 THERMOCHEMISTRY
(5) If a thermochemical equation is multiplied by a number then enthalpy is multiplied by the same
number.
e.g.
A(g) + B(g)  C(g) + D(g) H = x1 kJ
2A(g) + 2B(g)  2C(g) + 2D(g) H = 2x1 kJ
INTENSIVE PROPERTY
The property which does not depend upon the mass of substance is called intensive property.
e.g. density, refractive index, specific heat, etc.
EXTENSIVE PROPERTY
Mass dependent properties are called extensive properties

e.g.
H, S, G
* Two extensive property can be added or additive.

* Ratio of two extensive properties is Intensive.
* Intensive properties can not be added directly.
e.g. We can not add the density of two liquids to get the density of the final mixture of the two.
m
d
v
 m  dv
 dmix x(h1 + h2)A = d1h1A + d2h2A
d1h1A  d2h 2 A d1h1  d2h 2

 dmix = h1  h2 A  dmix = h1  h2
ENTHALPY
H = U + PV

Internal energy
H = U + PV + VP
(i) t constant Pressure
VP = 0 (as P = 0)
H = U + PV
(ii) At Constant Volume:
PV = 0 as V = 0
H = U + VP
(iii) If both are changing:-
H = U + (P2V2 – P1V1)
* Enthalpy is function of temperature i.e. changes with change in temperature.
H = U + PV
= U + nRT
* Enthalpy is always defined at constant temperature and it varies with variation in temperature.
H = U + PV
= nCVT + nRT = nT(CV + R)
H = n CpT
 Enthalpy at cons tan t pressure.
H = E + nRT
Enthalpy at  Enthalpy at

a constant a constant
pressure Volume
n = no. of moles of gaseous product - no. of moles of gaseous reactant.
Note:-
In chemistry, At constant temp U  0
1 mole O2 (initially)
U = nCV T
As
After reaction  n changes

 n  0
 U  0
Also as after the reaction the nature of substance formed changes which may have different value of
internal energy at the same temp.
KIRCHOFF'S EQUATION
This gives the relation between enthalpy and temperature.

* Physical state is changed at constant temperature.
Molar heat capacity at

constant pressure of A (T2)
A
–T 1)
Cp(T 2 H2
A B (T2)
(T1)
1 )
H1 Cp (T 2–T 1
B Molar heat capacity of B
(T1)
According to Hess'Law
H2 + Cp(T2–T1) = H1 +Cp1 (T2– T1)
H2 – H1 = (Cp1 – Cp) (T2– T1)
= Cp (T2– T1)
H2  H1
Cp = T T
2 1
Where
Cp = Molar heat capacity of product –– Molar heat capacity of reactant
e.g.
N2(g) + 3H2(g)  2NH3(g)
Cp = 2Cp(NH3) – Cp(N2) – 3Cp(H2)
* If the above formula (Kirchoff's eqn) is to be written for molar heat capacity at constant volume then
U2  U1
C V 
T2  T1
* If Cp is function of temperature
Cp = T2 + T
T2
Then T Cp dT  H2  H1
1
HEAT OF FORMATION
Enthalpy change during the formation of 1 mole of a compound form its most stable common occurring
form (also called reference states) of elements is called heat of formation.
C(s) + O2(g)  CO2(g)
H = Hf(CO2)
CO(g) + 1/2O2(g)  CO2(g)
H  HfCO2(g)
(because CO2 has not been formed form its element in their most stable form)
Similarly
CH2–CHO + H2  C2H5OH
H  Hf(C2H5OH)
Heat of reaction
Element Most stable form
H H2(gas)
O O2(gas)
N N2(gas)
F F2(gas)
Cl Cl2(gas)
Br Br2(gas)
I I2(solid)
C C(grapnite)
P P(white)
S S(rhombic)
* All metal exist in solid form (reference states)
ENTHALPY AT STANDARD STATE :-(Hº)

T = 25ºC = 298 K
P = 1 atm
Conc = 1M
Hº = Heat of formation at standard state
If A(g) + B(g)  C(g) + D(g) is any reaction, Heat of reaction for any thermochemical equation can be
written as
Hº = Hfº(product) – Hfº(Reactant)
If we use the above concept for the above given reaction then
Hº = Hfº(c) + Hfº(D) –Hfº(A) + Hfº(B)
Assumption :–
The heat of formation of most stable form of an element is taken as zero.
C(graphite) + O2(g) CO2(g)
Hº = Hfº(CO2) – HfºC(s) –Hfº(O2)(g)
 Hº = Hfº(CO2) (As HfºC(s) = 0 and HfºO2(g) = 0)
Another example can be taken as

H2(g) + 1/2O2(g)  H2O(l)
Hº = Hfº(H2O) – Hfº(H2) – 1/2Hfº(O2)
O O
Hº = Hfº(H2O)
* Heat of formation is always –ve as the process is exothermic.
Ex.1 From the following data,

C(s, graphite) + O2(g)  CO2(g) Hº = –393.5 kJ/mole
H2(g) + 1/2O2(g) H2O(l) Hº = –286 kJ/mole
2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(l) Hº = –3120 kJ/mole
Calculate the standard enthalpy of formation of
C2H6(g) (in kJ/mole)
Sol. From eqn(1) Hfº(CO2) = –393.5 kJ/mole
From eqn(2) Hfº(H2O) = –286 kJ/mole
From eqn (3) rHº 4 Hfº(CO2) + 6Hfº(H2O) –2 ×Hfº(C2H6) – 7×HfºO2(g)
– 3120 = 4 ×(–393.5) + 6×(–286) – 2×Hfº(C2H6) (As Hfº O2(g) = 0 )
 –3120 = –1574 –1716 – 2 ×Hfº(C2H6)
 –3120 + 3290 = – 2 ×Hfº(C2H6)
 170 = – 2 ×Hfº(C2H6)
 Hfº = – 85 kJ/mole
HEAT OF COMBUSTION
It is the enthalpy change (always –ve) when One mole of the substance undergo complete combustion.
C(s) + O2  CO2(g)
Hº = HCºC(s) = Hfº(CO2) – HfºC(s) – Hfº(O2)
Hº = = HCºC(s) = Hfº(CO2)
Other example
O O
H2 + 1/2 O2  H2O(g)
Hº = HCº (H2) = Hfº (H2O) – Hfº(H2) – 1/2Hfº (O2)

Hº = Hfº (H2) = Hfº (H2O)
Note :–
Heat of combustion is always exothermic except N2 and F2.
* N2 + O2  2NO
(It is an endothermic reaction)
* O2 + F2  OF2
(Since O has normally tendency to accept electron and opposite is happening above hence reaction
is is considered endothermic)
* Heat of reaction for any thermochemical equation can be written as (in form of heat of combustion)
Hrº = Heat of combustion of reactant – Heat of combustion of reactant .
Hrº = HCº (Reactant) – HCº (Product)
Ex.2 The enthalpy change for the reaction
C3H8(g) + H2(g)  C2H6(g) + CH4(g) at 25ºC is – 55.7 kJ/mole calculate the enthalpy of
combustion of C2H6(g). The enthalpy of combustion of H2, and CH4 are – 285.8 and – 890.0 kJ/
mole respectively. Enthalpy of combustion of propane is –2220 KJmol–1.
Sol. As we know any thermochemical eqn can be written in terms of heat of combustion as follows
Hrº = Hcº (Reactant) – HCº (Product)
Hrº = Hcº (C3H8) + HCº (H2) – {Hcº(C2H6) + HCº(CH4) }

– 55.7 = (–2220 – 285.8) – {–890 +Hcº(C2H6) }
 Hcº(C2H6) (g) = – 1560.1 kJmol–1
Problems Based on Both HOC and HOF :

Ex.3 At 300K, the standard enthalpies of formation of C6H5COOH(s), CO2(g) and H2O(l) are –408, –
393 and –286 kJmol–1 respectively. Calculate the enthalpy of combustion of benzoic acid at
(i) constant pressure
(ii) constant volume.
Sol. 7C(s) + 3H2(g) + O2(g)  C6H5COOH(s) Hº = –408 kJ
 Hfº(C6H5COOH) = – 408 kJ
C(s) + O2(g)  CO2(g) Hº = –393 kJ
 Hfº(CO2) = –393 kJ
H2(g) + 1/2O2(g)  H2O(l) Hº = –286 kJ
 Hfº(H2O) = –286 kJ
C6H5COOH(s) + 15/2O2(g)  7CO2(g) + 3H2O(l)
HCº(C6H5COOH) = 7 HfºCO2 + 3Hfº(H2O) – 4Hfº(C6H5COOH)
= 7 ×(–393) + 3× (–286) + 408
HCº(C6H5COOH) = – 3609 + 408
= –3201 kJ/mol
enthalpy of combustion at constant pressure = – 3201 kJ mol–1
Also
H = U + ngRT
–3201 = U + (–0.5) × 8.31 × 10–3 × 300
(As n = 0.5, R = 8.314 × 10–3 kJ)
 U = – 3201 + 1.2471
U = –3199.7529
 enthalpy of combustion at constant volume = – 3199.7529
BOND ENERGY
It is defined for gaseous molecules. "The enthalpy change during the breaking of one mole of bond into
isolated gaseous atoms is called bond energy of the compound"
e.g. H2(g)  2H(g)
Hº = H  H
* ge fdlh Hkh reaction dks Heat of formation of product – Heat of formation of Reactant ds form esa fy[k ldrs gsa
vkSj vxj mij okys eqn dks Hkh oSls gh fy[kk tk;s rks
Hº =  H  H = 2H ºH(g) – H º(H )
f f 2
  H  H = 2H ºH(g)
f
 Hfº H(g) =
H  H
2
Similarly
HfºO(g) =
O  O
2
 NN
HfºN(g) =
2
* Let us consider the similar bond breaking In CH4
CH4(g)  C(g) + 4 H(g)
H = 4  C  H =H ºC(g) + 4H ºH(g) – H º(CH )

f f f 4
** Enthalpy of reaction in terms of bond energy for a thermochemical eqn can be written as
Hfº = B.E.(Reactant) – B.E. (products)
Ex.4 Using the bond enthalpy data given below, calculate the enthalpy change for the reaction
C2H4 (g) + H2(g)  C2H6(g)
Data :
Bond C–C C=C C–H H–H
Bond Enthalpy 336.81 606.68 410.87 431.79
(kJ/mol) (kJ/mol) (kJ/mol)
Sol. rHº =  reac tant   product

H º =  C  C  4 C  H   H  H   C  C  6 C  H
r
Hrº = 606.68 + 4×410.87 + 431.79 –336.81 –6×410.87

= 2681.95 –2802.03
Hrº = –120.08 kJ/mol
HEAT OF HYDROGENATION
"Enthalpy change during the addition of 1 mole of H2 to an unsaturated compound. is called heat of
hydrogentation."
Hydrogenation is an exothermic process. of therefore heat of hytdrogentaiton is always –ve.
e.g.
CH2 = CH2 + H2  CH3 –CH3
Hrº = Hº (Hydrogenation) (CH2 = CH2)
+ H2
 Hrº = Hº (Hydrogenation)

of cyclohexene
Ex.5 Compare the heat of hydrogenation of the following alkene

(1) C – C – C = C (2) C – C = C – C (cis) (3) C – C = C – C (trans)
(4) C – C = C (5) C = C – C = C
C
1
Sol. Stability of alkene 
Heat of hydrogenation
The above concept is true as long as no. of double bonds are equal as heat of hydrogenation is
defined for per mole of double bond. It will be certainly larger for higher number of double bonds
irrespective of their stability.
(1) C – C – C = C (2 × H)
(2) C – C = C – C ( 6 × H)
(cis)
(3) C – C = C – C (6 × H)
(trans)
C
(4) C=C (6 × H)
C
(5) C = C – C = C (2 double bonds)
As we know trans > cis (stability)
 Heat of hydrogen (trans) < Heat of hydrogenation (cis)
H
CH3 – CH = CH – CH3 CH3– CH –CH = CH2
(less stable) ( + I of CH3 reduce the stability)
CH3 H CH2 H
C=C C–C
CH3 H CH3 H
(more stable) (more stable as nothing is

trying to reduce its stability)
of therefore decreasing order of heat of hydrogenation of alkene

5>1>2>3>4>
Ex.6 Find Hf of HCl(g) if bond energies of H2, Cl2 and HCl are 104, 58, 103 kcal/mole respectively.
Sol. H – Cl  H(g) + Cl(g)
 H  Cl = H ºH(g) + H ºCl(g) – H ºHCl(g)

f f f
1 1
103 =
2  H  H + 2  Cl  Cl – H ºHCl(g)
f
1 1
103 = ×104 + ×58 – Hfº HCl(g)
2 2
HfºHCl(g) = – 22 kcal/mol.
HEAT OF ATOMISATION
" When one mole of any substance is converted into gaseous atoms enthalpy change during the
process is called heat of atomisation." It is always + ve due to endothermic nature of the process.
HEAT OF SUBLIMATION
Enthalpy change during the conversion of one mole of solid to 1 mole of gaseous phase directly
without undergoing into liquid phase is called enthalpy of sublimation or heat of sublimation,
It is always + ve due to endothermic nature of the process.
e.g.
C(s)  C(g)
Hº = HsubºC(s) = Hfº C(g) – Hfº C(s)
O
HsubºC(s) = Hfº C(g)
HsubºC(s) = Hfº C(g) =HºatmosationC(g)
Ex.7 Using the given data, calculate enthalpy of formation of acetone(g) [All values in kJmol–1]
bond enthalpy of C–H = 413.4, C – C = 347.0 (C = O) = 728.0

( O = O ) = 495.0 , H – H = 435.8 subH of C = 718.4
O
Sol. CH3 – C – CH3 3C(g) + 6H(g) + O(g)
O
6  C  H +  C  O + 2  C  C = 3H ºC(g) + 6H ºH(g) + H ºO(g) –
f f f
Hfº( CH3 – C – CH3 )
O
6 1
6 × 413.4 + 728 + 2 × 347 = 3 × 718.4 + × 435.8 + ×495.0 – Hfº( CH3 – C – CH3 )
2 2
O
Hfº( CH3 – C – CH3 ) = – 192.3 kJmol-1
Ex.8 The enthalpy of combustion of acetylene is 312 kcal. If enthalpy of formation of CO2 and H2O
are –94.38 and –68.38 kcal respectively
Calculate C  C bond enthalpy.
Given that enthalpy of atomisation of 150 kcal and H – H bond enthalpy and C – H bond
enthalpy are 103 kcal and 93.64 kcal respectively.
5
Sol. HC  CH + O  2CO2 + H2O
2 2
HCº(CH  CH) = 2Hfº(CO2) + Hfº(H2O) – Hfº(C2H2)
– 312 = 2 × (–94.38) + (–68.38) – Hfº(C2H2)
Hfº(C2H2) = 54.86
CH  CH  2C(g) + 2H(g)
 C  C + 2  C  H = 2H ºC(g) + 2H ºH(g) – H º(CH  CH)

f f f
1
C  C +2 × 93.64 = 2 × 150 + 2 ×
2
× 103 –54.86   C  C = 160.86 kJmol –1
RESONANCE ENERGY
"The energy difference between resonance hybrid and most stable canonical structure is called
resonance energy".
Resonance energy is always –ve as nature of the process is exothermic.
Ex.9 The enthalpy of formation of ethane, ethylene and benzene from the gaseous atoms are –
2839.2,
–2275.2 and –5506 kJmol–1 respectively. Calculate the resonance energy of benzene. The
bond enthalpy of C – H bond is given as equal to + 410.87 kJ/mol.
Sol. 2C(g) + 6H(g)  C2H6 Hº = –2839.2
C2H6  2C(g) + 6H(g) Hº = 2839.2
C – C + 6C – H = 2839.2 Hº = 2839.2
C – C + 6 × 410.87 = 2839.2
C – C = 373.98 ... (1)
2C(g) + 4H(g)  C2H4(g) Hº = –2275.2
C2H4  2C(g) + 4H(g) Hº = 2275.2
C = C + 4C – H = 2275.2
C = C) = 631.72 ...(2)
6C(g) + 6H(g)  C6H6 Hº = –5506

C6H6  6C(g) + 6H(g) Hº = 5506
 3C = C + 3C – C + 6C – H + x = 5506
Putting all the values from eqn , 1, & ( 2) we get x = 23.68
 Resonance energy of benzene = – 23.68 kJ/mole
BOMB CALORIMETER
O2 gas
w
mole w m gm of
M water
Heat evolved = mst + Ct


Heat capacity of container
ms t  Ct 
Heat of combustion = – w
 
M
M
=– ms t  Ct  = – M  tms  C = – M  t [C' + C]
w w w
Heat capacity Heat capacity

of water of container
M
 H = –  t  C  Heat capacity of system
w
Ex.10 When 1.0 gm of fructose C6H12O6 (s) is burnt in oxygen in a bomb calorimeter, the
temperature of the calorimeter water increases by 1.56ºC. If the heat capacity of the
calorimeter and its contents is
10.0 kJ/ºC. Calculate the enthalpy of combustion of fructose at 298 K.
Sol. Heat capacity of the system

M
HC = C  t 
w
180
= 10  1.56 = –2808 kJ/mole
1
HEAT OF SOLUTION
Enthalpy change during the dissolution of 1 mole of salt in excess of solvent.
KCl(s) + aq  KCl (aq)
Hº = Heat of soln of KCl (s)
Note :-
(1) Heat of solution is always exothermic for the anhydrous form of salts which can form their hydrates.
e.g. CuSO4, Na2SO4, FeSO4, ZnSO4, CaCl2, LiCl etc.
CuSO4(s) + aq  CuSO4(aq) H < 0
(2) Heat of solution is endothermic for the hdyrated form of the salt.
CuSO4 . 5H2O + aq  CuSO4(aq) H > 0
(3) Heat of soln is endothermic for the salts which do not form their hydrates.
e.g. NaCl, NaNO3, KCl etc.
INTEGRAL HEAT OF SOLUTION

Enthalpy change when 1 mole of salt is dissolved in given amount of solvent.
e.g. KCl(s) + 20 H2O  KCl (20H2O) _____________(1) H2 = x
KCl(s) + 100 H2O  KCl (100H2O) _____________(2) H2 = y
HEAT OF DILUTION
Reversing the eqn (1) and adding in (2)
KCl(20H2O) + 80H2O  KCl(100H2O)
H = y – x
enthalpy change when the conc. of salt changes from one to another on the basis of dilution
 H = y – x = Heat of dilution
HEAT OF HYDRATION
Ethalpy change during the formation of hdyrated form of salt from its anhydrous form. It is always
exothermic.
CuSO4(s) + 5H2O  CuSO4.5H2O
H = Heat of hydration of CuSO4(s)
Ex.11 Heat of soln of CuSO4(s) and CuSO4.5H2O is 15.9 and 19.3 kJ/mol respectively. Find the heat
of hydration of CuSO4(s)
Sol. CuSO4(s) + aq  CuSO4(aq) ___________(1)
H = –15.9
CuSO4.5H2O + aq  CuSO4(aq) ___________(2)
H = 19.3
Reversing eqn (1) and adding (2)
CuSO4(s) + aq  CuSO4(aq)
H = 15.9
CuSO4.5H2O + aq  CuSO4(aq)
H = 19.3
______________________________________________
CuSO4.5H2O  CuSO4(s)
H = 35.2
 CuSO4(s)  CuSO4.5H2O
H = –35.2
 Heat of hydration of CuSO4(s) = –35.2 kJ/mol
HEAT OF NEUTRALISATION
Enthalpy change during neutralisation of 1 gm equivelant of Acid with 1 gm equivelant of base in
dilute soln is called heat of neutralisation.

HCl(aq) + NaoH(aq)  NaCl + H2O
H+ + Cl– + Na+ + OH–  Na+ + Cl– + H2O
H+(aq) + OH–(aq)  H2O(aq)
Hº = –13.7 Kcal
H2SO4(aq) + 2NaOH(aq) Na2SO4 + 2H2O
2H+ + SO42– + 2Na+ + 2OH–  2Na+ + SO42– + 2H2O
2H+ + 2OH–  2H2O
H = –13.7 × 2
Note :-
In case of weak Acid or weak bases the observed value is little lower because of a part of it is used
in dissociating weak Acid or weak base which is not at all completely ionised at dilute solution
unditions.
These are however, completely ionised at infinite dilution. e.g.
CH3COOH + NaOH  CH3COONa + H2O
H = –13.7 + x
As we know, H+ + OH–  H2O H = –13.7 kcal ____(1)
– +
CH3COOH  CH3COO + H Hº = x ____(2)
Add eqn (1) + (2)
__________________________________
CH3COOH  OH–  CH3COO– + H2O Hº = y
Ex.12 100 ml 0.5M H2SO4(strong Acid) is neutralised by 200 ml 0.2 M NH4OH. In a constant pressure
calorimeter which results in temperature rise of 1.4ºC. If heat capacity of calorimeter
constant is
1.5 kJ/ºC.
Which statement is/are correct.
Given: HCl + NaOH NaCl + H2O + 57 kJ
CH3COOH + NH4OH  CH3COONH4 + H2O + 48.1 kJ
(A) Ethalpy of neutralisation of HCl v/s NH4OH is –52.5 kJ/mol
(B) Ethalpy of dissociation (ionisation) of NH4OH is 4.5 kJ/mol
(C) Ethalpy of dissociation of CH3COOH is 4.6 kJ/mol
(D) H for 2H2O(l)  2H+(aq) + 2OH–(aq) is 114 kJ
Sol. (A) Total heat evolved due to the neutralization = C × t = 1.5 × 1.4 = 2.1
M. eq of H2SO4 = 100 ×0.5 = 50
M.eq of NH4OH = 20 × 0.2 = 40
Since NH4OH is limiting hence energy will evolved according to it.
 0.04 gm eq produces 2.1 kJ
2 .1 210
1 gm eq produces = 1 = = 52.5
0.04 4
 Heat of neutralisation = –52.5 kJ
(B) –57 + x = – 52.5
 x = – 52.5 + 57 = 4.5
 Enthalpy of dissociation of NH4OH = 4.5 kJ/mol
(C) 57–(x + y) = 48.1

 x + y = 8.9
 4.5 + y = 8.9  y = 4.4

 enthalpy of dissociation of CH3COOH = 4.4 kJ/mol
(D) As we know
H+ + OH–  H2O H = –57
+ –
 2H + 2OH  2H2O H = –57× 2
 2H2O  2H+ + 2OH– H = 114 kJ
 Option A, B, and D are correct.
BORN HABER CYCLE

Ionisation Energy :-
The minimum amount of energy required to remove one electron form the outermost shell of an
isolated gaseous atom is called ionisation energy of the element.
Electron affinity:-
Amount of energy released when an extra electron is added to an isolated gaseous atom.
Lattice Energy :
Amount of energy released when 1 mole of gaseous cation and 1 mole gaseous anion combine to
each other and form 1 mole of ionic compound is called lattice energy.
Na+(g) + Cl–(g)  NaCl(s) + heat

Lattice energy
q1q 2
Hlattice  2
r 
 r 
Ex.13 The born-Haber cycle for formation of rubidium chloride ((RbCl) is given bellow (the
enthalpies are in kcal mol–1)
1 105
Rb(s)  Cl2 (g)   RbCl(b)
2
+20.5 –159.5
28.5
+
Rb (g)
Rb(g)
Cl(g)  Cl(g)
X
96.0
find the value of X?

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STOICHIOMETRY - 1 Page # 3

LAWS OF CHEMICAL COMBINATION

(a) Law of conservation of mass [Lavoisier]

(b) Law of constant composition [Proust]

(c) Law of multiple proportions [Dalton]

(d) Law of reciprocal proportions [Richter]

At. Mass 1 At. Mass 32

(e) Gay Lussac law of combining volumes :

METHODS OF CALCULATIONS OF MOLE

RELATIONSHIP BETWEEN GRAM AND AMU

Ex.2 Calculate the following for 49 gm of H2SO4

(b) Since 1 mole = 6.023 × 1023 molecules.

AVERAGE ATOMIC WEIGHT

EMPIRICAL FORMULA, MOLECULAR FORMULA

Empirical formula : Formula depicting constituent atom in their simplest ratio.

156 + 12 + 48 + 3.02 + 10 –23 NA

density of subs tan ce

density of subs tan ce

Vapour density : It is defined only for gas.

dgas PMgas / RT Mgas M

• density of Cl2 gas with respect to O2 gas

Molecular wt of Cl2 gas

• STOICHIOMETRY : Stoichiometry is the calculations of the quantities of reactants and products

• CONCEPT OF LIMITING REAGENT.

Ex.11 In the gravimetric determination of phosphorous, an aqueous solution of dihydrogen phosphate

SOME EXPERIMENTAL METHODS

FOR DETERMINATION OF ATOMIC MASS

FOR MOLECULAR MASS DETERMINATION

(a) Victor Maeyer’s process : (for volatile substance)

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

This is one good practicle application of POAC.

• For % determination of elements in organic compounds :

(b) Duma’s method : (for nitrogen)

use PV = nRT to calculate moles of N2, n.

(c) Kjeldahl’s method : (for nitrogen)

• Flourine can’t be estimated by this

Since Ag atoms are conserved, applying POAC for Ag atoms,

Mass of solute Mass of solute

VOLUME STRENGTH OF H2O2

Volume, strength of H2O 2

100 1000 500

RELATION SHIP BETWEEN MOLARITY, MOLALITY & DENSITY OF SOLUTION

RELATION SHIP BETWEEN MOLALITY & MOLE FRACTION

mole fraction of A 1000

mole fraction of solute 1000

Second Method : Let wt of solvent = 1000 gm molality = 1.33

OXIDATION & REDUCTION

Both oxidising & Reducing Agents :

Nature of Oxides Based on Oxidation Number :

Average Oxidation Number : Find Oxidation Number of Fe in Fe3O4.

(A) Volumetric analysis :

(I) Non-redox system

Titrimetric Method of Analysis :

Law of Chemical equivalence :

Weight of ' A'

(2) In case of redox reaction.

Ex.5 Find the n factor of KMnO4 in different medium.

Ex.6 Find the n factor of Na2S2O3 in the following reactions.

n factor of overall reaction = n1 × n2 / n1 + n2

(b) From ion electron method :

Total mass of NaOH available = 500 × 2 × 10–3 = 1.0 mole

CALCULATION OF AVAILABLE CHLORINE FROM A SAMPLE OF BLEACHING POWDER