Escolar Documentos
Profissional Documentos
Cultura Documentos
STOICHIOMETRY
v v STOICHIOMETRY
v v
Synopsis...
PART - I
(Laws of chemical combination, amu, Atomic and molecular masses, average
atomic mass, gm. atom & gm.molecule)
2g
H
H2S H2O
S O
32g 16g
i) N 2 g 3H 2 g
2 NH 3 g
1vol 3vol 2vol
i.e, One volume of N2 reacts with three volumes of H2 to give two volumes of NH3.
iii) H 2 g Cl2 g
2 HCl g
1vol 1vol 2vol
CAPS-5 : How much volume of oxygen will be required for complete combustion of 40ml of acetylene
(C2H2) and how much volume of CO2 will be formed ? All volumes are measured at NTP ?
Sol : 2C2 H 2 5O2
4CO2 2 H 2O
2vol 5vol 4vol
1
1 amu = 1.9924 1023 1.66 1024 g 1.66 1027 kg
12
ATOMIC MASS
Atomic mass of an element can be defined as The number, which indicates how many times, the
1
mass of one atom of the element is heavier in comparision to th part of the mass of one atom of
12
C-12.
Mass of one atom of the element
Atomic mass of an element 1
Mass of one atom of C 12
12
Mass of one atom of the element
Atomic mass of an element
1amu
The atomic masses of some elements on the basis of C-12 are given below:
Hydrogen : 1.008 amu 2. Oxygen : 16 amu
Chlorine : 35.5 amu 4. Magnesium : 24 amu
Copper : 63.5 amu 6. Iron : 55.847 amu
Sodium : 22.989 amu 8. Silver : 107.868 amu
Nitrogen : 14 amu 10. Sulphur : 32 amu
ACTUAL MASS OF AN ATOM
The actual mass of an atom (absolute mass) of an element =
The atomic mass of an element in amu 1.66 1024 g
number is known as Avogadros number N A , named in the honour of Amedeo Avogadro (1776-
1856)
Note : Mass of one atom of C-12 isotope 1.9924 1023 g
12
Number of atoms present in 12g of C-12
1.9924 1023 6.023 10
23
So, one gram atom of every element consists of Avogadro number of atoms.
GRAM - MOLECULAR MASS (OR) GRAM MOLECULE
A quantity of substance whose mass in grams is numerically equal to its molecular mass is called
gram molecular mass.
In other words, molecular mass of a substance expressed in grams is called gram molecular mass or
gram molecule.
For Example :
i) The molecular mass of chlorine is 71 amu and therefore, its gram - molecular mass (or) gram
molecule is 71g.
ii) Molecular mass of O2 is 32 amu gram molecular mass of O2 = 32g.
iii) Molecular mass of nitric acid ( HNO3 ) = 1 14 (3 16) 63 amu
Gram - molecular mass of nitric acid = 63g
Note : Gram - molecular mass should not be confused with the mass of one molecule of substance in gms.
For example: Gram - molecular mass of oxygen is 32 gms where as mass of one molecule of oxygen
is 32 1.66 1029 g
CAPS-8
1. Calculate number of gram atoms in:
a. 48 gm of O2 b. 8 gm of H2
Solution:
a. one gm. atom of oxygen - 16 gms
? - 48 gms
48
No.of gm atoms = =3 gm. atoms
16
b. 1gm of H2 - 1 gm. atom.
8 gm of H2 - ?
8 gm atoms.
2. Calculate the number of atoms present in
a. 6g of Mg b. 8 gm of O2
Solution:
a. 24gm of Mg contains - NA of atoms (1 gm atom)
6 gm of Mg contains - ? atoms
6 1
N A 6 1023 1.5 1023
24 4
b. 16gm of oxygen contains - NA of atoms (1 gm atom)
4 gm of oxygen contains - ?
4 1
N A 6 1023 3 1023 atoms
8 2
3. Calculate the mass of
a. 1.5 gm of atom of Cl2 b. 2 gm atoms of sodium
Solution:
a. 1 gm atom of Cl2 - 35.5 g
1.5 gm atom of Cl2 = 1.5 35.5 50.45gm
b. 1 gm atom of Sodium - 23g
2 gm atoms of sodium = 23 2 46gm
PART - 2
(Mole concept)
Mole:
Just like for the counting of articles, the unit dozen is commonly used irrespective of their nature, similarly
chemists use the unit mole for counting of atoms, molecules, ions etc.
The mole was introduced by ostwald in 1896.
This is the Latin word moles meaning heap or pile.
A mole is defined as the number of atoms in 12.00g of carbon - 12.
The number of atoms in 12g of C - 12 has been found experimentally to be 6.023 1023 .
12
Number of atoms in 12g of C - 12
Mass of an atom of C 12
12
23
1.9924 10 23 6.023 10
4.5
Sol. Number of moles 0.25mol.
18
18g of H 2O contains ______10 N A of electrons
4.5g of H 2O contains ______ ?
4.5
10 N A of electrons
18
=2.5 6 1023
1.5 10 24 electrons.
3. Calculate the charge present on 1 mole of electrons.
Sol. Charge on one electron = 1.609 10 19 coloumbs.
PART-3
(Percentage composition of elements in a compound - Emperical formula and Molecu-
lar Formula)
Percentage composition of compounds :
The composition of any compound represents the relative amount of all the constituent elements by weight.
ZA
Percentage of an element = 100
M
where,
Z = No. of atoms of that element in each molecule
A = atomic weight of the element
M = molecular weight of the compound
The percent analysis of a substance is useful to determine the formula of unknown compound.
Eg. i) In H2O : M H 2O = 18
24
i) % of Mg = 100 9.75%
246
32
ii) % of S = 100 13.00%
246
176
iii) % of O = 100 71.54%
246
14
iv) % of H = 100 5.69%
246
126
v) % of H2O = 100 51.21%
246
Molecular formula of any compound represents the exact number of atoms of different elements present in
each molecule of the compound.
Emperical formula of any compound represents the simplest atomic ratio of the different elemetns present
in the compound.
Conversion
Mole ratio = % Simple mole
Element % composition into whole E. F
atomic mass ratio
number
Write % If simple mole
composition ratio are
Write the Write the whole
here. If sum% Divide all the fractional, thus
symbols of Divide % of no.s obtained as
given is not 100, mole ratio by multiply all with
elements element by subscript with
then subtract smallest mole same number to
present in the atomic weight the symbols of
this sum from ratio convert into
molecule elements
100 and use it as whole no. or
oxygen % nearly whole no
Example : An oxide of iron contains 69.94% Fe and 30.06% O. Determine its E.F (Fe : 55.85 ; O = 16.0)
Solution :
% Simplemole Whole
Element Moleratio E. F
composition ratio no. ratio
69.94 1.25
Fe 69.94 1.25 12 2
55.85 1.25
Fe2O3
30.06 1.88
O 30.06 1.88 1.52 3
16 1.25
CAPS - 13 :
1. Calculate the M.F of a hydrocarbon which contains 85.7% carbon and has molecular mass 84
Sol :% C = 85.7 and % H = 14.3
This data gives E. F compound to be CH2
Moleof H 2O
x (or) 0.887/18 x x 2
Moleof BaI 2 9.520/ 391
Quantitative estimations :
Determination of % analysis of elements in organic compounds or quantitative estimation of elements in
organic compounds.
I. Estimation of C and H :
A known weight of organic compound is burnt in oxygen and the products H2O and CO2 formed are
absorbed in conc. H2SO4 and KOH(aq) respectively. The % of C and H are obtained using the formulae.
2 weight of H 2O
% H 100
18 weight of organic compound
12 w eight of C O 2
% C 14 w eight of organic com pound 100
12 0.528
= 100 61.07%
44 0.236
2 weight of H 2O
% of H 100
18 weight of organic compound
2 0.324
= 100 15.25%
18 0.236
28 Volume of N 2 at STP
% of N 100
22, 400 weight of organic compound
28 56
100 23.73%
22, 400 0.295
E.F CH
PART - 4
(Chemical Stoichiometry : Calculations based on chemical equations)
Introduction:
Chemical stoichiometry describes the quantitative realtionships that exist between substances undergoing
chemical changes.
A chemical equation represents an actual chemical change in terms of symbols / formula of reactants and
products.
If the number of atoms in reactant side and product side are not same then reaction is said to be unbal-
anced.
Eg : H 2 O2 H 2O
If the number of atoms in both sides are equal then reaction is said to be balanced.
The numbers written before atoms / molecules in a balanced chemical equation are known as Stoichio-
metric coefficients.
All the chemical equations can be treated as algebraic equations and coefficient 1 is not written.
Eg : 1 2 H 2 1 2 Cl2
HCl
(or) H 2 Cl2
2 HCl
(or) 2 H 2 2Cl2 4 HCl
Thus, a balanced chemical equation shows conservation of mass and atoms only.
Significance of chemical equations :
A chemical equation provides qualitative and quantitative details of a chemical reaction. A balanced chemi-
cal equation gives following informations about ratio of the reactants and products.
i) Mole ratio ii) Molecules ratio iii) Mass ratio iv) Volume ratio
Eg : Consider a balanced chemical equation as
aA bB cC dD
Sr. INTER IIT-JEE MATERIAL :: 17 ::
CHEMISTRYv v v v v v v v v v v v v v v v v v v v v v v v STOICHIOMETRY
This equation gives information about
i) Mole ratio :
a mole A b mole B c mole C d mole D
Here symbol signifies
Stoichiometryically equivalent to.
ii) Molecules ratio :
a x NA molecules of A b x NA molecules of B
c x NA molecules of C
d xNA molecules of D
iii) Mass Ratio :
a M A g of A b M B g of B c M C g of C
d M D g of D
MA , MB , MC , MD are molar masses of A, B, C and D respectively.
iv) Volume ratio :
When all reactants and products are gases.
a vol A b vol B c vol C d vol D
Consider for example, the reaction represented by a balanced chemical equation
N2 g 3H2 g
2NH3 g
It is thus evident that the coefficients in a balanced chemical equation can be interpreted as the relative no.
of moles, molecules or volume involved in the reaction.
The stoichiometric relation can be used to given conversion factors for relating quantities of reactants and
products in a chemical reaction.
The chemical stoichiometric problems may be classified on the following relationship.
a) Weight - Weight relationship - Gravimetric Analysis
b) Weight - volume relationship
c) Volume - volume relationship
i) For gases - gas analysis (or) Eudiometry
ii) For solutions - Volumetric analysis (or) titration
NOTE : Eudiometry and volumetric analysis will be discussed separately.
Methods of solving stoichiometric problems :
1. Mole Method (Based on mole concept)
Step - I : Write the complete and balanced reaction concerned.
Step - II : The stoichiometric coefficients in the balance reaction represents the relative number of moles of the
different reaction components concerned, with the help of mole.
Step - III : Use unitary method to get required amount.
Sol : C2 H 6 7 2 O2
2CO2 3H 2O
1 mol 2 mol
= 30 gm 2x44 gm
30gm C H
2 6
produces 2x44gm CO2 on complete combustion.
2 44
1.5gm C2H6 will produce 1.5 4.4 gm CO2
30
2. Principle of atomic conservation (POAC) method :
As the reactions are balanced by conserving the atoms of each element, the mole method may be applied
to such calculations, without balancing the reaction.
The solution of above problem may be done by POAC method as :
Moles of C - atoms in C2H6 = moles of C-atoms in (or) 2 x mole of C2H6 = 1 x mole of CO2
1.5 w
2 1 w 4.4 gm
30 44
3.Based on Equivalent concept (Equivalent method)
The number of gm equivalents of each reactants reacted will remain the same and the same number of gm
equivalents of each product will form.
The solution of above problem may be done by equivalent concept as :
No.of gm equivalents of C2H6 = No. of gm equivalents of CO2
1.5 w
w 4.4 gm
30
14
44
7
[Note : Equivalent method based problems are done thoroughly further in equivalent weights concept].
Problem solving based on mole concept :
I. Calculations based on mass - mass relationship :
In such calculations, masses of reactants are given and mass of the product is required and vice - versa.
CAP-17. Calculate the number of grams of MgCl2 that could be obtained from 17.0g of HCl, when HCl is
reacted with an excess of magnesium oxide.
Sol : Balanced equation,
M gO 2 H C l
M gC l 2 H 2 O
1m ol 2 m ol 1m ol 1m ol
(2 36.5) g (24 71) g
73 g 95 g
Sol : NH 4Cl S
NH 3 g HCl g
1mol 1mol
53.5 g 1mol
53.5g NH4Cl will give
1
26.25 mole NH 3 = 0.5 mole
53.5
From, PV = nRT
1 V 0.5 0.0821 300
V = 12.315lit
CAP-20. Calculate the volume of H2 liberated at 27C and 760mm pressure by treating 1.2g of Mg with excess
of HCl.
Sol : Mg 2 HCl
MgCl2 H 2
1mol 1mol
24 g 22.4 L at STP
24g Mg liberates
22.4 L of H2
22.4
1.2g Mg will liberate 24 1.2 1.12L
Volume of H2 under given conditions can be calculated by applying :
PV
1 1 PV
2 2
T1 T2
P1 = 760mm P2 = 760mm
T1 = 273K T2 = 27 + 273 = 300 K
V1 = 1.12 L V2 = ?
760 1.12 300
V2 = =1.2308 L
273 760
III. Calculations based on volume - volume relationship
These calculations are based on two laws :
i) Avagadros law ii) Gay - Lussacs law
For example :
N 2 g 3H 2 g
2 NH 3 g Avagadro ' s law
1mol 3mol 2mol
1 22.4 L 3 22.4 L 2 22.4 L
Under similar conditions of temperature and pressure, equal moles of gases occupy equal volumes.
N 2 g 3H 2 g
2 NH 3 g
1vol 3vol 2vol
Under similar conditions ratio of coefficients by mole is equal to ratio of coefficient by volume.
CAP-21.What volume of air containing 21% oxygen by volume is required to completely burn 1kg of carbon
containing 100% combustible substances ?
Sol : C s O2 g
CO2 g
1mol 1mol
12 g 22.4 L
1000g ?
1000
22.4lit
12
100L of air contains
21L of O2
1000
?
22.4 L of O2
12
1000 22.4
100 8888.5 L of air
12 21
CAP-22. What volume of O2 gas at NTP is necessary for complete combustion of 20lit of propane measured at
27C and 760mm pressure ?
Sol : C 3 H 8 +SO 2
3CO 2 +4H 2 O
1vol 5 vol
1L 5L
1L of propane requires
5L of O2
20L of propane will require
5 20 100 L of O2 at 760mm and 27C.
This volume will be converted to STP conditions.
Given conditions STP conditions
P1 =760mm P2=760mm
V1=100lit V2 = ?
T1 = 27 + 273 = 300K T2 = 273
PV
1 1 PV 760 100 273
2 2 V2 91L
T1 T2 300 760
Sol : xg (2 x) g
CaCO3 MgCO3
}
2g
CaCO3 H 2 SO4
CaSO4 CO2 H 2 O
1mol 1mol
100g 98g
xg 98
x
100
PART - 5
(EUDIOMETRY)
Eudiometry or gas analysis involves the calculations based on gaseous reactions in which the amounts
of gases are represented in volumes, measured at the same pressure and temeprature. Some basic
assumptions related with calculations are :
1. Gay - Lussacs law of volume combination holds good. According to this law, the volumes of gaseous
reactants reacted and the volumes of gaseous products formed, all measured at the same temperature and
presume, bears a simple ratio.
N 2g 3 H 2g
2 N H 3 g
1vol 3vol 2vol
Problem may be solved directly in terms of volume, in place of mole.
2. For non-reacting gaseous mixture, Amagats law holds good. According to this law, the total volume of a
non-reacting gaseous mixture will be equal to sum of partial volumes of all the component gases.
V = V1 + V2 + ..............
3. The volume of solids or liquids is considered to be negligible in comparison to the volume of gas.
2 H 2g O 2g
2 H 2 O l
2mole 1mole 2mole
2vol 1vol 0vol
4. Air is considered as a mixture of oxygen and nitrogen gases only.
5. Nitrogen gas is considered as an unreative gas.
The problems will be of two profiles
1) Amount determination
2) Molecular formula determination
AMOUNT DETERMINATION
CAP-40. 40ml of a mixture of C2H2 and CO is mixed with 100 ml of O2 gas and the mixture is
exploded. The residual gases occupied 104 ml and when these are passed through KOH solu-
tion, the volume become 48 ml. All the volume are at same the temperature and pressure.
Determine the composition of original mixture.
Sol : Let the mixture contains x ml C2H2 . The volume of CO becomes (40 - x) ml.
5
C2 H 2 + O 2
2CO 2 +H 2 O
2
5
1vol. vol 2vol 0vol
2
5
x ml x ml 2x ml 0
2
2 C O + O2
2CO 2
2vol 1vol 2vol
1
(40 - x)ml (40 - x) (40 - x)ml
2
In this problem, unknown is only one but number of informations are more. Hence, the problem may be
solved by different methods. Some of them are :
Method - I : Residual volume = vol. of O2 unreacted + vol. of CO2 formed
5 1
10.4 100 2 x 2 40 x 2 x 40 x
5 1
10.4 100 x
2 2
x = 16
Method - II : When the residual gases are passed through KOH solution, the volume contracted from 104 ml
to 48 ml. It is due to absorption CO2 gas formed. Hence,
Volume of CO2 formed = (104 - 48) ml
2x + (40 - x) = 56
x = 16
y y
Cx H y x O2
x CO2 H 2O
4 2
y
1 vol x vol x vol 0 vol
4
From equation,
vol. of CO2 formed = 60 ml
or. 20x = 60
x=3
and. vol. of O2 used = 100 ml
y
20 x 100
4
y=8
Hence, the hydrocarbon is C3H8
CAP-43. When a gaseous, olefinic hydrocarbon is burnt completely in excess of oxygen, a contrac-
tion in volume equal to double the volume of hydrocarbon is noticed. Identify the hydrocarbon.
Sol : Let the molecular formula of olefinic hydrocarbon is CxH2y and its V ml is burnt completely.
3x
Cx H 2 y O2
xCO2 xH 2O
2
3x
1vol vol x vol 0 vol
2
3x
V ml .Vml x. Vml 0
2
The contraction in volume is
3x x
V .V x.V V 1 ml
2 2
x
From question, V 1 2V
2
x=2
Hence, the hydrocarbon is C2H4 (Ethene)
CAP-44. At high temperature, gaseous S4N4 decomposes into nitrogen gas and sulphur vapours. It
is found that for each volume of S4N4 decomposed, 2.5 volume of total gaseous products are
formed. Determine the molecular formula of sulphur vapour.
Sol : Let the molecular formula of sulphur vapour is Sx
xS 4 N 4
4S x 2 x N 2
x vol. 4 vol. 2x vol
1vol. 4/x vol. 2 vol.
4
Total Vol of products = 2 vol.
x
But, from question, it should be 2.5 vol.
PART-6
(Oxidation states and Redox Reactions)
OXIDATION - REDUCTION:
OLD CONCEPT
Oxidation is the process involving addition of oxygen or removal of hydrogen or both. Emamples:
Fe FeO (Addition of oxygen)
CH 3CH 2OH CH 3CHO (removal of hydrogen)
CH 3CH 2OH CH 3COOH (both)
Reduction is just reverse process. It involves addition of hydrogen or removal of oxygen or both.
ZnO Zn (removal of oxygen)
C2 H 4 C2 H 6 (addition of hydrogen)
CH 3COOH CH 3CH 2OH (both)
This concept have the following drawbacks
a) It includes only the reactions involing oxygen and hydrogen atoms. For example
Fe FeO and Fe FeCI 2
Both the processes are similar because iron is forming a compound in which its valency is two.
The first process is oxidation but second process is not, it does not involve oxygen or hydrogen
atoms.
b) There may be some process involving oxygen and hydrogen atoms but can not be classified as
oxidation or reduction.
CH 2 CH 2 CH 2 CH 2
OH OH
The process involves addition of oxygen as well as hydrogen and hence it cannot be classified as oxidation
or reduction by this definition.
The old definition may be modified by replcing oxygen atom with electronegative atom or group and replac-
ing hydrogen atom with electropositive atom or group.
Fe FeCI 2 (Oxidation, addition of Cl atoms)
CH 2 CH 2 CH 2 CH 2
(Oxidation, addition of -OH groups)
OH OH
reduction
Fe Cl2 FeCl2
Oxidation and reducation are always simultaneous process.
Oxidation
MODERN CONCEPT
In terms of electrons : Oxidation is the process involving loss of electrons and reduction is the process
involving gain of electrons. Examples
Zn Zn 2 2e (Oxidation)
2Cl- Cl2 2e (Oxidation)
Cu 2 2e Cu (Reduction)
MnO4 8H 5e Mn 2 4 H 2O (Reduction)
17 p 17 p
Cl Cl
Electrons except shared electrons 16e 16e Hence, O.S. of Cl= 0
Shared electrons 2e
Electrons redistribution 1e 1e
Net charge 0 0
(iii) H2O2 molecule
1p 8p 8p 1p
H O O H
Electrons except shared electrons 0e 6e 6e 0e Hence, O.S. of H = +1
2e 2e 2e
Shared electrons
Electorns redistribution 2e 2e O.S. of O = 1
1e 1e
Net charge +1 -1 -1 +1
8p 6p 8p
O C O
6e 2e 6e
Shared electron 4e 4e Hence O.S.of C = + 4
Electron redistribution 4e 4e O.S.of O = -2
Net charge -2 +4 -2
The re-distribution of electron may be made simply by assuming the covalent bonds, ionic and assigning the
charge on atoms on the basis of electronegativities and bond order.
(v)H2SO4 molecule
-2
O
+1 +1 O.S.of H = + 1
+2 -1 -1
H -1 -1
O +1 S +1 O H S = +6
+2 O = -2
-2
O
I I2
Substances in which, the central atom is neither in minimum nor in maximum O.S. can behave like
both O.A. and R.A., both. Some examples are
as O.A 2
C
2
CO
H 2 O 2 acts 4
as R.A.
as O.A. CO 2
H 2O
1
H 2 O2 H 2O2 acts
as R.A. 0 as O.A 2
O2 S
4
SO 2
as R.A. 6 6
SO3,SO24
b) Cl2 OH Cl ClO3 H 2O
Step I: Oxidation: Cl 2 ClO3
Reduction: Cl 2 Cl
Step II: Oxidation: Cl 2 2ClO3
Reduction: Cl 2 2Cl
Step III: Oxidation: Cl2 12OH 2ClO3 6H 2O
Reduction: Cl 2 2Cl
Step IV: Oxidation: Cl2 12OH 2ClO3 6H 2O 10e
Reduction: Cl2 2e 2Cl
Step V: Oxidation: Cl2 12OH 2ClO3 6H 2O 10e
Reduction: [Cl2 2e 2Cl ] 5
________________________________________________
6Cl2 12OH 2ClO3 6H2O 10Cl
or, 3Cl2 6OH ClO3 5Cl 3H 2 O is the balanced reaction
Step III onwards may be replaced as
Step III: Oxidation: Cl 2 6H 2 O 2ClO3 12H
Reduction: Cl 2 2Cl
Step IV: Oxidation: Cl2 6H 2O 2ClO3 12H 10e
Reduction: Cl2 2e 2Cl
Step V: Oxidation: [Cl2 6H 2 O 2ClO3 12H 10e] 1
Reduction: [Cl 2 2e 2Cl ] 5
______________________________________________
6Cl2 6H 2 O 2ClO3 10Cl 12H
or, 3Cl2 3H 2 O ClO3 5Cl 6H
To remove H ion, add equal number of OH ions on both sides.
3Cl2 3H 2O 6OH ClO3 5Cl 6H 6OH
or, 3Cl2 3H 2O 6OH ClO3 5Cl 6H 2 O
or, 3Cl2 6OH ClO3 5Cl 3H 2 O is the balanced reaction.
M Na 23
Eg: i) E Na 23.
1 1
M Al3 27
ii) E Al3 9
3 3
M Na 2 40
iii) E Ca 2 20
2 2
M Cl 35.5
iv) E Cl 35.5
2 1
M SO 2 96
v) E SO 2 4
48
4
2 2
M PO 3 95
vi) E PO 3 4
31.67
4
3 3
M NO 30
vii) E NO 30
1 1
III Equivalent weight of a salt:
It is the number of gms of the salt formed by transfer of 1 mole electron. Hence.
Molecular weight of the salt
E Salt
no.of e transferred in salt formation
Molecular weight
no.of metal atoms Its valency
Formula mass of salt
133.5
iv) E AlCl3 44.5 (or) E E Al3 E Cl 9 35.5 44.5
3 1
106
v) E Na 2CO3 53 (or) E E Na E CO2 23 30 53
2 3
100
vi) E CaCO3 50 (or) E E Ca 2 E CO2 20 30
2 3
310
vii) E Ca 3 ( PO 4 )2 51.67 (or) E E Ca 2 E PO3 20 31.67 51.67
3 2 4
342
viii) E Al2 (SO4 )3 57 (or) E E Al3 ESO2 9 48 57
3 2 4
98
iii) E H2SO4 98 1 E HSO2 1 97 (where one H is replaced)
1 4
60
iv) E CH3COOH 60 1 E CH COO 1 59
1 3
63
v) E HNO3 63 1 E NO 1 62
1 3
Note:
In oxy acids only those hydrogens are acidic which are attached to oxygen directly.
Oxyacids are having at least one = 0 group and one OH group with the central atom Eg: H 3 PO 4 .
If reaction is not given, equivalent mass of an acid is defined for complete neutralization.
M 98 95
vi) E H3PO4 32.66 1 E PO3 1
3 3 4
3
1 31.66
O
||
HO P OH :Maximum 3 replaceable H 's in H PO
|
3 4
OH
M 82
vii) E H3PO3 41 1 E HPO2 1 40
2 2 3
O
||
M
viii) E H3PO2 66 1 E H PO 1 65
1 2 2
O
||
17
f) E NH3 17
1
[acidity of NH3 is 1:
NH 3 H 2 O NH 4 OH NH 4 OH
NH 3 HCl NH 4 Cl ].
VI Equivalent mass of an acidic salt:
An acid salt is that which contains replaceable hydrogen atoms, eg.
NaHSO4 , NaHCO3 , NaH 2 PO4 , Na 2 HPO4 etc.
Molecular weight
E acid salt replaceable ' H 'left in the salt
NOTE: The number of e s lost or gained or change in O.St should be according to the number of atoms of
responsible element present in the respective molecule or ion of the O.A.
CAP-52. Determine the equivalent weight of the following oxidising agents:
I KMnO 4 (reacting in acidic medium)
MnO 4 converts to Mn 2 in acidic medium.
i) O.St Method:
7
Mn O 4
H
Mn 2
Change in O.St 2 7 5
M 158
E MnO4 31.6
5 5
ii) e method:
MnO 4 8H 5e Mn 2 4H 2 O
1 mole of O.A gains 5 moles of e s n.factor 5
M 158
E MnO4 31.6
5 5
Change in O.St=2
Cl2 Cl ClO
Change in O.St=2
M M
ECl 2 E1 E2 M 71g
2 2
(ii) Equivalent weight of Cl2 with hot & conc.alkali
n2 10
Cl2 Cl ClO3
n1 2
M M M M 3M
ECl2 E1 E2 n n 2 10 5
1 2
3
71 42.6 g
5
n2 4
S2 SO 2 S
n1 2
M M 3
E S E1 E 2 32 24g
2 4 4
III Equivalent weight of a substance that is thermally decomposed:
change in O.St 6
oxidation
5 1
2K C lO32 2KC l 3O 2
Eg(i)
change in O.St 6
Re duction
oxidation
Change in O.St 2
5 1 3 0
PCl 5 PC l3 Cl 2
Eg(ii)
Re duction
change in O.St 3
n2 2
2 3 4
H
FeC 2 O 4 Fe3 CO 2
n1 1
M 142
47.33
3 3
Eg(ii) Equivalent weight of FeS2 in the half reaction,
Re duction
n 2 10
2 1 3 4
FeS2 Fe2 O3 SO 2
oxidation
n1 1
M M 118
E FeS2 n n 11 11 10.73
1 2
Equivalent volume:
It is volume occupied by the gaseous substance at STP corresponding to its gm equivalent weight.
22.4 L
Equivalent volume = .
n factor
Where n-factor is the factor by which molecular weight of the substance is divided to get its equivalent
weight.
Examples:
Determine the equivalent volume of the following gaseous compounds.
a) H 2 gas b) O2 gas c) Cl 2 gas
2 22.4
a) H 2 gas : E.wt.of H2 1g Eq.vol of H 2 gas = 11.2 lt
2 2
71 22.4
b) Cl 2 gas : E.wt of Cl2 35.5g Eq.vol of Cl 2 gas 11.2 lt
2 2
32 22.4
c) O2 gas : E.wt of O 2 8g Eq.Vol of O 2 gas 5.6 lt
4 4
CAP-53. Find the eq. volume of SO 2 gas in the reaction : SO 2 SO 42
22.4
n-factor = 2. Eq. vol of SO 2 11.2 lt
2
Principle of gm equivalence:
Number of g-equivalents of all reactants reacted will be equal and the same number of g-equivalents of
each product will form.
CAPS-54.
1. A metal oxide contains 47% oxygen by weight. Determine the equivalent weight of the metal.
Sol: If we take 100gm of oxide, it contains 47gm oxygen & hence rest, 53gm metal.
no.of g.equ. of metal = no.of g.eg.of oxygen.
Sr. INTER IIT-JEE MATERIAL :: 52 ::
CHEMISTRYv v v v v v v v v v v v v v v v v v v v v v v v STOICHIOMETRY
w w 53 47
E E 9.02
Metal E
Oxygen E 8
2. 5.04 gms of metal carbonate produces 2.4gm metal oxide on complete decomposition. What is the equiva-
lent weight of the metal.
Sol: no.of g-eq metal carbonate = no.of g-eq.of metal oxide.
5.04 2.4
E 12
E 30 E 8
3. 5.55 gm of a base neturalises completely 1.68 lt SO 2 gas at STP. Calculate the equivalent weight of a
base.
Sol: no.of g.eq. of base = no.of g.eq. of SO 2
5.55 1.68
E 37
E 11.2
4. How many gms of oxygen is needed for complete combustion of 6gm CH 4 ?
4 0 4 2
Sol: C H 4 O 2 CO 2 H 2 O
16 32
E.wt.of CH 4 2 Eq.wt of O 2 8
8 4
No.of g.eq. of CH 4 = no.of g.eq.of O2
6 w
w 24gms
2 8
The exact atomic weight of elements may be determined by using the following steps:
6.4
(i) atomic weight (approx) =
sp.heat
(ii) Equivalent weight determination from experiment
(iii) Valency = fractional, but close to an integer. Make it integer. It will give the correct v of the element.
(iv) Atomic weight (exact) = Eq. wt valency
CAP-55. The specific heat of a metal is 0.115 cal/oC-gm. The oxide of this metal contains 22.2g oxygen by
weight. Determine the exact atomic weight of the metal.
6.4 6.4
Sol: at.wt(approx) = 55.65
sp.heat 0.115
If we take 100gm of metal oxide, it contains 22.22 gm oxygen and remaining 77.78 gm will be metal.
Sr. INTER IIT-JEE MATERIAL :: 53 ::
CHEMISTRYv v v v v v v v v v v v v v v v v v v v v v v v STOICHIOMETRY
77.78 22.22
No.of g-eq. of metal = no.of g-eq. of oxygen
E 8
E = 28
at.wt.(approx) 55.65
Now, valency 1.9875 2
eq.wt. 28
Hence, exact at .wt. of metal = eq.wt valency = 28 2=56
c) Vapour density of volatile chloride method:
Let an element, M, of valency v, form a volatile chloride, MClV. Then,
mol.wt. of MClV=1 at.wt.of M+v at.wt.of Cl 2 V.D V E V 35.5 V(E 35.5)
2 V.D
V
E 35.5
Hence, with the known V.D. of volatile chloride and equivalent weight of element, we may determine the
valency of element.
at.wt. of element = eq.wt valency..
CAP-56. The vapour density of a volatile chloride of a metal is 95. The chloride contains 37.368gm chlorine by
weight. Determine the atomic weight of metal.
Sol: Let we take 100gm of metal chloride. It will contain 37.368gm chlorine and remaining 62.632 gm metal.
Now,
62.632 37.368
E 35.5
E = 59.5
2 V.D 2 95
Now, valency of metal, V 2
E 35.5 59.5 35.5
Hence, atomic weight of metal = E V 59.5 2 119
d) Law of Isomorphism: Isomorphous compounds are the compounds having similar molecular formula as
well as crystalline geometry.
Example: Cu 2S and Ag 2S
K 2SO 4 , K 2SeO 4 , K 2 WO 4 , K 2 CrO 4
MgSO4 7H2 O, ZnSO4 7H 2 O and FeSO4 7H 2 O ; etc
Isomorphous compounds differs only in a single element or ion and the elements differing should definitely
have the same valency. According to the law of isomorphism, the ratio of atomic weights of the element
differing in isomorphous compounds will be equal to their mass ratio combined with the same mass of other
elements.
At.wt.of A wt.of A
At.wt of B wt.of B combined with the same weight of other elements.
CAP-57. Cu 2S and Ag 2S are isomorphous compounds. Cu 2S contains 20.14% sulphur and Ag 2S contains
12.90% sulphur, by weight. If the atomic weight of copper is 63.5, determine the atomic weight of silver.
Sol: Cu 2S contains 20.14% sulphur and hence remaining 79.86% is copper. Hence, 1 gm sulphur will combine
79.86
with 3.965gm copper
20.14
PART - 8
(CONCENTRATION TERMS AND VOLUMETRIC ANALYSIS)
Solution :
It may be defined as the homogeneous mixture of two or more substances. The substance present in larger
amount is called solvent and the other substances present in smaller amounts are called solutes.
Concentration or strength of solution :
It normally represents the amount of solute present in the given amount of solution. Depending on the unit
of amount, different methods are used to express concentration. Some of them are :
i) Percentage method ii) gm / lt
iii) PPM iv) Molarity (M)
v) Molality (m) vi) Normality (N)
vii) Formality (F) viii) Mole fraction (XA)
ix) Volume strength
I. Percentage method :
It represents the amount of solute present in 100 amount of solution. The amount may be expressed in gm
or ml resulting the following four kind of percentage methods.
i) w/w (weight by weight method) : It represents the amount of solute (in gm) present in 100gm of
solution.
ii) w/v (weight by volume method) : It represents the amount of solute (in gm) present in 100ml of
solution.
iii) v/w (volume by weight) : It represents the amount of solute (in ml) present in 100gm of solution.
iv) v/v (volume by volume) method : It represents the amount of solute (in ml) present in 100ml of
solution.
CAPS-58.
Example - 1 : 250gm of a solution contains 20g solute. Determine the strength of solution in w/w
percent.
Sol : 250g solution contains 20g solute.
100g solution will contain
20
100 8 g solute
250
Hence, strength = 8% (w/w).
Example - 2 : 120 ml of a solution contains 0.02 mole of solute of molar mass, 60gm. Express the
strength of solution (w/v) percent.
Sol : Weight of solute = mole x molecular weight
= 0.02 60 1.2gm
Now, 120ml of solution contains 1.2gm solute
Sr. INTER IIT-JEE MATERIAL :: 55 ::
CHEMISTRYv v v v v v v v v v v v v v v v v v v v v v v v STOICHIOMETRY
1.2
100ml of solution will contain 120 100 1 gm solute
Hence, strength = 1% (w/v)
Example - 3 : The strength of a solution of density 1.2 gm/ml is 10% (w/w). Express the strength in
(w/v) percent.
100
Sol : Strength of solution is 10% (w/w), means if we take 100 gm ml solution, it will contain 10gm solute,
1.2
100
ml solution contains 10gm solute
1.2
100
100ml solution will contain 100 12 gm solute
100
1.2
Hence, strength = 12% (w/v)
II. Parts per million (PPM)
It represents the amount of solute (in gm) present in 106 gm of solution. It is normally used when strength
of solution is very low.
Mass of solute
PPM 106
Mass of solution
CAPS-59.
Example - 1 : The strength of a solution is 0.002% (w/w). Express it in ppm.
Sol : 0.002% (w/w) means 100gm of solution will contain 0.002gm solute. Hence,
0.002
Strength = 106 20 ppm
100
Example - 2 : The fluoride concentration in a sample of toothpaste is 500ppm. What is the mass of
fluoride present in a tube of toothpaste containing 200gm paste ?
Sol : 500 ppm means 106 gm paste will contain 500g fluoride
500
Mass of fluoride = 200 0.1gm
106
III. Strength (or) concentration (or) gm/lit :
It represents the amount of the solute in gms present in one litre of the solution.
Massof soluteingms
Strength of solution = volumeof solutioninml 1000
CAPS-60
Example - 1 : 10 gm urea is dissolved in 70gm water to get a solution of density 1.25gm/ml. Ex-
press the concentration of solution in gm/lit.
Sol : Weight solution prepared = 10 + 70 = 80 gm
w 80
Volume of solution = 64ml
d 1.25
64ml solution containing 10 gm solute,
1000ml solution will contain
10
1000 156.25 gm solute.
64
Strength = 156.25 gm/lit.
Sr. INTER IIT-JEE MATERIAL :: 56 ::
CHEMISTRYv v v v v v v v v v v v v v v v v v v v v v v v STOICHIOMETRY
Molarity (M) :
It represents The number of moles of solute present per litre of the solution.
No.of moles of solute
Molarity =
vol.of solution in litres
wA
M A VLt
wA 1000
M
M A Vml
( wA = weight of the solute ;
MA = molecular weight of the solute
Vml = volume of solution in ml.)
CAPS-61
Example - 1 : 4.9 gm H2SO4 is dissolved in water to get 250ml solution. What is the molarity of
solution.
4.9 1000
Sol : M 0.2 M
98 250
Example - 2 : Calculate the molarity of 10% (w/v) NaOH solution.
Sol : 10% (w/v) solution means 100ml of solution contains 10gm solute, NaOH. Hence,
10 1000
M 2.5M
40 100
Example - 3 : Calculate the molarity of 10% (w/v) NaOH solution of density 1.1 gm/ml.
100
Sol : 10% (w/w) solution means ml solution contains 10gm NaOH. Hence,
1.1
10 1000
M 2.75M
100
40
1.1
Example - 4 : How many moles of solute are present in 250ml of 0.8M KMnO4 solution.
Sol : No. of moles = Molarity x vol. of solution in litres.
250
0.8 0.02
1000
Dilution : Addition of excess solvent to the solution, without changing the amount of solute.
Dilution is reciprocal of concentration
1
i.e, Dilution =
concentration
Law of dilution :
The number of moles of solute present before and after dilution is constant.
weight of the solute
No. of moles =
mol.weight of the solute
(or) No. of moles = Molarity x VLt
Suppose M1 , M2 are the molarities and V1 , V2 are volumes of solution in lts before and after dilution
respectively.
CAPS-62
Example - 1 : 40ml of 2M-HCl solution is diluted to 100ml. What is the molarity of diluted solution.
Sol : 40 x 2 = 100 x M2 M2 = 0.8 M
NOTE :
As the dilution is reciprocal that of concentration it should be remembered that :
* If dilution increases by 10times molarity (concentration) decreases by 10times.
Eg : 10ml of 0.1M solution is diluted to 100ml
conc by 10 times
final conc. 0.01
* If dilution increases by 5 times, conc by 5 times
Eg : 20ml of 0.2M solution is diluted to 100ml.
dilution is by 5 times
conc. should decrease by 5 times
0.2
find molarity = 0.04
5
Eg : 40 ml of 0.5 M solution is diluted 160ml.
dilution is by 4 times
conc. should by 4 times
0.5
= 0.125 is the final molarity
4
Eg : If 50ml of 0.8 M solution is diluted to 400ml.
dilution is by 8 times
conc. should by 8 times
0.8
0.1 M is the final conc.
8
Example - 2 : 20ml of 0.5 M solution is diluted to 100ml. 25ml of this solution is taken and further
diluted to 100ml. Then find the final conc. of the solution.
i) 1st dilution : 20ml is diluted to 100ml
5 times dilution conc. by 5 times
0.5
0.1
5
ii) 2nd dilution : This 0.1M solution of 25ml is diluted to 100ml
4 times dilution conc. by 4 times.
0.1
0.025 M is final conc.
4
Example - 4 : 25ml of HCl solution is diluted to 100ml. 50ml of this solution is taken and diluted
further to get 400ml of 0.1M HCl. Then, what is initial conc. of HCl.
Sol : i) 25 M1 100 2
wA
E A Vlit
A w 1000
N= E A Vml
wA = weight of the solute in gms
Vml = volume of solution in mL.
EA = gm. equivalent weight of the solute
Molecular weight
=
n factor
Example : Calculate the normality of 5.88% (w/v) H2SO4 solution.
Sol : 5.88% (w/v) solution represents that 100ml solution contains 5.88 gm of H2SO4
wA 1000 5.88 1000
N 1.2N
E A Vml 98 100
2
Sr. INTER IIT-JEE MATERIAL :: 59 ::
CHEMISTRYv v v v v v v v v v v v v v v v v v v v v v v v STOICHIOMETRY
Relation between Moalrity and Normality :
wA 1000 wA 1000
N
E A Vml MA Vml
n factor
wA 1000
n factor
M A Vml
N Molarity n factor
CAPS-64
Find the normalities of
i) 0.1M HCl ii) 0.5M H2SO4
iii) 0.2M H3PO4 iv) 0.8M Ca(OH)2
v) 0.3M AlCl3 vi) 0.4M Al2(SO4)3
vii) 0.1M KMnO4 / H+ viii) 2M CH3COOH
Sol : i) 0.1N HCl ii) 0.5 x 2 = 1N H2SO4
iii) 0.2 x 3 = 0.6N iv) 0.8 x 2 = 1.6N Ca(OH)2
v) 0.3 x 3 = 0.9N AlCl3 vi) 0.4 x 6 = 2.4N Al2(SO4)3
vii) 0.1 x 5 = 0.5N KMnO4 viii) 2x1 = 2N CH3COOH
Law of dilution : is also applicable to normality i.e, before dilution and after dilution, no.of gm equivalents of
solute remains constant.
weight of the solute
No.of gm equivalents =
gm. eq. wt. of solute
(or) No.of gm equivalents = Normality x Vlt.
No.of milli g.equts = Normality x Vml
So, Before dilution After dilution
N1 x V1 = N2 x V2
Example - 1 : Calculate no.of gm equivalents in
a) 9.5g of MgCl2 b) 100ml of 0.1M H2SO4
9.5
neq 0.2 equts
Sol : a) 95
2
100
b) neq N Vli = 0.1 2 = 0.02
1000
CAPS-65.
Calculate no.of gm. equivalents of
i) 100ml of 0.1M KMnO4 / H+
100
Sol : neq 0.1 5 0.05
1000
ii) 200ml of 0.5M K2Cr2O7 / H+
200
Sol : neq 0.5 6 0.6
1000
iii) 500ml of 0.2M H2SO4
500
Sol : neq 0.2 2 0.2
1000
N AVA N BVB
H mix VA VB
Case - 3 : If neq Acid neq Base
Then, resultant solution is basic PH > 7.
N BVB N AVA
OH mix VA VB
CAPS-67.
Example - 1 : 20ml of 0.1M H2SO4 is added to 40ml of 0.5M NaOH solution. Then find the nature and
concentration of the resultant solution.
Sol : n m.eq H 2SO 4 20 0.1 2 4m.g.equts
n m.eq NaOH 40 0.05 1 2m.g.equts
As, n eq acid n eq base Resultant solution is acidic
42 2
H 0.033N
60 60
Example - 2 : 100ml of 0.2M HCl is added to 200ml of 0.05MCa(OH)2. Then, find the nature of
resultant solution.
Sol : n m.eq HCl 100 0.2 20
wA
= M w
A B Kg
w A 1000
m
MA w B
where, wB = weight of the solvent in gms.
Sr. INTER IIT-JEE MATERIAL :: 62 ::
CHEMISTRYv v v v v v v v v v v v v v v v v v v v v v v v STOICHIOMETRY
CAPS-68.
Example -1 : Calculate the molaltiy of 10%
(w/w) NaOH solution.
Sol : 10% (w/w) NaOH 10gm of NaOH present in 100g of solution.
weight of solvent (wB) = 100 - 10 = 90g
10 1000
m 2.78m
40 90
Example - 2 : Calculate the weight of 6% (w/v) urea solution whose density is 1.2g/ml.
Sol : 6% (w/v) urea solution
6 gm of urea in 100ml of solution
6 gm of urea in (100x1.2) g of solution
wB = 120 - 6 = 114.
6 1000
m 0.8772m
60 114
Relation between Molarity & Molality :
Example : The density of 1.5M urea solution is 1.05gm/ml. Calculate the molality of the solution.
Sol : 1.5 M urea solution 1.5moles of urea in 1L of solution
1.5 moles of urea in (1000x1.05)g of solution
1.5x60g of urea in 1050g of solution
wB = 1050 - 90 = 960g of solvent
90 1000
m 1.56m
60 960
NOTE : From the above conceptual work, the relation between molarity (M) and molality (m) can be put in the
form of formula as :
1000 M
m
1000 d M M A
where M = Molarity of solution
MA = mol.wt of solute in gms.
d = density of the solution in gm/ml
CAPS-69
1. Find the molality of 2% (w/v) Glucose solution whose density is 1.02 gm/ml.
2. Find the molality of 1.2M NaOH solution whose density is 1.5gm/ml.
Molefraction (X) :
Molefraction of any component in a mixture represents its number of moles present in 1mole of the
mixture.
Let a solution be prepared by mixing n1 moles of solute and n2 moles of solvent. Then, the total no.of moles
of solution becomes (n1 + n2).
n1
Hence, Molefraction of solute (X1) = n n
1 2
n2
Molefraction of solvent (X2) = n n
1 2
X1 X 2 1
NOTE :
1. All the units including volume terms will be temperature dependent, eg : molarity, normality, formality etc
are temperature dependent.
2. Molefraction, % by mass, molality etc., as they does not involve volume terms, they are temperature
independent.
3. Rise in temperature usually results in increase in volume, so molarity, normality etc decrease as tempera-
ture is increased.
Example - 1 : A solution is made by mixing 64gm CH3OH and 46gm C2H5OH. Calculate the mole-
fraction of methanol in the solution.
W 64
Sol : n CH3OH 2
M 32
46
n C2 H5OH 1
46
n1 2
X CH3OH 0.67
n1 n 2 2 1
Relation between molefraction and molality :
Calculate the molefraction of solute in 1m aqueous urea solution.
Sol : 1m solution 1mole urea in 1kg water
n urea 1
X urea 0.01768
n urea n H 2O 1 1000
18
In general, if the solvent is water, then the relation between molality and molefraction is given by
m
XA
m 55.55
If solvent is not water, then :
m
XA
1000
m
MB
MB = Molecular weight of solvent
CAPS-70.
1. If 2gm of NaOH is dissolved in 180gm of water. Find the molefraction of NaOH.
2. Find the molefraction of 0.2m aqueous glucose solution.
Volume strength : This method of expression of strength is used only for H2O2 solution. It represents :
The number of milliliters of oxygen gas liberated at STP by 1ml of H2O2 solution.
For example : i) 10 volume H2O2 means 1 vol of H2O2 solution on decomposition gives 10 volumes of O2
at STP.
ii) 20 vol H2O2 1ml of H2O2 solution gives 20ml of O2 at STP by decomposition.
iii) 20ml of 20 vol H2O2 : It gives 20x20 = 400ml of O2 at STP
In redox titrations, the sudden changes in colours due to reactants themselves and hence in most of the
cases external indicators are not required.
Principles of titration :
Titration means stoichiometry and hence it runs on moles as well as equivalent concept. But, for simplicity
equivalent concept is preferred.
Principle : Number of g.equivalents of all reactants reacted will be equal and the same number of g.equivalents
of each product will form.
N VL Acid N VL Base
REDOX TITRATIONS:
For Redox titrations, at equivalent point : n eq oxidant n eq reductant
weight of oxidant weight of reductant
Mol.wt.of oxidant Mol.wt.of reductant
N VL oxidant N VL reductant
Common oxidising agents which are used in redox titrations are :
i) Acidified KMnO4 (Permanganometry)
ii) Acidified K2Cr2O7 (dichrometry)
iii) Iodine / Iodide (Iodimetry & Iodometry) etc.,
I) Titrations using acidified KMnO4 (Permanganometry) :
In strongly acidic medium
MnO4 8H 5e
Mn 2 2H2O ; E0 1.51V
N M n factor
w w
M/ 5 KMnO4 M/ 2 oxalicacid
M 126
E KMnO4 31.6 ; E oxalic acid 63
5 ( H 2 C 2 O 4 .2 H 2 O ) 2
2+
b) KMnO4 Vs Fe ions :
Fe2+ is readily oxidised by MnO 4 to Fe3+
In the laboratory, for practical purposes ferrous ammonium sulphate (Mohrs salt) is taken as a source of
Fe2+ ions.
5Fe 2 MnO 4 8H
5Fe 3 Mn 2 8H 2 O
Sr. INTER IIT-JEE MATERIAL :: 68 ::
CHEMISTRYv v v v v v v v v v v v v v v v v v v v v v v v STOICHIOMETRY
End point : MnO acts as self indicator and light pink colour of solution indicates end point.
4
w w
iv)
M / 5 KMnO4 M FAS
158 392
v) E MnO M 31.6 ; E FAS
4 5 5 1
NOTE : If titration is being carried out with solution of Ferrous oxalate, then :
Fe 2 C 2 O 24
Fe3 2CO 2 3e
n - factor = 3
E Fe C2 O 4 M 3
Estimation of Fe2+ and Fe3+ ions in solution :
In this estimation, the solution is titrated twice. First without reduction in which only Fe2+ reacts and Fe3+
remains unreacted.
In second step, same volume of solution is taken. Fe3+ ions are reduced to Fe2+ and then titrated. Here,
i) In step - 1 : meq KMnO4 (let x) = meq of Fe2+
ii) In step - 2 : meq KMnO4 (let y) = meq of Fe2+ + meq of Fe3+
meq Fe3+ = (y - x)
d. Analysis of sample containing oxalic acid and sodium oxalate :
Same volume of solution are titrated separately with NaOH and KMnO4 solution.
meq NaOH = meq oxalic acid
and meq KMnO4 = meq of oxalic acid + meq of sodium oxalate.
Titrations using K2Cr2O7 (dichrometry) :
In volumetric analysis, Cr2 O 72 is also used commonly as oxidant yet weaker than MnO 4 , Ce 4 etc.,
In most of its applications it is reduced to Cr+3.
Cr2O72 14H 6e
2Cr3 7H2O ; E0 1.33V
M Cr O2 294
E Cr O2 2 7
49
2 7
6 6
These titrations are made in acidic solutions, but, not in neutral or alkaline medium. In alkaline medium,
orange Cr2 O 72 changes to yellow CrO 24 .
It can be used as oxidising agent in present of HCl or Cl- also.
If same molarities of KMnO4 & K2Cr2O7 in acidic medium are used to titrate separately Fe2+ (aq), then
vol for MnO 4 6
1.2
vol for Cr2 O72 5
Thus, volume of MnO 4 required will be 1.2 times of volume of Cr2 O 72 .
w = 2.86 g
n - factor of Na2CO3 . 10H2O = 2
n - factor of H2SO4 = 2
Example - 4 : What volume of 0.4M - KMnO4 solution is needed for complete oxidation of 9.92gm
hypo, Na2S2O3 . 5H2O in basic solution ? The un balanced reaction is :
MnO 4 S2 O32 H 2 O MnO 2 SO42 OH
Sol : neq KMnO4 = neq Na2S2O3 . 5H2O
V 9.92
3 0.4
1000 248
8
V 266.67ml
7 4
M nO4
M nO 2 n factor 3
2 6
S2 O32
S O24 n factor 8
Example - 5 : How many mg of magnesium should be added in 200ml of 1.02N - HCl solution to
reduce its concentration to 1.0N ? (Assume no change in volume of solution on addition of
magnesium)
Sol : neqHCl taken = neqMg taken + neqHCl remained
200 w 200 1.0
1.02
1000 24
2
1000
w = 0.048gm = 48mg
Example - 6 : A certain amount of a mixture of H2C2O4 and NaHC2O4 requires equal volumes of
0.01M - KMnO4 and 0.2M - Ca(OH)2 solutions, in different experiments. Calculate the mole
ratio of H2C2O4 and NaHC2O4 in the original mixture.
Sol : Let a mole of H2C2O4 and b mole of NaHC2O4 are present in the original mixture with KMnO4.
neqKMnO4 = neqH2C2O4 + neqNaHC2O4
V
0.1 5 a 2 b2
1000
0.5V
2a 2b............. 1
1000
3 4
C 2 O 24
C O2
[x - factor = 2 ]
with Ca(OH)2 :
neqCa(OH)2 = neqH2C2O4 + neqNaHC2O4
(acid - base reactions)
V
0.2 2 a 2 b 1
1000
II. One substance reacts with more than one substance, Back titration, etc :
CAPS-73.
Example - 1 : 20ml of 0.2N - NaOH solution is mixed with 40ml of 0.3N - HCl solution. The excess
acid requires 50ml of Na2CO3 solution for complete neutralization. Calculate the strength of
Na2CO3 solution in gm/ lit.
Sol :As HCl is reacting with NaOH as well as Na2CO3 solution.
neq HCl neq NaOH neq Na2CO3
40 0.3 20 0.2 50 N
N = 0.16 N = 0.16 143 22.88 gm / Lt
Example - 2 : 0.03g of a metal is dissolved in 200ml of M/10 - H2SO4 solution. When the metal is
3M
dissolved completely, the excess acid required 50ml of NaOH solution for complete neu-
4
tralization. Determine the equivalent weight of the metal.
Sol : As H2SO4 solution is reacting with metal as well as NaOH solution.
neq H 2 SO4 neq metal neq NaOH
200 0.1 2 0.03 50 0.75 1
1000 E 1000
E 12
Example - 3 : 1.0gm of an equimolar mixture of carbonates of two bivalent metals requires 15ml of
0.5N - HCl solution for complete neutralization. If one metal is calcium, what is the atomic
weight of the other metal.
Sol : Let the weight of CaCO3 present is x gm. Then the weight of other metal carbonate MCO3, is
(1-x)gm. From question, moles of both carbonates are equal. Hence :
x 1 x
........... 1
100 A 60
where A = at weight of metal M
neq CaCO3 neq MCO3 neq HCl
x
1 x
15 0.5
100
2 A 60
2
1000
Example - 3 : 2.61gm sample of pyrolusite was boiled with 65ml of N-oxalic acid in presence of
excess of dil. H2SO4. The liquid was then filtered and residue is washed. The filtrate and the
washings were mixed and made upto 500ml. The solution requires 250ml of N/10 - KMnO4 for
complete oxidation of excess oxalic acid. Calculate the percentage of pure MnO2 in the pyro-
lusite sample (Mn = 55).
Sol : Here, oxalic acid is reacting with pure MnO2 as well as KMnO4. Hence,
neq oxalic acid neq MnO2 neq KMnO4
65 1 w 250 1
10 w 1.74 gm
1000 87 1000
2
1.74
% of MnO2 inthe sample 100 66.67%
2.61
Example - 4 : 200gm of a sample of KI is dissolved in 20ml of 1.2M - KMnO4 solution in acidic
medium. After complete reaction, the solution is diluted to 150ml. 25ml of this diluted solution
requires 40ml of 0.5M - K2Cr2O7 solution for complete reaction with excess KI. Calculate the
% purity of KI sample (K = 39, I = 127).
Sol: Here, KI will react with both KMnO4 & K2Cr2O7. Hence,
neq KI neq KMnO4 neq K 2Cr2O7
40
150 0.5 6
w 20 1.2 5 25
166
1 1000 1000
w 139.44 gm
1
I 20
K I n fa c to r 1
7
M n O 4
M n 2 n fa c to r 5
6
C r 2 O 7 2
C r 3 n fa c to r 6
40
[The factor 150 will represent the total volume of K2Cr2O7 needed to react completely with all KI
25
left in 150ml solution]
50 1
50 w
1000 50
w 0.05 gm
0.05
Temporary Hardness = 106 500 ppm of CaCO3
100
= 119.63 H2SO4
Hence, the % of oleum is labelled as 119.68%
Amount, of water added to 100g oleum = 19.68g
as,. 18g of water reacts with 80g SO3.
Determination of available Cl2 in Bleaching powder :
Available Cl2 :
with excess of acid, bleaching powder liberates Cl2 which is called available chlorine.
For estimation of available chlorine, a weighed quantity of bleaching powder is treated with acetic acid and
KI and the Cl2 liberated reacts with KI and liberates equal equivalents of I2.
The amount of I2 liberated is estimated by treating with standard solution of sodium thiosulphate.
The reactions are as follows :
i)
ii)
iii)
Let wg bleaching powder is dissolved in Vml water V1 ml of this solution is treated with excess of
CH3COOH / KI and a few drops of KI are added in it.
The I2 liberated is titrated with N-hypo solution. At the end point, blue colour of solution disappears.
Let V2ml of hypo are used, then available Cl2 may be estimated as follows :
Amount of bleaching powder in Vml solution meq of Cl2 in V1 ml solution = meq of I2
= meq of hypo
= N x volume (in mL)
= n x M x V2
% available Cl2 =
% of available Cl2 =
= 12.51%
2. Estimation of
Eq.mass of
3. Estimation of present in pyrolusite:
,
(or)
Eq. Mass of .
5. Estimation of , Eq.mass of
9. Estimation Eq.mass of .
PART-9
(Significant Figures)
There is always some degree of uncertainty in every scientific measurement except in counting. The
uncertainty in measurement mainly depends upon two factors:
(i) Skill and accuracy of the observer,
(ii) Limitation of the measuring scale.
To indicate the precision of a measurement, scientists use the term significant figures. The significant
figures in a number are all the certain digits plus one doubtful digit. The number of significant figures gives
the information that except the digit at extreme right, all other digits are preciese or reproducible. For
example, mass of an object is 11.24g. This value indicates that actual mass of the object lies between
11.23g and 11.25g. Thus, one is sure of first three figures (1, 1 and 2) but the fourth figure is somewhat
inexact. The total significant figures in this number are four.
The following rules are observed in counting the number of significant figures in a given measured
quantity:
(i) All non-zero digits are significant. For example,
42.3 has three significant figures.
243.4 has four significant figures.
24.123 has five significant figures.
(ii) A zero becomes significant figure if it appears between two non-zero digits. For example.
5.03 has three significant figures.
5.604 has four significant figures.
4.004 has four significant figures.
(iii) Leading zeros or the zeros placed to the left of the number are never significant. For example,
0.543 has three significant figures.
0.045 has two significant figures.
0.006 has one significant figures.
(iv) Trailing zeros or the zeros placed to the right of the number are significant. For example,
433.0 has four significant figures.
433.00 has five significant figures.
343.000 has six significant figures.
(v) In exponential notation, the numerical portion gives the number of significant figures. For example.
has three significant figures.
has three significant figures.
(vi) The non-significant figures in the measurement are rounded off.
(a) If the figure following the last number to be retained is less than 5, all the unwanted figures are
discarded and the last number is left unchanged, e.g.,
5.6724 is 5.67 to three significant figures.
(b) If the figure following the last number to be retained is great than 5, the last figure to be retained is
increased by 1 unit and the unwanted figures are discarded, e.g.,
8.6526 is 8.653 to four significant figures.
(c) If the figure following the last number to be retained is 5, the last figure is increased by 1 only in case it
happens to be odd. In case of even number the last figure remains unchanged.
2.3524 is 2.4 to two significant figures.
7.4511 is 7.4 to two significant figures.
(c)
Correct answer = 0.21
Note: (i) Same procedure is followed if an expression involves multiplication as well as division.
(ii) The presence of exact numbers in an expression does not affect the number of significant figures in the
answer.
Examples are:
(a) (b)
_____