BASIC PRINCIPLES 9

The reaction is also termed neutralisation, i. e., a reaction For example, carbon dioxide can be obtained by using anyone
between an acid and a base to form a salt and water molecule. of the following methods: '
I I
(a) by heating calcium carbonate,
FeCl 3 + 3HOH Fe(OHh + 3HCl
L..::....----l (b) by heating sodium bicarbonate,
Water
(c) by burning carbon in oxygen,
Reaction of above type is termed hydrolysis. (d) by reacting calcium carbonate with hydrochloric acid.
Whatever sample of carbon dioxide is taken, it is observed
1.8 LAWS OF CHEMICAL COMBINATION that carbon and oxygen are always combined in the ratio of
12 : 32 or 3 : 8.
In order to understand the composition of various compounds, it The converse of this law that when same elements combine in
is necessary to have a theory which accounts for both qualitative the same proportion, the same compound will be formed, is not
and quantitative observations during chemical changes. always true. For example, carbon, hydrogen and oxygen when
Observations of chemical reactions were most significant in the combine in the ratio of 12 : 3 : 8 may form either ethyl alcohol
development of a satisfactory theory of the nature of matter. (C2 H 5 0H) or dimethyl ether (CH 3 0CH 3 ) under different
These observations of chemical reactions are summarised in experimental conditions.
certain statements known as laws of chemical combination.
(iii) Law of multiple proportions: This law was put
(i) Law of conservation of mass: The law was fIrst stated forward by Dalton in 1808. According to this law, if two
by Lavoisier in 1774. It is also known as the law of elements combine to form more than one compound, then the
indestructibility of matter. According to this law, in all chemical different masses of one element which combine with a fIXed
changes, the total mass Qf a system remains constant or in a mass of the other element, bear a simple ratio to one another.
chemical change, mass is neither created nor destroyed. This ..Hydrogen and oxygen combine to form two compounds H 2 0
law ~as tested by Landolt. All chemical reactions follow this (water) and H 2 0 2 (hydrogen peroxide).
law. Thus, this law is the basis of all quantitative work in
In water, Hydrogen 2 parts Oxygen 16 parts
chemistry.
In hydrogen peroxide, Hydrogen 2 parts Oxygen 32 parts
Example: 1.70 g ofsilver nitrate dissolved in 100 g ofwater
is taken. 0.585 gofsodium chloride dissolved in 100g ofwater is The masses of oxygen which combine with same mass of
hydrogen in these two compounds bear a simple ratio 1 : 2.
added to it and chemical reaction occurs. 1.435 g of silver
chloride and 0.85 g of sodium nitrate are formed. Nitrogen forms fIve stable oxides.
Np Nitrogen 28 parts Oxygen 16 parts
Solution: Total masses before chemical change
Nitrogen 28 parts Oxygen 32 parts
Mass of AgN0 3 + Mass ofNaCI + Mass of water
Nitrogen 28 parts Oxygen 48 parts
=1.70g + 0.585g + 200.0g Nitrogen 28 parts Oxygen 64 parts
202.285 g N20 s Nitrogen 28 parts Oxygen 80 parts

Total masses after the chemical reaction, The masses of oxygen which combine with same mass of
nitrogen in the five compounds bear a ratio 16 : 32 : 48 : 64 : 80
= Mass of AgCl + Mass of NaN0 3 + Mass of water
or I : 2 : 3 : 4 : 5.
1.435 g + 0.85 g_+ 200.0 g (iv) Law of reciprocal proportions: This law was given
= 202.285g· by Richter in 1794. The law states that when definite mass of all
element A combines with two other elements Band C to form
Thus, in this chemical change,
two compounds and if Band C also combine to form a
Total masses of reactants = 'total masses of products compound, their combining masses are in same proportion or
bear a simple ratio to the masses of Band C which combine
This relationship holds good when reactants are completely
with a constant mass of A.
converted into products.

~(~)-----~-----
In case, the reacting materials are not completely consumed,
the relationship will be
Total masses of reactants = Total masses of products

r~ fR
+ Masses of unreacted reactants
(ii) Law of definite or constant proportions: This law
was presented by Proust in 1799 and may be stated as follows:
A chemical compound always contains the same element
combined together in fixed proportion by mass, i.e., a NaCI
chemical compound has a fIXed composition and it does not
For example, hydrogen combines with sodium and chlorine to
depend on the method of its preparation or the source from
form compounds NaH and HCI respectively.
which it has been obtained.
10 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

In NaH, Sodium 23 parts Hydrogen one part . Example 4. In an experiment, 2.4 g of iron oxide on
In HCI, Chlorine 35.5 parts Hydrogen one part reduction with hydrogen yield 1.68 g of iron. In another
Sodium and chlorine also combine to fonn NaCI in which 23
experiment, 2.9 gO/iron oxide give 2.03 g of iron on reduction
with hydrogen. Show that the above data illustrate the law of
parts of sodium and 35.5 parts of chlorine are present. These are
constant proportions.
the same parts which combine with one part of hydrogen in NaH
and HCl respectively. Solution:
In the first experiment

/
(~)
~. ~o
. The~ssoflrorioxide = 2.4 g
The mass ofJron after reduction 1.68g

S(B)~~O(c)
The mass of oxygen = Mass of iron oxide - Mass of iron
(2.4 - 1.68) O.72g
Ratio of oxygen and iron = 0.72: 1.68 1: 2.33
. 802 .
• In the second experiment
Hydrogen combines with sulphur and oxygen, to fonn The mass of iron oxide = 2.9 g
compounds H 2 S and H 20 respectively. The mass of iron afteueduction 2.03 g
In H2 S, Hydrogen 2 parts SUlphur 32 parts The triass of oxygen (2.9.;.. 2.03) ~ 0.87 g
In H 20, . Hydfogen 2 parts Oxygen 16 parts
Ratio of oxygen and iron = 0.87: 2.03 =1: 2.33
Thus, according to this law, sulphur should combine with Thus, the data illustrate the law of constant proportions, as in
oxygen in the ratio of 32 : 16 or a simple multiple of it. Actually, both the experiments the ratio of oxygen and iron is the same.
both combine to fonn S02 in the ratio of 32 : 32 or 1 : 1.
The law of reciprocal proportions is a special case of a more EXample S. Carbon combines with hydrogen to form three
general law, the law of equivalent masses, which can be stated compounds A, B and C. The percentages ofhydrogen in A, Band
as under: Care 25, 14.3 and 7.7 respectively. Which law of chemical
"In all chemical reactions, substances always react in the . combination is illustrated?
ratio oftheir equivalent masses." Solution:
(v) Law of gaseous volumes: This law was enunciated by
Gay-Lussac in 1808. According to this law, gases react with Compound % of Hydrogen % of Carbon
each other in the simple ratio of their volumes and if the product
is also in gaseous state, the volume of the product also bears a A 25.0 (100 - 25.0) = 75.0
simple ratio with the volumes of gaseous reactants when all B 14.3 (100 -14.3) = 85.7
volumes are measured under similar conditions of temperature
and pressure. . C 7.7 (100 - 7.7) = 92.3

ratio 1: 1:2 In Compound A

H2 + Cl z = 2HCI
I vol I vol Zvol 25 parts of hydrogen combine with 75 parts of carbon
2H z + O2 = 2H zO ratio 2: 1: 2 I part of hydrogen combines with 75/25
2vol I vol 2vol = 3 parts of carbon
2CO+ Oz 2002 ratio 2: 1 : 2 In Compound B
2 vol I vol 2 vol
14.3 parts of hydrogen combine with 85.7 parts of carbon
N2 + 3H2 = 2NH3 ratio [Link] 1 part of hydrogen combines with 85.7/14.3
I vol 3vol 2 vol
= 6.0parts of carbon
In Compound C
: :::::I_SOME SOLVED EXAMPLES\I:::::: 7.7 parts of hydrogen combine with 92.3 parts of carbon
Ex~mple 3. What mass of sodium chloride would be 1 part of hydrogen combines with 92.3/7.7
decomposed by 9.8 g of sulphuric ~id, if 12 g of sodium = 12.0 parts of carbon
bisulphate and 2.75 g of hydrogen chloride were produced in a Th1,lS, the masses of carbon in three compounds A, B and C,
reaction assuming that the law ofconservation of mass, is true? which combine with a fixed mass of hydrogen are in the ratio of
Solution: NaCI + H 2S0 4 = NaHS0 4 + HCl 3 : 6 : 12 or 1 : 2 : 4. This is a simple ratio. Hence, the data
According to law of conservation of mass, illustrate the law of multiple proportions:
Total masses of reactants = Total masses of products Example 6. Two compounds each containing only tin and
oxygen had the following composition:
Let the mass ofNaCI decomposed be x g, so Mass % of tin Mass % of oxygen
x + 9.8 12.0+ 2.75 Compound A 78.77 21.23
= 14.75 Compound B 88.12 11.88
x= 4.95g Show how this data illustrate the law ofmultiple proportions?
 BASIC PRINCIPLES 11

Solution: . Example 9. Carbon monoxide reacts oyith oxygen to form

In Compound A carbon dioxide according to the equation, 2CO + O 2 = 2COz.
21.23 parts of oxygen combine with 78.77parts of tin In an experiment, 400 mL of carbon monoxide and 180 mL of
oxygen were allowed to react, when 80% ofcarbon monoxide was
I part of oxygen combines with 78.77/21.23
transformed to carbon dioxide.
= 3.7 parts of tin All the volumes were measured under the same conditions of
In Compound B temperature and pressure. Find out ·the composition of the final .
11.88 parts of oxygen combine with 88.12 parts of tin mixture.
1 part of oxygen combines with 88.12111.88 Solution: 2CO + 02 = 2C0 2
2 vol I vol 2 vol
= 7.4 parts of tin
Thus, the mass of tin in compounds A and B which From the above equation, it is observed that volume of oxygen
combine with a fixed mass of oxygen are in the ratio 00.7: 7.4 required for the transformation of carbon monoxi& into carbon
or 1 : 2. This is a simple ratio. Hence, the data illustrate the law of dioxide is half the volume of carbon monoxide and the volume of
multiple proportions. carbon dioxide produced is same as that of carbon monoxide.
. Example 7. Illustrate the law of reciprocal proportions Volume of carbon monoxide transformed
from the following data: KCI contains 52.0% potassium, KJ = 80x 400 320mL
contains 23.(iO/o potassium and ICI contains 78.2% iodine. 100
Solution: In KCI: Potassium 52.0%, Hence, volume of oxygen required for transformation
Chlorine (100- 52)= 48% = ~ x 320= 160mL
2
In KI: Potassium 23.6%;
Volume of carbon dioxide produced
Iodine (l00 - 23.6) = 76.4%
= 320mL
23.6 parts of potassium combine with 76.4 ~arts of iodine
52.0 parts of potassium will combine with So, the composition of fmal mixture is
(76.4/23.6) x 52.0 168.3 parts of iodine. Carbon monoxide = (400 - 320)
The ratio of masses of chlorine and iodine which combines =80mL
with same mass ofpotassium = 48: 168.3 or I: 3.5 Carbon dioxide = 320 mL
In ICI: Iodine 78.2% and chlorine Oxygen = 180 - 160 = 20 mL
= (100-78.2) 21.8% Example 10. How much volume ofoxygen w(/l be required
for complete combustion of40mL of acetylene (C 2 H 2 ) and how
The ratio of chlorine and iodine in ICI = 21.8: 78.2 ::::: I: 3.5. much volume of carbon dioxide will be formed? All volumes are
Hence, the data illustrate the law of reciprocal proportions. measured at NTP.
Example 8. Zinc sulphate crystals contain 22.6% of zinc
and 43.9% of water. Assuming the law of constant proportions to
Solution: 2C 2 H2 + 5°2 - 4C0 2 +2H 2O
2 vol 5 vol 4 vol
be true, how much zinc should be used to produce 13.7 g ofzinc 40 mL
5 4
x40 mL x40 mL
sulphate and how much water will they contain? 2 2
40 mL 100 mL 80 mL
Solution: 100 g of zinc sulphate crystals are obtained from
So, for complete combustion of 40 mL of acetylene, 100 mL
= 22.6g zinc
of oxygen are required and 80 mL of carbon dioxide is formed.
I g of zinc sulphate crystals will be obtained from
=: 22.6/100g zinc 1'.91 DALTON'S ATOMIC THEORY
13.7 g of zinc sulphate crystals will be obtained from The concept that matter is composed of very small particles was
= 22.6 x 13.7 given by Indian and Greek philosophers. As early as 400 to 500
100 B.C. the Greek philosopher Democritus suggested that matter
= 3.0962gof zinc cannot be forever divided into smaller and smaller parts. The
ultimate particles were considered as indivisible. These particles
100 g of zinc sulphate crystals contain water were called atoms. The word atom has been derived from the
43.9g Greek word 'atomos' meaning 'indivisible'. These early ideas,
1g of zinc sulphate crystals contain water however, were not based on experiments but were mere
:::: 43.9f100g speculations. The existence of at'Oms was accepted by Boyle in
his bo'Ok 'The Sceptical Chymist' (1661) and by Newton in his
13.7 g of zinc sulphate crystals shall contain water b'Ooks ' Principia' and 'Opticks' (1704). The 'Old ideas were put 'On
43.9 3 a scientific scale by John Dalton in the years 1803 to 1808 in the
::::: 100 xl .7= 6.0143g
f'Orm of a theory known as Dalton's Atomic Theory which is a
12 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

landmark in the history of chemistry. The main points of Dalton's Some elements exist in more complex molecular forms. The
atomic theory are: molecule of phosphorus consists of four phosphorus atoms and
(i) Elements consist of minute, indivisible, indestructible the molecule of sulphur consists of eight sulphur atoms. Such
particles called atoms. molecules having more than two atoms are said to be polyatomic.
(ii) Atoms of an element are identical to each other. They A representation of the molecule of an element involves use of a
have the same mass and size. subscript to the right of the elemental symbol. The diatomic
(iii) Atoms of different elements differ in properties and have molecule of chlorine is represented as C1 2 , whereas molecules of
different masses and sizes. phosphorus and sulphur are represented as P4 and S8'
(iv) Compounds are formed when atoms of different elements respectively.
combine with each other in simple numerical ratios such The molecule is the smallest possible unit of a compound
as one-to-one, one-to-two, two-to-three and so on. which shows the properties of the compound. The molecules of
(v) Atoms cannot be created, destroyed or transformed into all compounds contain two or more different types of atoms.
atoms of other elements. These differ from the molecules of elements which contain only
(vi) The relative numbers and kind of atoms are always the one type of atoms.
same in a given compound. Thus, it becomes clear that atoms are the components of
The theory convincingly explained the various laws molecules and the molecules are components of elements or
of chemical combination, but the theory has undergone a compounds.
complete shake up with the modem concept of structure of atom. The formula is a group of symbols of elements which
However, the Daltonian atom still retains its significance as the represents one molecule of a substance. The formula of a
unit participating in chemical reactions. The following are the substance represents its chemical composition. Water consists of
modified views regarding Dalton's atomic theory: molecules containing two hydrogen atoms and one oxygen atom
(i) The atom is no longer supposed to be indivisible. The which are represented as H 2 0. The subscript to the right of the
atom is not a simple particle but a complex one. symbol for hydrogen indicates the number of hydrogen atoms
(ii) Atoms of the element may not necessarily possess the contained in a molecule. No subscript follows the symbol for
same mass but possess the same atomic number and oxygen which means, by convention, that only one atom of
show similar chemical properties (Discovery of oxygen is contained in the molecule.
isotopes). The subscripts representing the number of atoms contained in
(iii) Atoms of the different elements may possess the same a molecule of a compound are in no way related to the number of
mass but they always have different atomic numbers and atoms present in the molecule of a free element. Although both
differ in chemical properties (Discovery of isobars). hydrogen and oxygen are composed of diatomic molecules, a
(iv) Atoms of one element can be transmuted into atoms of water molecule contains only one atom of oxygen and two atoms
other element. (Discovery of artificial transmutation). of hydrogen. The two hydrogen atoms present in H2 0 are not
molecular hydrogen but rather two hydrogen atoms that have
(v) In certain organic compounds, like proteins, starch,
chemically combined with an oxygen atom.
cellulose, etc., the ratio in which atoms of different
elements combine cannot be regarded as simple. There For a chemical formula to be correct, it must contain two
are a number of compounds which do not follow the law pieces of information: (i) it must indicate the elements in the
of constant proRortions. Such compounds are called make up of the compound, and (ii) it must indicate the combining
non-stoichiometric compounds. ratio of atoms of these elements in the particular compound. The
first information is provided by including in the formula correct
chemical symbols for all the elements in the compound. The
1.~Oi ATOMS, MOLECULES AND FORMULAE second piece of information is provided by subscripts, i.e.,
An atom is the smallest particle of an element. The atom of numbers written to the right slightly below the chemical symbols
hydrogen is the smallest and the lightest. Atoms take part in of the elements.
chemical combination and remain as indivisible. All atoms do not Nitric acid is a combination of hydrogen, nitrogen and oxygen
occur free in nature. Avogadro introduced the idea of another giving a base formula RNO. These elements combine in the ratio
kind of particles called the molecules. A molecule is the smallest I : 1 : 3. Therefore, the correct formula for nitric acid is RN0 3 •
particle of an element or compound that can have a stable Some compounds are composed of ions rather than of
and independent existence. A molecule of an element consists molecules. Ions differ from atoms and molecules by being
of one or more atoms of the same element. Certain elements are electrically charged particles of matter. The charges may
capable of existence as single atoms and their atoms can be be positive or negative I and generally vary in magnitude.
regarded as molecules. A molecule of an element that consists of The positively charged idns are called cations and negatively
one atom only is called monoatomic molecule as in the case of charged ions are called: anions. Simple cations· and anions
inert gases. Oxygen is not stable in atomic form but is stable in come into existence by IQss and acceptance of an electron or
molecular form. A molecule of oxygen is diatomic in nature, i. e., electrons by neutral atoms respectively. Ions that consist of
its molecule consists of two oxygen atoms. Hydrogen, nitrogen, several atoms held together by chemical bonds similar to those
fluorine, chlorine, bromine, iodine are also diatomic like oxygen. involved in the molecules are called polyatomic ions or complex
 BASIC PRINCIPLES 13

ions. These complex ions differ from molecules in the sense that Common Name Chemical Name Chemical Formula
they bear a charge. Some of the common complex ions are:
Indian nitre Potassium nitrate KN0 3
N03" Nitrate PO~- Phosphate NH 4+ Ammonium
Limestone Calcium carbonate CaC0 3
so~- Sulphate CIO; Perchlorate PH4+ Phosphonium Lunar caustic Silver nitrate AgN03

SO~- Sulphite CO;- Carbonate MnO; Permanganate

Laughing gas Nitrous oxide Np
Litharge Lead monoxide PbO
When ions are present in a compound, the number of positive
Muratic acid Hydrochloric acid HCI
charges on a cation must balance with the negative charges on an
anion to produce electrically neutral matter. Since, the charge on Mohr's salt Ferrous ammonium FeS04(NH4)2S04
the anion may not always be equal to that on the cation, the sulphate ·6Hp
number of anions will not always be equal to the number of Milk of magnesia Magnesium hydroxide Mg(OH)2
cations. Microcosmic salt Sodium ammonium Na(NH 4 )HP04
Calcium nitrate consists of calcium and nitrate ions, Each hydrogen ortho-
calcium ion carries 2 units positive charge while each nitrate ion phosphate
carries I unit negative charge. Thus, to make net charge zero, two Marsh gas (Damp fire)Methane CH 4
nitrate ions will link with one calcium ion and the formula will be
Ca(N03 h, [Ca 2+ + 2NOi ]. Names and formulae of some Oleum Sulphuric acid H2~07
common chemical compounds are listed below: (Fuming)
Oxone Sodium peroxide Na 202
Common Name Chemical Name Chemical Formula
Plaster of Paris Calcium sulphate I
CaS0 4 ,-H2O
Alum Ammonium (NH4)2 S0 4' Al.2( S04)3 hemihydrate 2
aluminium sulphate '24H2O
Philosphers's wool Zinc oxide ZnO
Aspirin Acetyl salicylic acid C9H g04
Phosgene Carbonyl chloride COCl 2
Battery acid or Sulphuric acid H2SO 4
oil of vitriol Pearl ash Potassium carbonate K 2C0 3

Blue vitriol Copper sulphate CuS0 4,5HP Pyrene Carbon tetrachloride CCl 4

Baking soda Sodium bicarbonate NaHC0 3 Picric acid 2,4,6-Trinitrophenol C6H 2(OH)(N°2)3

Bleaching powder Calcium CaOCl 2 Quick lime Calcium oxide CaO

chlorohypochlorite Red lead (Minium) Lead tetroxide PbP4
BoraX Sodium tetraborate Na2BP7,I OH20 Sugar Sucrose C12H22011
Butter of tin Stannic chloride SnCI 4·5H2O Slaked lime (Milk of Calcium hydroxide Ca(OH)2
Caustic soda Sodium hydroxide NaOH lime)

Caustic potash Potassium hydroxide KOH Sid ammoniac Ammonium chloride NH4CI
Sugar oflead Lead acetate (CH 3COO)2Pb
Carbolic acid Phenol CJIsOH
Chile saltpetre Sonium nitrate NaN0 3 Sand Silicon dioxide Si02

Carborundum Silicon carbide SiC Table salt (Common Sodium chloride NaCI·
salt)
Corrosive sublimate Mercuric chloride HgCl2
TEL Tetra-ethyl lead Pb(C 2H s)4
Calomel Mercurous chloride Hg2Cl 2
Tear gas Chloropicrin CCl 3N02
Dry ice Carbon dioxide (solid) CO 2
Washing soda Sodium carbonate Na2C03,IOH20
Formalin Fonnaldehyde HCHO
(40% solution) Water glass Sodium silicate Na2Si03

Grain alcohol (Spirit) Ethyl alcohol . C2H sOH White vitriol Zinc sulphate ZnS°4 ,7H 2O

Green vitriol Ferrous sulphate FeS04,7H20

1~1~i! ATOMIC AND MOLECULAR MASS
Gypsum Calcium sulphate CaS04 ·2H20
One of the most important concepts derived from Dalton's atomic
Gammexane (BHC) Benzene hexachloride C6~C4;
theory is that of atomic mass, i. e" each element has a
llydrolith Calcium hydride CaH2 characteristic atomic mass. As atoms are very tiny particles, their
Hypo (Antichlor) Sodium thiosulphate Na2~03·5Hp
absolute masses are difficult to measure. However, it is possible
to determine the relative masses of different atoms if a small unit
14 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

of mass is taken as a standard. For this purpose, mass of one atom Thus,
of hydrogen was assumed as unity and was accepted as standard. 23
Tbe atomic mass of an element can be defined as tbe number lamu' 1.9924 x 10- = 1.66 X 10- 24 g or 1.66 x 10- 27 kg
wbich indicates how many times tbe mass of one atom of the 12 .
element is heavier in comparison to the mass of one atom: of
hydrogen.
A =Atomic mass of an element
Mass of one atom of the element
A == Atomic mass of an element =----------------------
lamu
Mass of one atom of the element
The atomic masses of some elements on the basis of carbon-l 2
Mass of one atom of hydrogen are given below:
In 1858, oxygen atom was adopted as a standard on account of Hydrogen 1.008 amu Iron 55.847 amu
the following reasons: Oxygen 16.00 amu Sodiuml 22.989 amu
(i) It is much easier to obtain compounds of elements with
Chlorine 35.453 amu Zinc 65.38 amu
oxygen than with hydrogen as oxygen is more reactive than
hydrogen. Magnesium 24.305 amu Silver 107.868 amu
(ii) The atomic masses of most of the elements. become Copper 63.546 amu
approximately whole numbers but with hydrogen as standard the
atomic masses of most of the elements are fractional. The actual mass of an atom of an element
The mass of one atom of natural oxygen was taken to be 16.0. The atomic mass of an element in amu x 1.66 x 10-24 g
Thus, atomic mass of an ~lement So, the actual mass of hydrogen atom
1.008 x 1.66 x 10-24 == 1.6736 X 10-24 g
element
Similarly, the actual mass of oxygen atom
16 th part of the mass of one atom of oxygen
16 x 1.66 x 10-24 = 2.656 X 10-23 g
Mass of one atom of the element x 16 It is clear from the above list of atomic masses that atomic
Mass of one atom of oxygen masses of a number of elements are not nearly whole numbers.
Actually, the above values are average relative masses. Most of
By accepting oxygen as a standard, the atomic mass of the elements occur in nature as a mixture of isotopes.
hydr6gen comes as 1.008, sodium 22.991 and sulphur 32.. 066. (Isotopes-the atoms. of the same element having different
In 1961, the International Union of Chemists selected a new atomic masses). With very few exceptions, however, elements
unit for expressing the atomic masses. They accepted the stable have constant mixtures of isotopes. Chlorine is found in nature as
isotope of carbon (12 C) with mass number of 12 as the standard. a mixture containing two isotopes CI-35 (34.969 amu) and CI-37
(36.966amu).These are found in the ratio of75.53% (CI-35) and
Atomic mass of an element can be defined as the number
24.47% (CI-37). Therefore, the average relative mass of chlorine
which indicates bow many times the mass of one atom of the
is calculated as:
element is heavier in comparison to 112 th part of the mass of
(34.969 x 0.7553)+ (3'6.966 x 0.2447)= 35.46 amu
one atom of carbon-ll (12 C).
Based on the average mass, the atomic mass of chlorine is
A == Atomic mass of an element 35.46 or 35.5 amu but it is never possible to have-an atom having
a relative mass 35.5 amu. It can have relative mass of about 35.0
Mass of one atom of the element or 37.0 amu depending on the particular isotope. Thus, average
~ th part of the mass of one atom of carbon -12 relative mass of any naturally occurring sample of chlorine is
35.46 or 35.5 amu as it is a mixture of two isotopes present in
= Mass of one atom of the element x 12 definite proportion. The same reasoning applies to all other
Mass of 'One atom of carbon -12 elements.
[The quantity' A' was formerly known as atomic weight. The average atomic masses of various elements are
However, this term is no longer used as the word 'weight' means det~ed by multiplying the atomic mass of each [Link] by its
gravitational force.] fractional abundance and adding the values thus obtained. The
Atomic mass unit: The quantity .
~
12
mass of an atom of fractional abundance is determined by· dividing percentage
abundance by hundred.
carbon-12 (12 C) is known as the atotinc~aSS unit and is
~ " m·X a+nxb
abbreviated as amu. The actual mass of one atom of carbon-l 2 is Average ISOtOPIC mass = - - - - - -
. m+n
1.9924 x 10-23 g or 1.99.24 x 10-26 kg.
here, a, b are atomic masses of isotopes in the ratio m : n.
*The term Dalton is used for one atomic mass unit, 1 Dalton = 1 amu.
 11. BASIC PRINCIPLES 15

..
Average IsotOPIC mass =-x X a+ X
b the mass of a molecule of a substance relative to the mass of an
100 100 atom of hydrogen as 1.008 or of oxygen taken as '16.00 or the
mass of one atom of carbon taken as 12. Molecular mass is a
here, x, y are percentage abundance of the two isotopes
number which indicates how many times one molecule of a
(y= 100-x).
substance is heavier in comparison to l~th of the mass of
Example 11. Boron has two isotopes boron-1O and boron-II
whose percentage abundances are 19.6% and 80.4% respectively. oxygen atom or l~ th of the mass of one atom of carbon-12.
What is the average atomic mass of boron?
M = Molecular mass
Solution: Mass of one molecule of the substance .
Contribution of boron-1O 10.0 X 0.196 = 1.96amu
12 th mass of one atom of carbon -12
Contribution of boron-II =[Link] 0.804 = 8.844amu
The mass of a molecule is equal to sum of the masses of the
Adding both =1.96+ 8.844 10.804amu atoms present in a molecule. One molecule of water consists of2
Thus, the average atomic mass of boron is 10.804 amu. atoms of hYQrogen and one atom of oxygen. Thus, molecular
. mass of water (2 x 1.008) + 16.06 18.016amu. One molecule
Example 12. Carbon occurs in nature as a mixture of of H 2 S04 (sulphuric acid) consists of2 atoms of hydrogen, one
carbon-12 and carbon-13. The average atomic mass ofcarbon is atom of sulphur and four atoms of oxygen. Thus, the molecular
12.011. What is the percentage abundance of carbon-12 in mass of sulphUric acid is
nature?
Solution: Let x be the percentage abundance of carbon-12;
=(2x 1.008)+ 32.00+ (4 x 16.00)
then (100 - x) will be the percentage abundance of carbon-I 3 . = 98.0160r 98.016amu

Therefore. 12x + 13(100- x) = 12.011 . Gram-molecular Mass or Gram Molecule

100 100' A quantity. of substance whose . mass. in grams is
or 12x+ 1300-13x= 1201.1 numerically equal to its molecular mass' is called gram-
or x= 98.9 molecular mass. In other words; molecular mass of a substance
expressed in grams is called gram-molecular mass ot gram
Abundance of carbon-12 is 98.9%. molecule. For exampl~, the molecular mass of chlorine is 71 and,
Gram-atomic Mass Or Gram Atum therefore, its gram-molecular mass or gram molecule is 71 g.
When numerical value of atomic mass of an element is Similarly, molecular mass of oxygen (02 ) is 32, i. e.,
expressed in grams, the value becomes gram-atomic mass or 2x 16= 32amu.
gram atom. The atomic mass of oxygen is 16 while gram-atomic Gram-molecular mass of oxygen 32 g
mass or gram atom of oxygen is 16 g. Similarly, the gram-atomic
masses of hydrogen, chlorine and nitrogen are 1.008 g, 35.5 g Molecular mass of nitric acid (HN0 3 ) is 63, i. e. ,
and 14.0 g respectively; Gram~[Link] [Link] = 1+ 14 + 3 x 16 = 63 amu
every element consists of same number of atoms. This number Gram-molecular mass of nitric acid = 63 g
is called Avogadro's number. The value of Avogadro's number
is 6.02 x 1023 . . Gram-molecular mass should not be confused with the mass
Absolute mass of one oxygen atom of one molecule of the substance in grams. The mass of one
molecule of a substance is known as its actual mass. For
= 16amu =16x 1.66 x 10- g
24
example, the actual mass of one molecule of oxygen is equal to
Therefore, the mass of 6.02 x 10 23 atoms of oxygen will be . 32x 1.66 x 10-24 g, i~e., 5.32 x 10-23 g.
= 16x 1.66 x 10-24 x 6.02 X 1023 The number of gram molecules of a substance present in a
16g (gram-:atomic mass) given mass of a substance can be determined by the application
of following formula:
Thus, gram-atomic mass can be defined as the absolute
mass in grams of 6.02 x 10 23 atoms of any element. No. of gram molecules
Mass of a substance in grams
Number of gram atoms of any element can be calculated with
the help of the following formula: Molecular mass of the substance in grams
Mass of the element in grams . Molar mass in grams
No. of gram atoms Mass of smgle molecule - 23
Atomic mass of the element in grams 6.023 x 10
Molecular Mass = Molar mass in amu x 1.66x 10- 24 grams
Like an atom, a molecule of ~ substance is also a very small 'Example 13. Calculate the mass of 2.5 gram atoms of
particle possessing a mass of the order OflO-24 to 10-22 g. Similar oxygen.
to atomic mass, molecular mass is also expressed as a relative
Solution: We know that,
mass with respect to the mass of the standard substance which is Mass of the element in grams
an atom of hydrogen or an atom of oxygen or an atom of No. of gram atoms = - - - - - - - - - - - - -
carbon-12. The molecular mass of a substance may be defined as Atomic mass of the element in grams
16 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

So, Mass of oxygen = 2.5 x 32 80.0g (ii) Molecule: The smallest particle of a substance (element or
compound) which has free or independent existence and possesses
Example 14. Calculate the gram atoms in 2.3 g ofsodium. all characteristic properties of the substance. A molecule of an
element is composed of like atoms while a molecule of a compound
Solution: No. of gram atoms 2.3 == 0.1 contains fixed number of atoms of two or more different elements. A
23
[Atomic mass of sodium 23 g] molecule may be broken down into its constituent atoms but the
atom is indivisible during a chemical change.
Example 15. Calculate the mass of 1.5 gram molecule of Avogadro after making the above differentiation, presented a
sulphuric acid. hypothesis known as Avogadro hypothesis which can be stated
Solution: Molecular mass of as follows:
H 2 S04 =2x 1+ 32+ 4 x 16= 98.0amu "Under similar conditions of temperature and pressure,
Gram-molecular mass of H 2 S04 =98.0g equal volumes of aD gases contain equal number of molecules."
Mass of 1.5 gram molecule of H 2 S04 =98.0x 1.5=147.0g Avogadro hypothesis explains successfully the formation of
hydrogen chloride.
Example 16. Calculate the actual mass ofone molecule of Hydrogen + Chlorine = Hydrogen chloride
carbon dioxide (C0 2 ),
I vol I vol 2 vol
Solution: Molecular mass of CO 2 = 44 amu nmolecules nmolecules 2n molecules
larrru 1.66xlO- 24 g I molecule I molecule 2 molecules
24 I 1
So, The actual mass of CO 2 == 44 x 1.66 x 10- '2 molecule '2 molecule I molecule
23 I atom I atom I molecule
7.304 X 10- g
(Both hydrogen and chlorine are diatomic in nature.)
Thus, the hypothesis explains that the molecules of reacting
1i.~_~~ AVOGADRO'S HYPOTHESIS gases break up into constituent atoms during chemical change
According to Dalton's atomic theory, elements react with each which then combine to form new molecules of the product or
other in the simple ratio of their atoms. Gay-Lussac proposed that products.
gases combine in simple ratio of their volumes. In an attempt to
correlate Dalton's atomic theory with Gay-Lussac law of gaseous Applications of Avogadro's hypothesis
volumes, Berzelius stated that under similar conditions of 0) Atomicity*: Atomicity means number of atoms present
temperature and pressure, equal volume of all gases contain in one molecule of an elementary gas. Hydrogen, oxygen,
the same number of atoms. This hypothesis was subsequently nitrogen, chlorine, etc., are diatomic in nature. Noble gases are
found to be incorrect as it failed to interpret the experimental monoatomic while ozone is triatomic in nature. Avogadro's·
results and contradicted the very basic assumption of Dalton's hypothesis helps in determining the atomicity of elements.
atomic theory, i. e., an atom is indivisible. For example, the (ii) Relationship between molecular mass and vapour
formation of hydrogen chloride from hydrogen and chlorine density: The vapour density of any gas is the ratio of the
could not be explained on the basis of Berzelius hypothesis. densities of the· gas and hydrogen under similar conditions of
Hydrogen + Chlorine = Hydrogen chloride
temperature and pressure.
I vol I vol 2 vol Density of gas
n atoms natoms 2n compound atoms Vapour Density (V.D.)
Density of hydrogen
I atom I atom 2 compound atoms
Jiatom Ji atom I compound atom Mass of a certain volume of the gas
Mass of same volume of hydrogen at
i. e., for the formation of I compound atom of hydrogen the same temp. and pressure
chloride, ~ atom of hydrogen and ~ atom of chlorine are needed.
In other words, each atom of hydrogen and chlorine has been If n molecules are present in the given volume of a gas and
divided which is against Dalton's atomic. theory. Thus, the hydrogen under similar conditions of temperature and pressure,
hypothesis ofBerzelius was discarded. Mass of n molecules of gas
The Italian scientist, Amedeo Avogadro, in 1811, solved the V.D.=---------------------
Mass of n molecules of hydrogen
above problem by proposing two types of particles from which
whole of the matter is [Link]. Mass of I molecule of gas
(i) Atom: The smallest particle of an element that can take
part in chemical change but generally cannot exist freely as such. Mass of I molecule of hydrogen

*Atomicity can be ascertained with the values of ratio of two specific heats of gases ( ~; )

1.66 (Monoatomic), = lAO (Diatomic), Cp 1.33 (Polyatomic)

Cv · .. Cv
 BASIC [Link] 17
Molecular mass of gas apples or one gross books means 144 books or one gross oranges
Molecular mass of hydrogen means 144 oranges. In a similar way, for counting of atoms,
molecules, ions, etc., chemistS use the unit mole. The term mole
Mol. mass
was introduced by Ostwald in 1896. This is the Latin word
2 'moles' meaning heap or pile. A mole (mol) is defined as the
(since, moL mass of hydrogen = 2) number of atoms in 12.00 g of carbon-12. The number of atoms
Hence, 2x V.D.=Mol. mass in 12 g of carbon-12 has been found experimentally to be
6.02xlQ23, This number is also known as Avogadro's number
This fonnula can be used for the detennination of molecular
masses of volatile substances from vapour density. Vapour named in honour of Amedeo Avogadro (1776 - 1856). .
density is measured mainly by two methods: Thus, a mole contains 6.02 x 1023 units. These units can be
(a) Victor Meyer and (b) Duma's methods. atoms, molecules, ions, electrons or anything else.
. (iii) Gram-molecular volume: I g mole of any gas 1 mole of hydrogen atoms means 6.02 x 1023 hydrogen atoms.
occupies 22.4 litres or 22400 mL of volume at NTP or STP
1 mole of hydrogen molecules means 6.02 x 1023 hydrogen
conditions. 11<
The density of hydrogen at NTP is 0.00009 g mL- l . Thus, molecules.
0.00009 g of hydrogen will occupy volume at NTP 1 mL 1 mole of potassiiun ions means 6.02 x 1023 potassium ions.

1 g of hydrogen occupies volume at NTP = 1 mL 1 mole of electrons means 6.02 x 1023 electrons.
. 0:00009
The type of entity must be specified when the mole
Ig mole of hydrogen (2.0 16 g) occupies volume at NTP designation is used. A mole of oxygen atoms contains 6.02 x 10 23
i 2.016 = 22400 mL = 22.4 litre oxygen atoms. and a mole of oxygen molecules contains
0.00009 6.02 x 1023 oxygen molecules. Therefore, a mole of oxygen
According to Avogadro's hypothesis, equal volumes of molecules is equal to two moles of oxygen' atoms,
different gases contain same number of molecules under similar i. e. , 2 x 6.02 x 1023 oxygen atoms.
conditions of temperature and pressure. Thus, 22.4 litre or 22400 How much does one mole weigh? That depends on the nature
mL of any gas at NTP will contain one gram mole or its molecular of particles (units). The mass of one mole atoms of any element
mass in grams. is exactly equal to the atomic mass in grams (gram-atomic
Loschmidt number: Number of molecules in 1 em3 or 1 mL mass or gram atom) of that element.
of a gas at S.T.P. is known as Loschmidt number. For example, the atomic mass of aluminium is 27 amu. One
. 6.023x10 23 amu is equal to 1.6{i x 10-24 g. One mole of aluminium contains
LOSChmidt number = --.---
22400 6.02 x 1023 alJlIl1inium atoms.
= 2. 68x 1018 molecules mL-1 Mass of one atom aluminiUm = 27 x 1.66 x 10-24 g
(iv) Molecular formula: Avogadro's hypothesis helps in Mass of one mole aluminium =27 x 1.66 x 10-24 X 6.02 x 1023
[mding the molecular formulae of gases. Under similar =27g
conditions of temperature and pressure, 2 volumes of ozone after This is the atomic mass of aluminium in grams or it is one
decomposition give 3 volumes of oxygen. gram atomic mass or one gram atom of aluminium.
Deco~tion Similarly, the mass of 6.02 x 10 23 moleC"!Iles (1 mole) of a
Ozone ) Oxygen
2 vol 3 vol substance is equal to its molecular mass in grams c.r
gram-molecular mass Or gram molecule. For example,
2 molecules 3 molecules molecular mass of water is 18 amu. Thus, mass of one mole of
I molecu1e 3/2 molecules water will be 18 x 1.66 x 10-24 X 6.02 x 1023 , i. e., 18 g. This is
the molecular mass of water in grams or one gram-molecular
1 molecule 3 atoms
mass or one gram molecule.
Thus, the fonnula of ozone is ° 3, Mole concept is also applicable to ionic compounds which do
not contain molecules. In such cases, the fonnula of an ionic
1~t3 MOLE CONCEPT. compound represents the ratio between constituent ions. The
mass of 6.02 x 1023 fonnula units represents one mole of an ionic
For the counting of articles, the unit dozen or unit gross is compound.
commonly used irrespective of their nature. For example, one
dozen pencils means 12 pencils or one dozen apples means 12

... O°C or 273 K temperature and one atmosphere or 760 rom ofHg or 76 cm ofHg pressure are known as the standard conditions of temperature and
pressure (STP) or normal conditions oftemperature and pressure (NTP).
18 I G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

One mole ofBaC1 2 = 6.02 x 1023 BaCl 2 units Number of water mOlecules in one mole of water
23
= 208.2g BaCl 2 6.02 x 10
Molecular mass (fomrula mass) of BaCl 2
Number of molecules of water in 0.05 moles
:::: 6.02 x 1023 Ba 2+ ions + 2 x 6.02
X 10
23 CI- ions 0.05 x 6.02 x 1023
= 137.2+ 71.0 = 208.2g 3.01Ox 1022
One mole of a substance will have mass equal to formula As one molecule of water contains one oxygen atom,
mass of that substance expressed in grams. So, number of oxygen atoms in 3.010 x 1022 molecule of
It has been established by Avogadro's hypothesis that one water 3.010x 1022
gram-molecular mass of any gaseous substance occupies a
volume of 22.4 litres at NTP. One gram-molecular mass is Example 19. Calculate the mass of a single atom of
nothing but one mole of substance. Thus, one mole, sulphur and a single molecule ofcarbon dioxide.
i. e. , 6.02 x 1023 molecules of any gaseous substance occupies Solution:
22.4 litres as volume at NTP.
The following formulae satisfy the above discussion. Gram-atomic mass of sulphur = 32g
1 mole of a substan[Link] 6.02 x 1023 particles ofthe substance Gram-atomic mass
Mass of one sulphur atom
Number of moles of a sub~tance 6.02 x 1023
Mass of substance in gram 32
::::---- 5.33 X 10-23 g
Mass of one mole of the substance in gram 23
6.02 x 10
No. of particles
Further, Number of moles = 23 Formula of carbon dioxide = CO 2
6.02 x 10
Molecular mass of CO 2 12+2xI6=44
Thus, Gram-molecular mass of CO 2 44 g
No. of particles = Mass of substance in gram Gram-molecular mass
6.02 x 10 23 Mass of one mole of the substance in gram Mass of one molecule of CO 2
6.02x
Mass of one atom of an element
Gram atom of an element = 4 4 = 7.308 x 10-23 g
6.02 x 1023
6.02 x 1023
Mass of one molecule of a substance Example 20. What is the mass of3.01 xl 022 molecules of
Gram-molecular mass of the substance ammonia?
=
6.02 x Solution: Gram-~olecular mass of ammonia 17 g
Number of molecules
:::: Vohune of gas in litres at NTP x 6.02 x 1023 Number of molecules in 17g (one mole)ofNH3 = 6.02 x 1023
22.4 Let the mass of 3.01x 1022 moieculesofNH3 be =xg

3.01 x 1022 x
,£ : :: ::: _SOME SOLVED eXAMPLES\ :::: : : ; So,
6.02x 1023 17
Example 17. A piece ofcopper weighs 0.635 g. How many 22
or x 17x 3.01x 10 =0.85g
atoms ofcopper does it contain? IeEE (Bihar) 19921
6.02x 1023
SolutiOn: Gram-atomic mass of copper:::: 63.5 g
Example21. From 200 mg of CO2 , 1021 molecules are
Number of moles in 0.635 g of copper 0.635 == 0.01
63.5 removed. How many moles ofCO2 are left?
23
Number of copper atoms in one mole = 6.02 x 10 Solution:
Number of copper atoms in 0.01 moles [Link] 6.02 x 1023 Gram-molecular mass ofe02 :::: 44 g
6.02 x 1021
Example 18. How many molecules o/water-and oxygen Mass of 10 21 molecules of CO2 . 44 x 1021 = 0.073 g
6.02 x 1023
atoms are present in 0.9 g ofwater?
Mass of CO 2 left = (0.2 - 0.073) = 0.127 g
Solution: Gram-molecular mass of water :::: 18 g

Number of moles in 0.9g·of water = 0.9 = 0.05 Number of moles of CO 2 left 0.127 = 2.88 x 10- 3
18 44
 BASIC PRINCIPLES I 19

23
::Example 22. How many molecules and atoms of oxygen 6.02 x 10
are [Link] 5,6 lUres of oxygen (0 2 )at NTP?
x 60x 60x 24 x 365
Solution: We know that, 22.4 litres of oxygen at NTP
contain 6.021< 1023 molecules of oxygen, = 19,089x 109 years = 1.9089x 1010 years

So, 5,6litres of oxygen at NTP contain .if

= 5,6 x 6,02 x 1023 molecules

22.4
23
1. Ill> mgof a compound on vaporisation in Victor Meyer's
1.505 x 10 molecules apparatus displaces 44.8 mL of air measured at STP. The
molecularmass of the compound is: [CEE (Kerala) 20041
1 molecule of oxygen contains 2 atoms of oxygen (a) 116 (b) 232 (c) 58 (d) 44,8 (e) 46.4
[Ans. (c)]
So, 1.505 x 1023 molecules of oxygen contain [Hint: Molar mass of compound
2 x 1.505 X 1023 atoms = Mass of22400 mL vapour at STP
23
3.01 X 10 atoms = OJ 16 x 22400 = 58]
44.8
Example 23. How many electrons are present in 1.6 g of
2. A gas has a vapour density 11.2. The volume occupied by I g
methane?
of the gas at NTP is: (JCECE 2004)
Solution: Gram-molecular mass of methane, (a) I L (b) 11.2 L (c)22.4 L (d) 4 L
(CH 4 ) 12+ 4 = 16g [Ans. (a)]
Number of moles in 1,6 g of methane [Hint: Molar mass 2 x 11,2 = 22.4 g
:::: 1.6 OJ 22.4
Volume of I g compound at STP ;=. - - = I L]
16 22.4
3. 3 g of hydrocarbon on combustion with 11.2 g of oxygen
Nunlber of molecules of metharie in 0.1 mole
produce 8,8 g of CO2 and 5.4 g of H 20. The data illustrate
:::: 0,1 x 6,02 x 1023 the law of:
6,02 x 10 22 (a) conservation of mass (b) multiple proportions
(c) constant proportions (d) reciprocal proportions
One molecule of methane has = 6 + 4 = Ioelectrons [Ans. (a)]
[Hint: L Masses of reactants L Masses of products
22
So, 6,02 x 10 molecules of methane have (3 + 11.2) g (8,8 + 5.4) g
Hence, law of conservation of mass is verified.]
10 x 6,02 X 1022 electrons
4. The maximum number of molecules is present in:
23
6,02 x 10 electrons [CBSE (PMT) 2004; Manipal (Medical) 20071
(a) 15 L ofIt2 gas at STP (b) ~ L ofN2 gas at STP
Example 24. The electric charge on the electron is
(c) 0,5 g ofH2 gas (d) 10 g of 02 gas
1.602 x 10- 19 coulomb, How much '~harge is present on 0,1 mole
[Ans. (a)]
ofCu 2+ ions? [Hint:
Solution: Charge on one mole of ele«trons 15
Number of molecules in 15 L H2 = - x N = 0.669 N
:::: 6,02 x 1023 x 1.602 X 10-19 coulomb 22.4
:::: 96500 coulomb :::: 1 faraday Number of molecules in 5 L No =_5_ x N = 0.223·N
- 22.4
Charge on one mole of Cu 2+ ions
= 2 x 96500 coulomb 2 faraday Number of molecules in 0,5 g H2 = 0.5 xN =: 0,25 N
2
Charge on 0.1 mole of Cu 2+ ions
Number of molecules in 10 g 0, =: .!Q x N = 0.312 N]
=[Link] 2 0.2faraday - 32
ExalJlple 25. How many years it would take to spend one 5. Insulin contains 3.4% sulphur. Then, the minimum molecular
mass of the insulin is about:
Avogadro snumber ofrupees at a rate oflO lakh of rupees in one
second? (MLNR 1990)
(a) 940 amu (b) 9400 amu
(c) 3600 amu (d) 970 amu
Solution: Number of rupees spent in one secon[Link] 10 6
[Ans. (a)]
Nunlber of rupees spent in one year [Hint: .: 3.4 g sulphur is present in 100 g insulin
:::: 106 X 60x 60x 24 x 365
:. 32 g sulphur will be present in 100 x 32 g insulin = 940
Avogadro's number of rupees will be spent 3,4

:. Molar mass of insulin is about 940 amu]

20 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

6. 25 g of MC1 4 contains 0.5 mol chlorine then its molecular active metals. A known mass of the active metal· is reacted with
mass is: (DPMT 2007) dilute mineral acid. Hydrogen gas thus evolved is measured
(a) 100g mol- 1 ,b) 200g mol- l under experimental conditions. The volume of hydrogen is then
reduced to NTP conditions. The mass of liberated hydrogen is
(c) 150g mol- l (d) 400g mol- l
determined using density of hydrogen (0.00009 at NTP).
[Ans. (b)]
[Hint: I mol of MCI 4 contaiils 4 mol of chlorine Equivalent IllIlSS Mass of element x 1.008
.,' 0.5 mol chlorine is present in 25 g of MCl 4 Mass of hydrogen

;;4 mol chlorine will be present in~ x 4, i.e.,200 g ofMCI 4.] Mass of element x 1.008
0.5
Volume in mL ot' hydrogen displaced atNTPx 0.00009

'1.'14 EQUIVALENT MASSES OR CHEMICAL Mass of element x 11200

EQUIVALENTS Volume in mL of hydrogen displaced at NTP

Equivalent mass of a substance (element or compound) is defmed (ii) Oxide formation method: A known mass of the
as the number of parts by mass of the substance which element is changed into oxide directly or indirectly. The mass of
combine or displace directly or indirectly 1.008 parts by mass oxide is noted.
of hydrogen or 8 parts by mass of oxygen or 35.5 parts by Mass of oxygen (Mass of oxide Mass of element)
mass of chlorine or 108 parts by mass of silver.
The equivalent mass is a pure number. When the equivalent Thus, the equivalent mass of the element
:-
mass of a substance is expressed in grams, it is called gram Mass of element x8
equivalent mass. For example, equivalent mass of sodium is 23, (Mass of oxide Mass of element)
hence, its gram equivalent mass is 23 g. • /
Mass of element x 8
The equivalent mass of a substance may ha~e different values
under different conditions. The -equivalent mass of an element Mass of oxygen
may vary with change of valency. For example, copper fornts two (iii) Chloride formation method: A known mass of the
oxides CUO and Cu 2 0. In CUO, 63.5 parts of copper combine element is changed into chloride directly or indirectly. The mass
with 16 parts of oxygen. Thus, equivalent mass of copper in this of the chloride is determined.
oxide is 6~5 31.75. In Cu 20' 2 x 63.5 parts ofcopper combine Mass of chlorine (Mass of chloride Mass of element)
with 16 parts of oxygen; thus, the equivalent mass of copper in Thus, the equivalent mass of the element
this oxide is:
Mass of element x 35.5
2 x 63.5 = 63.5
(Mass of chloride Mass of element)
2
Relation between atomic mass, equivalent mass and Mass of element x 35.5
valency: Suppose an element X combines with hydrogen to
. fom a compound, XH n , where n is the valency of the element X.
(iv) Metal to metal displacement method: A more active
n parts by mass of hydrogen combine with atomic mass of metal can displace less active metal from its salt's solution. For
elementX. example, when zinc is added to copper sulphate, copper is
1 part by m\lSS of hydrogen combines with precipitated. A known mass of active metal is added to the salt's
Atomic mass of element solution of less active metal. The precipitated metal after drying
n is accurately weighed. The masses of the displacing metal and the
.. Atomic mass of element. h . displaced metal bear the same ratio as their equivalent masses. If
B y ab ove defiImtlOn, IS t e eqUlva- El and E2 are the equivalent masses of two. elements and
n ml and m2 their respective masses, then,
lent mass of the element.
Atomic mass ml =~
Thus, Equivalent mass m2 E2
n
Knowing the equivalent mass of one metal, the equivalent
or Atomic mass Equivalent mass x Valency
mass of th.e other metal can be calculated.
Note: 'Detailed discussion'on equivalent masses of compounds (acids,
bases, salts, oxidising agents, reducing agents, etc.,) will be (v) Double decomposition method: This method is based
taken in chapter on volumetric analysis. on the following points:
The following methods are, used for the determination of (a) The mass of the compound reacted and the mass of
equivalent mass of elements. product formed are in the ratio of their equivalent masses.
(i) Hydrogen displacement method: This method is used (b) The equivalent mass of the compound (electrovalent) is
for those elements which can evolve hydrogen from acids, i.e., the sum of equivalent masses of its radicals.
 BASIC PRINCIPLES 21

(c) The equivalent mass of a radical is equalto the fonnula (a) 4 (b) 2 (c) 3 (d) 1.5
mass of the radical divided by its charge. [ADS. (d)]

AB+CD ~AD+CB , of metal = 16 = ~

[Hint: Equivalent mass n
ppt.
Mass of AB Equivalent mass of AB Where x atomic mass of metal
nvalency of metal
Mass of AD Equivalent mass of AD Molecular fonnula of metal oxide M 20 n
Eq. mass of A + Eq. mass of B Mass of metal oxide := 2 (16n) + 16(n) = 1.5]
Mass of metal ' 2 (l6n)
Eq. mass of A + Eq. mass of D \
Knowing the equivalent masses of Band D, equivalent mass 1.15' ME"rHODS FOR THE DETERMINATION
of A can be calculated. OF ATOMIC MASS
(i) Dulong and Petit's Law: According to this law, the
product of atomic mass and specific heat of a solid element is
7. An unknown element fonns an oxide. What will be the approximately equal to 6.4. The product of atomic mass and
equivalent mass of the element if the oxygen content is 20% specific heat is called atomic heat. Thus,
by mass: [JEE (W8) 2008] Atomic mass x Specific heat = 6.4
(a) 16 (b) 32 (c) 8 (d) 64
[ADS. (b)] or . mass (approximate
AtOlTIlC . ) = - - .6.4
---
. Mass of element . Specific heat
[Hint: Eqwvalent mass of element := x8
Mass of oxygen In above fonnula, the specific heat must he in cal/g unit.
80 The equivalent mass of the element is determined
= x 8 =32]
20 experimentally and the valency, which is always a whole number,
8. A metal M of equivalent mass E fonns an oxide of molecular can be obtained by dividing approximate atomic mass with the
fonnulaMxOy- The atomic mass of the metal is given by the equivalent mass and changing the value so obtained to the nearest
correct equation: [PMT (Kerala) 2008] whole number. In this way, exact atomic mass can be determined
(a) 2E(y/ x) (b).xyE by multiplying equivalent mass with valency.
(c) EI y (d) y/ E Example 26. A chloride of an element contains 49.5%
E x chlorine. The specific heat of the element is 0.056. Calculate the
(e)-x
2, y eqUivalent mass, valency and atomic mass of the element.
[Ans. (a)] Solution: Mass of chlorine in the metal chloride = 49.5%
[Hint: Let atomic mass of metal Mis' a'. Mass of metal (100- 49:5) 50:5
Mass of metal = a x x
. Mass of metal
Mass of oxygen = 16 X Y Eqmvalent mass of the metal '" x 35.5
. Mass of element Mass of chlorine
Eqwvalent mass of element = x8
Mass of oxygen 50.5 x 35.5 36.21
E=~x8 49.5
16y According to Dulong and Petit's law,

a 2E(~)] ·
ApproXlmate . mass 0 fth e metaI = -----.",....---
atOlTIlC
.
6.4
. Specifjc heat
9. The percentage of an element Mis 53 in its oxide of mlllecular 6.4 114.3
fonnula M 203' Its atomic mass is about: 0.056
[PET (Kerala) 2oo8J
(a) 45 (b) 9 (c) 18 (d) 38 Valency = Approximate atomic mass _ 114.3 3.1 '" 3
(e) 21 Equivalent mass 36.21
[Ans. (e)]
., . Mass of element Hence, exact atomic mass = 36.21 x 3 = 108.63
[HIDt: Eqwvalent mass of element = '. x 8
. Mass of oxygen Example 27. On dissolving 2.0 go/metal in sulphuric
53 " acid, 4.5lg o/the metal sulphate wasformed. The specific heat of
=-x[Link]
47 the metal is 0.051 cal g-I. What is the valency of the metal and
Atomic mass = Equivalent mass x Valency exact atomic mass?
=9x3 =27 amu.] Solution: Equivalent mass of SO~- radical
10. The equivaLent weight of a metal is double than that of
oxygen. How many times is the weight of its' oxide greater Ionic mass = 96 = 48
than the weight of metal? Valency 2
22 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

Mass of metal sulphate = 4.51 g Examples of isomorphous compounds are:

Mass of metal 2.0g (a) K 2 S04 and K 2Cr0 4 (potassium sulphate and potassium
Mass of sulphate radical (4.51 ~ 2.0) == 2.51 g chromate)
2.51 g of sulphate combine with 2.0 g of metal. °
(b) ZnS04 ·7H2 and FeS04·7H 20 (zinc sulphate and
ferrous sulphate)
So, 48 g of sulphate will combine with (c) KCI04 and KMn0 4 (potassium perchlorate and
potassium permanganate)
=2. x 48 = 38.24 g metal
2.51 (d) K2 S04·Al2 (S04 ll' 24H2 0and K2S04·Cr2(S04k24H20
(potash alum and chrome alum).
Equivalent mass of metal = 38.24
The following conclusions have been deduced from the
According to Dulong and Petit'slaw, phenomenon of isomorphism:
(i) Masses of two elements that combine with same mass of
Approximate atomic mass 6.4 =~ = 112.5 other elements in their respective compounds are in the ratio of
Specific heat 0.057
their atomic masses. .
Approximate atomic mass
Valency = . Mass of one element (A) that combines
Equivalent mass with a certain mass of other elements Atomic mass of A
Mass of other element (B) that combines .Atomic mass of B
= 112.5 = 2.9"" 3 with the same mass of other elements
38.24
(ii) The valencies of the elements forming isomorphous
Exact atomic mass 38.24 x 3 114.72
compounds are the same.
(ii) Canniizaro's method: Atomic mass of an element Example 28. Potassium chromate is isomorphous to
may be defined as the smallest mass of the element present in the potassium sulphate (K 2 S0 4 ) and is found to contain 26.78%
molecular mass of anyone of its compounds. For this purpose, chromium. Calculate the atomic mass ofchromium (K = 39.10).
the following steps are followed: Solution: Since, the formula of potassium sulphate is
(a) Molecular masses of a number of compounds in which the K 2S04, so the formula of potassium chromate should be
element is present are determined. K 2Cr04 as it is isomorphous to K 2S0 4.
(b) Each compound is analysed. Mass of the element is If the atomic mass of chromium is A, then
determined in the molecular mass of each compound. . formula mass of potassium chromate should be
(c) The lowest mass ofthe element is taken its ato~c mass. = 2x 39.1+ A + 64 =(142.2+ A)
The following table shows the application of this method:
% of chromium A x 100
Vapour· Molecular % of carbon Mass of carbon In (142.2+ A)
Compound .density mass = by mass In one molecular mass 100A
(V,D.) lV.D. compound of the compound . So, 26.78
(142.2+ A)
75.0 x 16
Methane 8 16 75.0 = 12 g
100 100A = 26.78 (142.2+ A)
80.0 x 30
Ethane 15 30 80.0 =24 g or A 26: 78 x 142.2 52.00
100 73.22
Carbon 42.9 x.28
14 28 42.9 =12 g (iv) Atomic mass fmm vapour density of a chloride: The
monoxide 100
following steps are involved in this method:
Carbon 27.3 x44
22 44 27.3 = 12g (a) Vapour density of the chloride of the element is
dioxide 100
determined.
81.8 x 44
Propane 22 44 81.8 =36 g (b) Equivalent mass of the element is determined.
100
Let the valency ofthe element bex. The formula of its chloride
Least mass of carbon is 12 g.
Thus, the atomic mass of carbon is 12.
.
will be MCI x'
Molecular mass = Atomic mass of 1M + [Link]
(iii) The law of isomorphism: Isomorphous substances
form crystals which have same shape and size and can grow in = A + [Link]
the saturated solution of each other. They have a property of Atomic mass Equivalent mass x Valency
forming mixed crystals. Isomorphous substances have same
composition, i. e., they have same number of atoms arranged A =Exx
similarly. Molecular masS = E x x + [Link]
 BASIC PRINCIPLES 23
2 V.:O. x(E+ 35.5) Molecular formula mass
where, n
2V.D~ Empirical formula mass
x
E + 35.5 Molecular formula gives the following informations:
Knowing the value of valency, the atomic mass can be (i) Various elements present in the molecule.
determined. (ii) Number of atoms of various elements in the molecule.
Example 29. One gram ofa chloride was found to contain (iii) Mass ratio of the elements. present in the molecule.
0.835 g of chlorine. Its vapour density is 85. Calculate its The mass ratio of carbon and oxygen in CO 2 molecule is
molecular formula. 12 : 32 or 3 : 8.
Solution: Mass of metal chloride = Ig (iv) Molecular mass of the substance.
(v) The number written before the formula indicates the
Mass of chlorine = 0.835 g number of molecules, e.g., 2C0 2 means 2 molecules of
Mass of metal = (1- 0.835) = 0.165 g carbon dioxide.
. I f I 0.165x 35.5 (iii) Structural formula: It represents the way in which
E qillva ent mass 0 meta = - - - -
0.835 atoms of various elements present in the molecule are linked with
=7.01 one another. For example, ammonia is represented as:
2 V.D.
Va1ency 0 f the meta1= - - - H
E+ 35.5
2x 85 I
= N--H
7.01 + 35.5 I
4 H
Formula of the chloride = MC1 4
The formula indicates that three hydrogen atoms are linked to
Example 30. The oxide of an element contains 32.33 per one nitrogen atom by three single covalent bonds. '
cent of the element and the vapour density of its chloride is 79.
Calculate the atomic mass of the element.
1.17 PERCENTAGE COMPOSITION OF A
Solution: Mass of the element = 32.33 parts COMPOUND
Mass of oxygen (100- 32.33) = 67.67 parts Percentage composition of a compound is the relative mass of the
Equivalent mass of the element = 32.33 x 8 = 3.82 each of the constituent element in 100 parts of it. It is readily
67.67 calculated from the formula of the compound. Molecular mass of
2V.D. 2x 79 a compound is obtained from its formula by adding up the masses
VaIency 0 ftheeIement =4 of all the atoms of the constituent elements present in the
E + 35.5 3.82+ 35.5
molecule.
Hence, the atomic mass of the element = 3.82 x 4 Let the molecular mass of a compound be M and X be. the
mass of an element in the molecule.
= 15.28
Mass·of element
Percentage of element = x 100
1.16" TYPES OF FORMULAE M
X
As already stated in section 1.1 0, a formula is a group of symbols =-xI00
M
of the elements which represents one molecule of the substance.
Formula represents chemical composition of the substance. . Example 31. Calculate the percentage composition of
There are three kinds of formulae in the case of compounds. calcium nitrate.
(i) Empirical formula: .It represents the simplest relative Solution: The formula of calcium nitrate is Ca(N03 h.
whole number ratio of atoms of each element present in the
Thus, the formula mass or molecular mass
molecule of the substance. For example, CH is the empirical
formula of benzene in which ratio of the atoms of carbon and = At. mass of Ca + 2 x At. mass of N + 6 x At. mass of oxygen
hydrogen is 1 : 1. It also indicates that the ratio of carbon and 40 + 2 x 14 + 6 x 16
hydrogen is 12 : 1 by mass.
164
(ii) Molecular formula:· Molecular formula of a compound
is one which expresses as the actual number of atoIris of each % of Ca 40 x 100 = 24
element present in one molecule. C6H6 is the molecular formula 164
of benzene indicating that six carbon atoms and six hydrogen
%ofN= 28 x 100= 17
atoms are present in a molecule of benzene. Thus, 164
Molecular formula = n x Empirical formula %ofO 100-(24+17)=59
24 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

Example 32. . Determine the percentage of water of

crystallisation, iron, sulphur and oxygen in pure ferrous sulphate
(FeS04·7H20 ). .
11. A gas mixture contains 50% helium and 50% methane by
Solution: The formula mass of ferrous sulphate volume. What is the percentage by mass of methane in the
mixture? IeEE (Kerala) 2004)
= At. mass of Fe -+ At. mass of S + 4 x At. mass ot:oxygen
(a) 19.97% (b) 20.05% (c) 50% (d) 75%
+7 x Mol. mass of J::i20
(e) 80.03%
= 56.0+ 32.0+ 4x 16.0+ 7x 18.0 [Ans. (e)]
[Hint: Molar and volume ratio will be same, i. e., 1 : L
= 278.0
:. Mass of 1 mole CH4 and He will be 16 and 4 g respectively.
So, % of water of crystallisation = 126 x 100 = 45.32 Mass of CH 4
278 Percentage by mass of CRt = x 100
Total mass
%of iron = 56 x 100=20.14 16
= x 100"" 80%]
278 20
12. The atomic composition of the entire universe is
%ofsulphur= 32 x 100=11.51
278 approximately iven in the table below:
64 of total no~ of atoms
%ofoxygen = - x ]00=23.02
278
H 93
(Oxygen present in water molecules is not taken into account.)
He 7
Example 33. It is found that 16.5 g of metal combine with
oxygen to form 35.60 g of metal oxide. Calculate the percentage Hydrogen atoms constitute what percentage of the universe
of metal and oxygen in the compound. by mass? .
Solution: (a) 77% (b) 23% (c) 37% (d) 73%
[Ans. (a)]
Mass of oxygen in oxide = (35.60- 16.50)= 19.10 g
[Hint: Mass of 93 'H' atoms = 93 amu
%of metal = 16.50 x 100= 46.3 Mass of7 'He' atoms = 28amu
35.60
93
. . 19.10 % Hydrogen by mass = x 100 = 77%]
%[Link] ~-- x tOO= 53.7 (93 + 28)
'., 35.60
13. Which pair of species has same percentage of carbon?
Exa~ple 34. Hydrogen. and [Link] are combined in the
(a) CH 3COOH and C 6H l2 0 6
ratio 1: 16 . by mass in hydrogen peroxide. Calculate the
(b) CH 3 COOH and C 2 H 5 0H
percentagtt4Jf·hydrogen and oxygen in hydrogen peroxide.
(c) HCOOCH~ and Cl2H22011
Solution: 1i part<; of hydrogen peroxide contain hydrog~n
. = 1part . (d) C 6H I2 0 6 and (42H22011
[Ans. (a)]
100 parts of hydrogen peroxide contain hydrogen
1 [Hint: Percehtage of carbon in acetic acid = 24 x 100 = 40%
=~x tOO = 5.88 60
17
%of oxygen =(100- 5.88)=94.12 Percentage of carbon in CJil206 = I!:. x 100 = 40%]
180
Example 35. On analysis of an impure sample of sodium
14. Which of the following alkanes has 75% of carbon?
chloride, the percentage ofchlorine was found to be 45.5. What is
(a) Cz»t. (b) CH4 (c) C3Hg (d) C4 HlO
the percentage ofpure sodium chloride in the given sample? '.
[Ans. (b)]
Solution: The molecular mass of pure sodium chloride (NaCI)
= At. mass of Na + At. mass of chlorine [Hint: Percentage of carbon in methane:: 12 x 100 = 75%]
16
= (23 + 35.5) = 58.5
15. Which of the following two oxides of nitrogen have 30.5%
% of chlorine in pure NaCI nitrogen?
35.5 x 100= 60.6 (a) NO (b) NOz (c) N z0 4 (d) N 2 0 5
58.4 [Ans. (b) and (c)]
Thus, [Hint: Percentage of nitrogen in NO z = 14 x 100= 30.5%
% of purity of NaCI in the sample 46
:;:: 45.5 x tOO = 75 28
Percentage of nitrogen in N z0 4 - x 100 = 30.5%]
60.6 . 92
 I
BASIC PRINCIPLES 25

1~1)'; DETERMINATION OF EMPIRICAL AND The empirical fonnula is C 2 H 6 0.

MOLECULAR FORMULAE Empirical fonnula mass (2 x 12) + (6 x 1) + 16 = 46
The. following steps are followed to detennine ~he empirical Example 38. A compound of carbon, hydrogen and
fonnula of the compound: nitrogen contains these elements in the ratio 9: 1 : 3.5. Calculate
(i) The percentage composition of the compound is the empirical formula. If its molecular mass is 108, what is the
detennined by quantitative analysis. molecular formula?
(ii) The percentage of each element is divided by its atomic Solution:
mass. It gives atomic ratio of the elements present in the
Element Atomic Relative number Simplest
compound. Element
ratio mass of atoms ratio
(iii) The atomic ratio of each element is the divided by the
minimum value of atomic ratio as to get the simplest ratio 0.75 = 3
Carbon 9 12 9 =0.75
of the atoms of elements present in the compound. 12 0.25
(iv) If the simplest ratio is fractional, then values of simplest
I I =4
ratio of each element is multiplied by a smallest integer to Hydrogen - =I
I 0.25
get a simplest whole number for each of the element. ' .
(y) To -get the empirical fonnula, symbols of various 3.5 == 0.25 0.25 = I
Nitrogen 3.5 14
elements present are written side by side with their 14 0.25
respective whole number ratio as a subscript to the lower
The empirical fonnula = C 3 H4N
right hand comer of the symbol.
The molecular fennula of a substance may be determined Empirical formula mass =(3x 12)+ (4x 1)+ 14;::: 54
from the empirical fonnula if the molecular mass of the substance n;::: Mol. mass ;::: 108 =2
is known. The molecular fonnula is always a simple multiple of [Link] 54
empirical fonnula and the value of simple mUltiple is obtained by
dividing molecular mass with empirical fonnula mass. Thus, molecular fonnula of the compound
= 2 x Empirical fonnula
Example 36. Calculate the empirical formula for a
compound that contains 26.6% potassium, 35.4% chromium and = 2x C3 H4 N= C6 HgN2
38.1% oxygen.· Example 39. A carbon compound containing only carbon
[Given K 39.1; Cr= 52; 0 = 16] and oxygen has an approximate molecular mass of 290. On
Solution: analysis, it is found to contain 50% by mass of each element.
Relative Simplest What is the molecular formula of the compo":nd?
Per- Atomic Simplest Solution:
Element number of whole number
centage mass. ratio
atoms ratio Simplest
I ti num ber SI mpIest whole number
Element AtomIc Reave
Potassium 26.6 39.1
26.6
=0.68 0.68 =1 Ix2=2 percentage mass of atoms ratio ratio
39.1 0.68

Chromium 35.4 52.0 35.4 == 0.68 0.68 =1 1x2=2 4.166 = 1.33

52 0.68 Carbon 50.0 12 4.166 4
3.125

Oxygen 38.1 16.0 38.1 = 2.38 2.38 = 3.5 3.5 x 2= 7

' 16 3.125 = 1
16 0.68 Oxygen 50.0 3.125 3
3.125
Therefore, empirical fonnula is K 2 Cr2 0 7• The empirical fonnula ;::: C4 0 3
Example 37. A compound contains 34.8% oxygen, 52.2% Empirical formula mass = (4 X 12)+ (3 x 16) = 96
carbon and 13.0% hydrogen. What is the empiricalformula mass Molecular mass 290
ofthe compound?
Solution: n = Mol. mass -290 = 3 apprmamate
. 1
y
Emp. mass· 96
Atomic Relative number Simplest
Element Percentage. Molecular fonnula = n x Empirical fonnula
mass of atoms ratio
3 x C4 0 3 = C12 0 9
34.8 = 2.175 2.175 = 1
Oxygen 34.8 16 Example 40. A compound on analysis, was found to
16 2.175
have the follOWing composition: (i) Sodium = 14.31%,
Carbon 52.2 12 52.2 =4.35 4.35 = 2 (ii) Sulphur ;::: 9.97%, (iii) Oxygen = 69.50%, (iv) Hydrogen
12 2.175 ;::: 6.22%. Calculate the· molecular formula of the compound
13.0 13.0 = 6 assuming that whole of hydrogen in the compound is present as
Hydrogen 13.0 13.0
2.175 water ofcrystallisation. Molecular mass ofthe compound is 322.
26 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

Solution: 17. A compound has an empirical formula c;H4o. An

Atomic Relative number independent analysis gave a value of 132.16 for its molecular
Element Percentage Simplest ratio mass. What is the correct molecular formula?
mass of atoms
[CET (Kerala) 2004[
0.622 = 2 (a) C4H40S (b) ~oHI2
Sodium 14.31 23 0.622
0.311 (c) <;03 (d) C6H I2 0 3
0.311 (e) C4 HgOs
Sulphur 9.97 32 0.311 =1
0.311 [Ans. (d)]
6.22 [Hint: Molecular formula = (C2H40)n
Hydrogen 6.22 1 6.22 = 20
0.311 n= Molecular mass = 132.16 = 3
4.34 =14 Empirical formula mass 44
Oxygen 69.50 16 4.34
0.311
Molecular formula = (C2H40)3 = CJI1203]
The empirical formula = Na2SH20014
18. An organic compound containing C and H has 92.30%
Empirical formula mass (2 x 23)+ 32+ (20 x 1)+ (14 x 16) carbon. Its empirical formula is:
=322 (a) CH (b) CH3
Molecular mass = 322 (c) CH2 (d) CH4
Molecular formula = Na 2SH 20 014 [Ans. (a)]
Whole of the hydrogen is present in the form of water. Thus, [Hint: Percentage of carbon =-12 x 100 = 92.30%
10 water molecules are present in the molecule.· . 13
So, molecular formula = Na 2SO 4 ·lOH2 ° 'Or'

Relative
Atomic Simplest
fUUSTRATfONSOF,OB]ECTlviQUESY}'ONS Element Percentage
mass
number of
ratio
atoms

Carbon . ~2.30 12 7.69

Hydrogen 7.70 7.70

Empirical formula = CH]

19. Two oxides of a metal contain 50% and 40% of metal M
respectively. If the formula of first oxide is MO, the formula
of 2nd oxide will be:
(a)M02
(c)M2 0
[Ans. (b)]
Hint:
% x Molecular mass = 43.86 x 146 = 4
Compound 1 Compound 2
° 100 Atomic mass 100 16
M 0 M 0
Molecular formula C1;H IO0 4
50% 50% 40% 60%
Molecular mass= 12 x 6 + 10 xl + 16 x [Link] 146
50 g 50 g 40t 60g
'Or'
50 60
Relative 1g -::lg 1g I.5g
Atomic Simplest 50 40
Element Percentage number of
mass ratio 2
, atoms
Carbon 49.30 12 4.10 1.5x2::3
Formula: MO M 20 3]
20. Two elements X and Y have atomic mass 75 and 16
Hydrogen 6.84 6.84 2:5 x 2 = 5
respectively. They combine to give a compound having
Oxygen 43.86 16 2.74 I x 2:: 2 75.8% X. The formula ofthe compound is:
(a) XY (b) X 2 Y
The empirical formula C3Hs02
(C)X 2Y2 (d)X 2Y3
2X73
n::: ";2 [Ans. (d)]
73
[Hint: Molecular mass of X 213 2 x 75 + 3 x 16 = 198
Molecular formula:: 2 X C3Hs02 C1;H IO0 4 ]
 BASIC PRINCIPLES 27
150
Percentage of' X = - x 100 = 75.80% Information Obtained from Chemical Equation
198
'Or' A balanced chemical equation provides the following
informations:
Relative
Atomic Simplest (i) What are the reactants and products involved in the
Element Percenta'ge number of
mass ratio
atoms chemical change?
X 75.80 75 1.01 Ix 2=2 (ii) The relative number of molecules of reactants and
y
products.
24.20 16 1.51 1.5 x 2 = 3
(iii) The relative number by parts of mass of reactants and
Formula = X 21'3] products.
21. The crystalline salt Na 2 S04 ·xH2 0 on heating loses 55.9% of (iv) Relative volumes of gaseous reactants and products.
its mass. The fonnula of crystalline salt is: For example, consider the following reaction:
(a) Na 2 S04 ·5H2 0 (b) Na 2 S04 ·7H2 0 CH 4(g)+ 20 2 (g)=C0 2 (g)+ 2H 20(g)
(c) Na 2 S04 ·2H2 0 (d) Na 2 S04 ·lOH2 0 This equation tells us that methane and oxygen are reactants
(e) Na 2 S04 ·6H2 0 [PMT (Kerala) 2007] and carbon dioxide and water are products~ One molecule of
JAns. (d)] methane reacts with two molecules of oxygen to produce one
[Hint: Molecular mass of Na 2S0 4 ·lOH20 molecule of coi' and two molecules of water or one mole of
=46+ 96+ 180= 322amu methane reacts with two moles of oxygen to produce one mole of
180 carbon dioxide and two moles of water or 16 g of methane reacts
% by mass ofHP = - x 100 = 55.9%]
. 322 with 64 g of oxygen to produce 44 g of CO 2 and 36 g of water.
This equation also tells that I vol. of methane reacts with 2 vol. of
oxygen to produce I vol. of CO 2 and 2 vol. of steam under
1.1.9; CHEMICAL EQUATION similar conditions of temperature and pressure.
A chemical equation is a symbolic representation of a chemical Limitations of Chemical Equation
change. A chemical equation fails to provide the following
The substances, in which the chemical change is brought, are informations:
called reactants and the substances which come into existence as (i) Actual concentration of the reactants taken and the actual
the result of chemical change are called products. The concentration of the products obtained.
relationship between reactants and products is represented in the (ii) Time taken for the completion of the chemical change.
form of a chemical equation. The symbols or formulae of the (iii) . Conditions applied for bringing the chemical change.
reactants are written on left hand side of equality (=) or ~ sign
(iv) Whether the reaction is reversible or irreversible.
and the symbols or formulae of products on right hand side. The
The following efforts have been made to make the chemical
symbols or formulae on both the sides are added by + sign. Such
equations more informative by introducing:
an equation is known as skeleton equation. The equation
(i) Experimental conditions: If a particular chemical
becomes balanced when total number of atoms of various
change occurs under certain temperature and pressure conditions,
elements are made equal on both the sides. Gases are always
these are mentioned above and below the (~ ) or ( = ) sign.
written in molecular form.
200 attn
KCl0 3 ~ KCl + 02 N2 + 3H 2 ~ 2NH3
450"C
This is the skeleton equation as it only represents reactant and
If the [Link] occurs in presence of a catalyst, it is written
products involved in the chemical change but the following
.above the ( ~ ) or ( = ) sign.
equation is a balanced equation as the number of atoms of various
Pt
elements is equal on both sides. 2S0 2 + 02 ~ 2S03
2KCl0 3 = 2KCl + 302 (ii) Heat evolved or absorbed: Heat evolved or absorbed in
Reactant ~
a chemical change can be represented by adding or subtracting
The following notations are also used in chemical equations as the amount of heat on right hand side.
to provide more information about chemical change: N2 + 02 ~ 2NO- 43.2kcals
(i) Upper arrow (i) IS written immediately after the C + O 2 ~ CO 2 + 94.3 kcals
gaseous product. (iii) Reversible or irreversible nature: Reversible
(ii) Lower arrow (.!.) is written immediately after the reactions are shown by changing the sign of equality (=) or
insoluble substance (solid) which deposits from a solution. arrow (~ ) with sign of double arrow (, ').
(iii) Symbols, (s) for solid, (I) for liquid and (g) for gas are N 2(g)+ 3H2(g)~ 2NH 3(g)
also written to represent the physical state of the reactants
and products. Types of Chemical Equations
(iv) Symbol (aq.) is written for substances dissolved in water. Chemical equations are of two. types:
(v) Symbol (~) is written over an arrow or over an equality (i) Molecular equations
sign to represent heating. (ii) Ionic equations.
28 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

Molecular equations are thoSe in which reactants and products Measures. This revised set of units is known as the
are represented in the form of molecules. International System of Units (abbreviated SI). Now the SI
BaCl 2 + Na 2 S0 4 BaS04 J, + 2NaCl units have been accepted by the scientists all over the world in all
2NaOH + H 2 S0 4 Na 2 S04 J, + 2H 2 0 branches of science, engineering and technology. '
Ionic equations are those in which reactants and products are The SI system have seven basic units. The various
written in ionic form. The molecular equation fundamental quantities that are expressed by these units along
BaCl 2 + Na2S04 BaS04 J, + 2NaCI with their symbols are tabulated below:
can be written in ionic form as:
Basic pbysical quantity Unit Symbol
Ba 2+ + 2CI- +2Na + + SO~- BaS04 J, + 2Na + + 2Cl-
Ba 2+ + SO~- = BaS04 J, Length Metre m
Note: Calculations based on chemical equations have been dealt in the Mass Kilogram kg
chapter 'Stoichiometry' in 'Inorganic Chemistry'.
Time Second s
1~20;' MEASUREMENT IN CHEMISTRY: Temperature Kelvin K
FUNDAMENTAL AN.D DERIVED UNITS Electric current Ampere amp orA
Chemistry is an experimental science. An experiment always Luminous intensity Candela cd
involves observation-of a· phenomenon under certain set of
conditions. The quantitative scientific observation generally Amount of substance Mole mol
requires the measurement of one or more physical quantities such
Sometimes, submultiples and multiples are used to reduce or
as mass, length, density, volume, pressure, temperature, etc.
enlarge the size of the different units. The names and symbols of
A physical quantity is expressed in terms of a number and a
sub-multiples and multiples are listed in the table given below.
unit. Without mentioning the unit, the number has no meaning. For
The name for the base unit for mass, the kilogram, already
example, the distance between two points is "four" has no meaning
contains a preftx. The names of other units of mass are obtained
unless a specific unit (inch, centimetre, metre, etc.,) is associated
by substituting other prefixes for prefix kilo. The names of no
with the number. The units of physical quantities depend on three
other base units contain prefixes.
basic units, i.e., units of mass, length and time. Since, these are
independent units and cannot be derived from any other units, they The use of SI system is slowly growing, however, older
are called fundamental units. It was soon realised that the three systems are still in use. Furthermore, the existence of older units
fundamental units cannot describe all the physical quantities such in scientific literature demands that one must be familiar with
as temperature, intensity of luminosity, electric current and the both old and new systems.'
amount of the .substance. Thus, seven units of measurement, Submultiples Multiples
namely mass, length, time, temperature, electric current, luminous
intensity and amount of substance are taken as basic units. All Prefix Symbol Sub-multiple Prefix Symbol Multiple
other units can be derived from them and are, therefore, called deci d 10- 1 deca da 10
derived units. The units of area, volume, force, work, density,
centi c 10-2 hecto h 102
velocity, energy, etc., are all derived units.
milli m 10-3 kilo k 103
SI Units of Measurement micro 10-6 mega M HI'
Jl
Various systems of units were in use prior to I91'l0. The 10-9
nano n giga G 109
common ones are the following:
pico P 10- 12 tera T 1012
(i) The English or FPS system: The system uses the foot,
the pound and the second for length, mass and time femto f 10- 15 peta P 1015

measurements respectively. It is not used now-a-days. atto a 10-18 exa E 10

18

(ii) MKS system: Here M stands for metre (a unit of zepto z 10-21 zeta Z 102 1
length), K for kilogram (a unit of mass) and S for second (a unit yocto 10-24 yotta Y 1024
of time). This is a decimal system. .
(iii) CGS system: Here the unit oflength is centimetre, the Greek Alphabets
unit of mass is gram and the unit of time is second. It is also a
Alpha A IX Nu N v
decimal system.
MKS system often known as metric system was very popular Beta B ~ Xi .:. ~
throughout the world, but the drawback with this system was that Gamma r y Omicron 0 '0
a number of different metric units for the same quantity were Delta 11 5 Pi n 11:
used in different parts of the world. In 1964, the National Bureau
of Standards adopted a slightly modified version of the metric
system, which had been officially recommended in 1960 by an
Epsilon
Zeta,
Eta
E
Z
H
,E Rho
Sigma
T\lu
P
L
p
cr
international body, General Conference of Weigbts and l'J 't 't
 BASIC PRINCIPLES 29
Theta e e UpsiloJ:l. r \) frequently by chemists. Certain other units which are not a part of
Iota I t Phi <I> .<\1 SI units are still retained for a limited period of time. The term
Kappa Chi atmosphere (atm), the unit of pressure, falls into this category.
K 1( X X
Few of the old units along with conversion factors are given
Lambda A A Psi lJ' lJf below:
Mu M j.t Omega Q ro Length: The interatomic distances are reported in units of
Numerical Prefix. angstrom (A), nanometre (nm) or picometre (pm).
lA= 10-8 cm= 10- 10 m
Prefix VaHue Prefix Value
Inm=10-7 cm=10-9 m=WA
Herni (II2) Deca 10
Mono Undeca 11 Ipm=W- IO cm 10- 12 m 10-2 A
Sesqui 1":
2
Dodeca 12 Inm 103 pm
DiorBi 2 Trideca 13 Mass: The basic unit of mass is generally taken as gram (g).
Tri 3 Tetradeca 14 The gram is 10-3 kg.
Tetra 4 Pentadeca 15 I kilogram (kg) = 103 g
, Penta 5 Hexadeca 16
Hexa 6 Heptadeca 17 1 milligram (mg)= 10-3 g
Hepta 7 Oetadeca 18 1 microgram (Ilg) =10-6 g
Oeta 8 Nonadeca 19 While dealing with atoms arid molecules, the term atomic
Nona 9 Eicosa 20 mass unit (amu) is used. One amu is taken exactly as ..!.. of the
. 12
SI Units for Some Common Derived Quantities mass ~f an atom of the carbon isotope, C : I2

(a) Area = length x breadth 1amu= 1.6605 x W~24 g = 1.6605 X 10-27 kg

= m x m = m 2 [square metre] Volume: The units of volume are reported as cubic
.(b) Volume length x breadth x height centimetre (cm 3) and cubic decimetre (dm 3). Cubic decimetre is
termed litre while cubic centimetre is termed miUilitre.
= mx mX m=m 3 [cubic metre]
llitre (lit or L) (Wcm)3 = WOOcm 3 = 10-3 m 3
· mass kg k -3
(c) Denslty=---=-= gm lmillilitre(mL)=(lcm)3 =lcm3 (cc) = 10-6 m 3
volume m 3
So, . I litre = 1000 mL
(d) Speed = distanc~ covered = ~etre = m S-I
time bme Temperature:. The celsius temperature scale which is not
. change in velocity ms- . -2·
I a part of SI system, is ·employed in scientific studies. This scale is
(e) Acceleration = = - - = ms based on the assignment of O°C to the normal freezing point of
time taken s .
water and 100°C to the normal boiling point of water. The celsius
(f) Force = mass x acceleration scale was formerly called the centigrade scale. .
The unit of temperature in SI system is Kelvin. A degree on
=kg x ms-2
the kelvin scale has the same magnitude as the degree on the
kg ms-2 (Newton, abbreviated as N) . celsius scale but zero on the kelvin scale is equal to -273.15"C.
The temperature (0 K) is often referred to as absolute zero.
(g) Pressure =force per unit area
So, K =: (OC+ 273.15)
k -2
g ms =kg m- I
or °c (K - 273.15)
m2
(Pascal-Pa) There is another important temperature scale known as
fahrenheit scale. In this scale, the normal freezing point of water
(h) Energy = force x distance travelled
is 32"F and normal boiling point is 212"F. Thus, 100"C equals
=kgms-2 xm 180"F. Both the scales are related by the following equations:
kg m 2 s-2 ( joule-J) oC=~ x (OF - 32)[since, 100 parts on celsius scale
9
Some Old Units Stili in Use = 180 parts on fahrenheit scale]
The use of some of the old units is still permitted. The 'litre' ,
for example, which is defined as I cubic decimetre is used
30 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

Pressure: There are three non-S1 units for pressure which Values of Some Useful Constants
are commonly used.
F\lndamental
(a) Atmosphere (atm) is defined as the pressure exerted by a Value In old units Value in SI units
constant
column of mercury of 760 mm or 76 cm height at O°C.
(b) Torr is defined as the pressure exerted by a I mm column 'Avogadro's
of mercury at O°C. number(N)
(c) Millimetre of mercury (mm Hg). Atomic mass . 1.6605 X 10-24 g 1.6605 X 10-27 g
These three units are related as: unit (amu)
Bohr radius (~) 0.52918A = 0.52918· 5.2918 X 10-11 m
latm=760torr 760mmHg 76cmHg 1.013 x 105 Pa
x 10-8 cm
Energy: Calorie has been used in the past as a unit of energy
Boltzmann 1.3807 X 10-23 JK- 1
measurement. The calorie was defmed as the. amount of heat constant (k)
required to raise the temperature of one gram of water from
14.5"C to 15.5°C. One calorie is defined as exactly equal to 4.184 Charge on e1ectron(-) 4.8029 x 10-10 esu (-) l.6021 X 10-19 coul
(e)
joules.
Ical 4.184 J or 11 = 0.2390 cal Charge to mass 1.7588 x 108 coul g-1
ratio el m of
1kcal = 1000 cal ==4.184 kJ electron
Conversion factors
I angstrom (A) = 10-8 cm=1O- IO m==IO-1 nm=10 2 pm
1 inch 2.54 cm.
39.37 inch = I metre
or

1 kg = 2.20 pounds (lb)

lcm =0.394 inch
1km=0.621mile
19 = 0.0353 ounce (0)
Electron rest
mass (me)
GaS constant
(R)
9.1091 x 10-28 g

1
0.0821lit atm deg- mol-

1.987
1

=2.0 cal deg-lmol- I

l
9.1091 X 10-31 kg

I
8.314 x 107 erg deg-1mor' 8.314 J K- mol-
.
1

..

1 pound (lb)=453.6g Molar volume 22.4 L mol- 1

1atomic IIm:ss unit (amu) == 1.6605 x 10- 24 g at NTP (Vm)
= 1.6605 x 1O- 27 kg Planck's constant 6.6252 x 10-27 erg sec 6.6252 X 10-34 J sec
(h)
= 1.492 x 10- 3 erg = 1.492 x 10- 10 J
Proton mass (mp) l.6726 x 10-24 g 1.6726 X 10-27 kg
3.564 X lOll cal =9.310 x 10 8 eV
Neutron mass 1.67495 x 10-24 g 1.67495 X 10-27 kg
=931.48 MeV (mn )
1atmosphere (atm) = 760 torr = 760 mmHg = 76cmHg Rydberg constant lQ9678 cm- 1
= 1.01325 x 10 5 Pa (R,,)

1calorie (cal)=4.1840x 10 7 erg =4.184 J Velocity of light 2.9979 x 1010 cm seC l 2.9979 X 108 m sec-I.
(c) in vacuum or 186281 miles sec-I
2.613 x 1019 eV
Faraday (F) 9.6487 x 104 C I equiv.
lcoulomb (coul) =2.9979 x 109 esu or 96500 C/equiv.
, 1curie (Ci) = 3.7 X 1010 disintegrations sec -I 0.8988xl0 1O N m 2C-2
lelectron volt (eV) 1.6021 x 1O-12 erg = L6021 x 10- 19 J or9x 109 N m 2e 2

= 3.827 xl 0-20 cal Derived SI Units

= 23.06 kcal mol- 1
Quantity with Symbol Unit (SI) Symbol
lerg 10-7 J = 2.389 x lO-scal 6.242 x 1011 eV
Velocity (v) metre per sec m
1electrostatic unit (esu) = 3.33564 x 10- 10 coul
Area (A) square metre
1faraday (F):= 9.6487 X 104 coul Volume (V) cubic metre
1dyne (dyne) = lO-s N Density (P) kilogram m- 3
1 joule = 107 erg = 0.2390 cal Acceleration (a) metre per sec2
llitre=1OOOcc 1000rnL=ldm3 Energy (E) joule (J) kgm 2
10- 3 m 3 Force (F) • newton (N) kgm
 BASIC PRINCIPLES 31

Power(W) watt0N) 243.4 has four significant figures.

Pressure (P) pascal (Pa) N m-2
. 24.123 has five significant figures.
(ii) A zero becomes significant figure if it appears between
Resistance (R) ohm(n) V A-I
two non-zero digits. For example,
Conduction (e) ohm-I, mho, siemens m-2 kg- I S3 A2 or n- I 5.03 has three significant figures.
Potential difference volt (V) kgm 2 S-3 A-I 5.604 has four significant figures.
4.004 has four significant figures.
Electrical charge coulomb (C) A-s (ampere-second)
(iii) Leading zeros or the zeros placed to the left of the
Frequency (v) hertz (Hz) cycle per sec number are never significant. For example,
Magnetic tesla (T) kg S-2 A-I =N A-I m- I 0.543 has three significant figures.
flux x density
0.045 has two significant figures.
Popular Units and their SI Equivalents 0.006 has one significant figure.
(iv) Trailing zeros or the zeros placed to the right of the
Physical quantity Unit with symbol .Equivalent in SI unit· number are significant. For example,
Mass 1 amu larnu = 1.6605 x 10-27 kg 433.0 has four significant figures.
19
433.00 has five significant figures.
Energy 1 electron volt (eV) 1.602 x 10- joule
343.000 has six significant figures.
Length I A 10- 10 m (10- 1 om) (v) In exponential notation, the numerical portion gives the
number of significant figures. For example,
Volume litre 10-3 m 3 =dm 3
1.32 x 10-2 has three significant figures.
Force dyne 10-5 N
1.32 x 10 4 has three significant figures.
Pressure I atmosphere 760 torr (760 mm Hg)
(vi) The non-significant figures in the measurements are
101325 pa or 105 pa rounded off.
1 bar 101325 pa or 105 pa (a) If the figure following the last number to be retained is
1 torr 133.322 N m-2 less than 5, all the unwanted figures are discarded and
the last number is left unchanged, e.g.,
Dipole moment debye,IO- 1S esu-cm 3.324 x 10-30 cm
5.6724 is 5.67 to three significant figures.
Magnetic flux density gauss (0) 10-4 T (b) If the figure following the last number to be retained
Area of nuclear I bam 10-28 m 2 is greater than 5, the last figure to be retained is
cross section increased by I unit and the unwanted figures are
discarded, e.g.,
Nuclear Diameter 1 fermi (1 femto) 10-15 m
8.6526 is 8.653 to four significant figures.
(c) If the figure following the last number to be retained
Significant Figures
is 5, the last figure is increased by 1 only in case it
There is always some degree of uncertainty in every scientific happens to be odd. In case of even number the last
measurement except in counting. The uncertainty in . figure remains unchanged.
measurement mainly depends upon two factors: 2.3524 is 2.4 to two significant figures. '
(i) Skill and accuracy of the observer,
7.4511 is 7.4 to two significant figures.
(ii) Limitation of the measuring scale.
To indicate the precision of a measurement, scientists use the Calculations Involving Significant Figures
term significant figures. The significant figures in a number are In most of the experiments, the observations of various
all certain digits plus one doubtful digit. The number of measurements are to be combined mathematically, i. e., added,
significant figures gives the information that except the digit at subtracted, multiplied or divided as to achieve the fmal result.
extreme right, all other digits are precise or reproducible. For Since, all the observations in measurements do not have the same
example, mass of an object is 11.24 g. This value indicates that precision, it is natural that the final result cannot be more prec~se
actual mass of the object lies between 11.23 g and 11.25 g. Thus, than the least precise measurement. The following two rules
one is sure of frrst three figures (1, 1 and 2) but the fourth figure should be followed to obtain th~ proper number of significant
is somewhat inexact. The total significant figures in this number figures in any calculation.
are four. Rule 1: The result of an addition or subtraction in the
The following rules are observed in counting the number of numbers having different precisions should be reported to the
significant figures in a given m;asured quantity: same number of decimal places as are present in the number
(i) All non-zero digits are significant. For example, having the least number of decimal places. The rule is illustrated
42.3 has three significant figures. by the following examples:
I
32 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

(a) 33.3 ~(has only one decimal place) posses~ed by the least precise term used in the calculation.
3.11 Examples are:
0.313 (a) 142.06
Sum 36.723 f-, (answer should be reported x 0.23 ~(two significant figures)
to one decimal place) 32.6738 ~ (answer should nave two

Correct answer = 36.7 significant figures)

Correct answer = 33
(b) 3.1421 (b) 51.028
0.241 x 1.31 ~(three significant figures)
0.09 ~(has 2 decimal places) 66.84668
Sum 3.473.1 ~ (answer should be reported to Correct answer = 66.8
2 decimal places) 0.90 = 0.2112676
(c)
Correct answer 3.47 4.26
(c) 62.831 ~(has 3 decimal places) Correct answer 0.21
- 24.5492 Note: (i) Same procedure is followed if an expression involves
multiplication as well as division. .
Difference 38.2818 ~ (answer should be reported
(ii) The presence of exact numbers in an expression does not
to 3 decimal places after affect the number of significant figures in the answer.
rounding off) Examples are:
Correct answer = 38.282 (a) 3.24 x 0.0866 = 0.055643 (b) 4.28 x 0.146 x 3 =44.84784
5.046 0.0418
Rule 2: The answer to a multiplication or division is
rounded off to the same number of significant figures as is Correct answer = 0.0556 Correct answer == 44.8

MISCELLANEOUS NUMERICAL EXAMPLES4'/////

."""" ..
Example 1. 0.44 g of a hydrocarbon on complete Solution: ~ccording to law of conservation of mass,
combustion with oxygen gave 1.8 g water and 0.88 g carbon Mass of lime + Mass of carbon dioxide = Mass of calcium
dioxide. Show that these results are in accordance with the law of carbonate
. conservation of mass.
560 g + Mass of CO 2 = 1000 g
Solution: A hydrocarbon is a compound which consists of
carbon and hydrogen only. It undergoes combustion forming Mass of CO 2 = 1000 - 560 = 440 g
carbon dioxide and water as products. Molecular mass of CO2 = 12 + 32 = 44 g (l mole)
Formula of carbon dioxide = CO 2 ;
Molecular mass 12 + 32 44 g No. of moles in 440 g of CO2 = 440 = 10
. 44
Formula of water H 2 0;
Molecular mass 2+ 16 = 18g 1 mole of CO 2 occupies volume at NTP = 22.4 litre
12 10 moles of CO 2 will occupy volume at NTP
Mass of carbon in 0.88 g of CO2 x 0.88 = 0.24 g
44
= 22.4 x 10·= 224 litre
Mass of hydrogen in 1.8 g of H 2 0 = 2 x 1.8 = 0.20 g Example 3. 10 mL of hydrogen combine with 5 mL of
18
Total masses of carbon and hydrogen in the products oxygen to yield water. When 200 mL of hydrogen at NTP are
0.24 + 0.20 = 0.44 g passed over heated CuO, the CuO loses 0.144 g of its mass. Do
these results correspond to the law ofconstant proportions?
This is equal to the mass of hydrocarbon before combustion.
Thus, the results are in accordance with the law of Solution: 1st Case:
conservation of mass. 2
Mass of 10 mL hytlrogen at NTP = - - x 10= 0.00089 g
Example 2. Calcium carbonate decomposes completely, 22400
on heating, into lime (CaO) and carbon dioxide (C0 2 ), 1 kg of 32
calcium carbonate is completely decomposed by heat, when 560 g Mass of5 mL of oxygen at NTP = - - x [Link] 0.00714 g
22400
of lime are obtained. How much quantity of carbon dioxide in
grams, moles and litres at NTP is produced in the process?
 BASIC PRINCIPLES I 37

8.923 0.884 X 10- 16 cm 3

Mass of 22400 mLofHg vapouratNl})"" - - x 22400 .
,',,' 1000 ' .
Volume 0.884 x 10- 16
199:87 g' Mass of virus = = -----
Specific volume 0.75
Hence, molecular mass of Hg 199.87g
::: 1.178xlO- 16 g
.,. 6.4
(c) Approxunate atotnlc mass = - - - ,6.4 193.93 Molar maSs of vi~ = Mass of single virus x 6.023 x 1023 .
Sp. heat 0.033 g
= 1.178 X 10- 16 x 6.023 X 1023
Valency of Hg = 193.[Link] 2 (nearest whole number)
100 . = 7.095 xl0 7

So, accurate atomic mass Eq. mass x Valency Example 27. Weighing 31 04 carats (1 carat::: 200 mg), the
Cullinan diamond was the largest natural diamond ever found.
= 100 x 2= 200g How many carbon atoms were present in the stone?
.. Mol. mass 199.88_
A tOI11lClty ==--- 1 Solution: Mass of the stone
At. mass 200
= 3104 x 200= 620800mg::::: 620.8g
Hence, mercury molecules are monoatomic. Number of atoms of carbon
Example 23. How many grams of CaO are required to
Mass in gram x 6.023 x IOZ3
neutralise 852g ofP401O? (lIT 2005)
Gram-atomic mass
Solution: The reaction will be:
6CaO+ P4010 ~2Ca3(P04h 620.8 x 6.023 x 10 23 =3.12 X 1015
12
852 g P40 lO == 3 mol P40 lO Example 28. A cylinder of compressed gas contains
1 mole of P4010 neutralises 6 moles ofCaO. nitrogen and oxygen in the ratio 3: I by mole. If the cylinder is
known to contain 2.5 x 104 g ofoxygen, what is the total mass of
.. 3 moles OfP401O will neutralise 18 moles [Link].
the gas mixture?
Mass of CaO= 18;- 56=1008g
Solution: Number of moles of oxygen in the cylinder
. ' Example 24. If 1 grain is equal to 64.8 mg, how many\
Mass in 2.5 x 10 4
moles of aspirin (mol. wt: == 169) are present" in ,'tt 5 grain aspirin \
tablet? . \ Molecular mass in gram 32
Solution: Mass of aspirin in the tablet == 64.8 x 5 324 mg = 781.25
== 0.324g NumberofmoiesofN 2 3x781.25 2343.75
Number of moles = Mass = 0.324 Mass of nitrogen in the cylinder 2343.75 x 28
Molar mass 169
65625g
1.92 x 10-3
= 6.5625 x 104 g
Example 25. If the volume occupied in a crystal by a
Total mass of the gas in the cylinder
molecule of NaCI is 47 x 10-24 mL, calculate the volume of the
crystal weighing Ig. = 2.5 xl 04 + 6.5625 X 104 9.0625 X 104 g
Solution: Number of molecules of NaCI Example 29. Atmospheric air has 78% N z ;21% 02;
Mass x 6.023 x 1023 0.9 % Ar and 0.1 % CO 2 by volume. What is the molecular mass
Molar mass
_1_' x 6.023 x 1023 = 1.03x·1022
ofair in the atmosphere?
Solution:
.
Molecular mass of mixture
58.5
,L %ofeach M 1
- - - - x 0 ar mass
Volume of crystal = L03 x 1022 x 47 X 10-24 = 0.484 mL 100
,Example 26. A plant virus is found to consist of uniform 78 21 0.9 0.1
= x 28+-x 32+-x40+-,x44=28.964
cylindrical particles of 150 A in diameter and 5000 A long. The 100 100 100 100
specific volume ofthe virus is 0.75cm 3 /g. Ifthe virus is considered
Example 30. The famous toothpaste Forhans contains 0.76
to be a single particle, find its molecular mass. (lIT 1999)
g of sodium per gram of sodium monofluoroorthophosphate
Solntion: Volume of cylindrical virus = nrzl

3.14 x C~O x 10- 8

r x 500Qx 10-
8
(Na3P04F)in 100mL.
(a) How many fluorine atoms arepresent?
(b) How much fluorine in milligrams is present?
38 G.R.B.
-
PHYSICAL CHEMISTRY FOR COMPETITIONS

Solution:
Molar mass ofNa3P04F 3 x 23 + 31+ 16 x 4 + 19= 183
183 g Na3P04Fcontains 19 g fluorine
22. x gram of CaC03 was completely burnt in air. The mass of the
.. 0.76g Na3P04Fcontains 19 x 0.76g fluorine solid residue formed is 28 g. What is the value of' x' in gram?
183
(EAMCET 20(5)
:::: 0.0789 g= 78.9 mg fluorine (a) 44 (b) 200 (c) 150 (d) 50
Number of fluorine atoms [Ans. (d)]
_M_ass_in--=-_ _ x 6.023 xl 0 23 [Hint: CaC0 3(s) CaO(s) + CO 2 (g)
lOOg 56g
Gram-atomic mass
56 g residue 100 g CaC0 3
= 0.0789 x 6.023 x 1023
19 :. 28 g residue 50g CaC03]
= 2.5 x 1021 atoms 23. The mass of carbon anode consumed (giving only carbon
dioxide) in the production of270 kg of Al metal from bauxite
t~;txample31. An alloy of iron (54.7%), nickel (45%) and by Hall process is:
manganese (0.3%) has a density of 8.17 g/cm 3 . How many (a) 270 kg (b) 540 kg (c) 90 kg (d) 180 kg
iron atoms are there in a block of alloy measuring [Ans. (c)]
10cmx 20cmx 15 cm? [Hint: 3C + 2Al Z0 3 --,--74Al + 3C02
3x 12g 4X27=108g
Solution:
Volume of the block of alloy = lOx 20x 15cm3 .: 108 g Al is produced by consuming == 36 g carbon
:. 270 x 103 g AI will be produced by consuming
:::: 3000cm 3
,Mass of the block 3000 x 8.l7g ::::2451Og 36 x 270 x 103 g carbon
108
Mass of i,ron in the block
54.7 x 24510; 13406.97 g 90 x 103 g':" 90 kg carbon]
100
24. The equivalent mass of an element is 4. Its chloride has
Number of iron atoms in the block __M_a_ss__ x 6.023x 10 23
Atomic mass vapour density 59.25. Then the valency ofthe element is:
004 003 ~2 WI
13406.97 x 6.023 x 1023 [Ans. (b)]
56
[Hint: Molecular mass of MCI n == 59.25 x 2 = 118.5
:::: 1.442 X 1026
a + 35.5 x n= 118.5 ... (i) .
iiS'Example 32. An analysis of pyrex glass showed 12.9%
B 20 3 , 2.2% A12 0 3 , 3.8% Na20, 0.4% K 20 and remaining is Equivalent mass x n + 35.5 x n =118.5
Si0 2. What is the ratio ofsilicon to boron atoms in the glass ? 4n + 35.5n == 118.5 ... (ii)
'(BCECE 20(7)
n= 3]
Solution:
25. Sulphur trioxideis prepared by the fol1owing two reactions:
Percentage compositio~ ofB z 0 3 12.9%
S8(s) + 802 (g) ~ 8S02~g)
Percentage composition of
SiOz 100 - [12.9 + 2.2 + 3.8 + 0.4] 2S02(g) + 02(g ) ~ 2S03 (g)
How many grams of S03 are produced from 1 mole S8?
80.7%
(a) 1280 (b) 640
,. Mass . 12.9
NumberofmoiesofB 20 3 == =-=0.184 (c) 960 (d) 320
, Molar mass 70 [ADs. (b)]
Number of moles of boron atoms 2 x 0.184 [Hint: From the given reaction, it is clear that, I mole Sg will
give 8 moles of S03'
Number of moles ofSi0 2 Mass = 80.7 = 1.345 :. Mass of S03 formed will be = 80 x 8 = 640 g.]
Molar mass 60 26. Calculate the number of millilitresa.t STP of H2 S gas needed
Number of moles of silicon atoms 1.345 to precipitate cupric sulphide completely from 100 mL of a
Number of atoms of silicon NA x 1.345 :::: 7.3 solution containing 0.75 g ofCuCI 2 in 1 L.
(a) 21.4 (b) 14.2
Number of atoms of boron NA x 0.184 1
(c) 41.2 (d) 124
Where, NA = Avogadro's number [Ans. (d)]
 BASIC PRINCIPLES 39
[Hint: CuCl 2 + H2S ~ CuS + 2HCI the values of x and yare:
(a) 40,40
Number of moles of H2S = Number of moles of CuCl 2
(c) 30,30
=~=~.00557 [Ans. (a)]
134.5
[Hint: In RHS, there are 40 hydrogen atoms, hence only
Volume of H 2S =0.00557 x 22400 =124.8 mL J option (a) will be suitable.]
27. In the reaction,
As 2 SS +xHN0 3 ~5H2S04 + yN0 2 +2H 3 As0 4
+ 12H2 0

SUMMARY AND IMPORTANT POINTS TO REMEMBER

~_. -fa' 111,- • ... ... .... 111,_ ,lilt
1. Chemistry: Branch of physical science which deals properties ofa compound are altogether different from the
with the properties, composition and changes of matter. It properties of elements from which it has been constituted.
has several branches. Main branches are (i) organic 12. Mixture: A material containing two or more substances
(ii) inorganic (iii) physical and (iv) [Link] is wide in its (elements or compounds) in any proportion, in which
scope and touches- almost every aspect of our lives. components do not lose their identity. Homogeneous mixtMre
2. Matter: It is anything which has mass and occupies space. has a single phase while heterogeneous has more than one
Matter exists in three physical states (i) solid (ii) liquid and phase. Mixture can be separated into components by
(iii) gas. It is chemically classified _into (a) elements physical methods.
(b) compounds and (c) mixtures. 13. Alloy: A homogeneous mixture of two or more
3. Energy: The capacity of doing work. It is of various forms. elements-metal and metal, [Link] and non-metal or
One form can be converted into another but cannot be created non-metal and non-metal. They have unique properties.
c or de~troyed. The total amount of matter and en~:rgy available 14. Physical change: A temporary: [Link] change in
in the universe is constant. The relationship between mass and chemical composition and mass. Physical properties alter. It
energy is given by Einstein equation, E = me 2 (where, can be reversed easily.
E energy, m mass, e velocity of light). 15. Chemical change: A permanent change, new substance is
4. Intensive properties: Do not depend on the quantity of formed which possesses different composition and
matter, e.g., colour, density, melting point, boiling point, etc. properties. It cannot be reversed easily. Chemical changes
5. Extensive properties: Depend on the quantity of matter, are of various types. The important ones are decomposition,
e.g., volume, mass, weight, etc. synthesis, substitution, addition, internal rearrangement,
6. Substance: A variety of matter, all samples of which have polymerisation, double decomposition, etc.
the same composition and properties. Pure substances are 16. Law of conservation of mass: (Lavoisier-:-1774) In a
divided into (i) elements and (ii) compounds. chemical change, mass is neither created nor destroyed. In
7. Element: A substance which cannot be decomposed into chemical reactions: ._.
anything more simpler by ordinary physical or chemical Total masses of reactants == Total masses of products.
means. 117 elements are known. 88 elements have been 17. Law of constant proportfons: (Proust-1799) A chemical
isolated from natural sources and remaining 29 have been compound always contains the same element combined
prepared by artificial means. Every element is represented by together in fixed proportion by mass.
a symbol which is a small abbreviation of its full and lengthy 18. Law of multiple proportions: (Dalton-l 808) When two
name. Oxygen is the most abundant element. Silicon, elements combine to form two or more compounds,_ the
aluminium, iron are second, third and fourth most abundant - different masses of one element which combine with a fixed
elements. Elements are classified as (i) metals mass of the other element, bear a simpl~ ratio to one another.
(ii) non-metals and (iii) metalloids. 19. Law of reciprocal proportions: (Richter-1794) When
8. Metals: Generally solids (Hg-exception). They have two different elements combine with the same mass of a
properties such as lustre, hardness, malleable, ductile, good third element, the ratio in which they do so will be the same
conductors of heat ·and electricity. Copper, zmc, iron, or simple multiple ifboth directly combine with each other.
aluminium are metals. In all chemical reactions, substances react in the ratio of their
9. Non-metals: Usually non-lustrous, brittle and poor equivalent mass~~.
conductors of electricity. Oxygen, carbon, nitrogen, 20. Law of gaseous volumes: (Gay-Lussac-1808) Gases
chlorine, helium, etc., are non-metals. react with each other in simple ratio of their volumes and if
10. Metalloids: Possess mixed properties of :metals and product is also in gaseous -state, its volume also bears a
non-metals both (e.g., As, 8b, 8n). simple ratio with the volumes of gaseous reactants under
11. Compound: Pure substance composed of two or more similar conditions of temperature and pressure.
different elements in a fixed proportion of mass. The
40 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

21. Dalton's atomic theory: Every element is composed of 31. Gram molar volume: The volume occupied by one
small indivisible, indestructible particles called atoms. gram-molecular mass of any gas at NTP (O°C or 273 K and
Atoms of the same element are identical but differ in one atm or 76 em ofHg as pressure). Its value is 22.4 litre.
properties, mass and size. of atoms of other elements. Atoms 32. Vapour density:
of differe1Jt elements combine in. simple ratio to form Density of a gas
compounds. The relative number. and kind of atoms are V.D.
Density of hydrogen
always the same in a given compound. Atoms cannot be
Mass of a certain volume of a gas
created or destroyed.
Mass of same volume of hydrogen
22. Atom: The smallest particle of an element that takes part
in a chemical reaction. under same temperature and pressure
23 •. Molecule: The smallest· particle of· art element or 2Y.D.= Molecular mass
compound that can have a stable existence. 33. Mole: Amole(mol) isdefmed~sthenutnber of atoms in
24. For:mula: Gronp of symbols of elements which represents P,9 g of carbon-12 .. The number Qfatoms..is 6,07X10 23 •
one molecule of a substance. It represents also the chemical This number is called Avogadro's number.
composition. Mass of substan~e in gram
1
N 0.0f moes=--------------------~-------
25. Atomic
.
mass: Atomic mass of an1 element is the·ratio. of·
. Mass of one mole of the substance in gram
mass of one atom of an [Link] 12th part of the mass of No. of particles
carbon.,,12. . i'
6.02 X 1023
Atomic mass of an element Volume of gas in Htres at NTP
= Mass of one atom of the element X 12 = 22.4
Mass of one atom of carbon-12 Mass of one atom of an element
26. Atomic mass unit (amu): ~th mass of carbon-12. It is Gram atom o'f an element
= 6.02 x
equal to 1.66 x 10-24 g.
Atomic mass of an el<~ment Mass of one molecule of a substance
Gram-molecular mass of a substance
Mass of one atom of the element
lamu 6.02 x 1023
34. Equivalent mass: The number of parts by mass of the
The actual mass of an atom of element Atomic mass in
substance which combine Or displace directly or indirectly
amu x 1.66 x 10-24 g. 1.008 parts by mass of hydrogen or 8 parts by mass of
The atomic masses of elements are actually average relative oxygen or 35.5 parts by mass of chlorine or 108 parts by
masses because elements occur as mixture of isotopes. mass of silver.
27. Gram-atomic mass or Gram atom: Atomic mass The equivalent mass of an element may vary with change of
expressed in grams. It is the absolute· mass· in grams of valency.
6.02 x 1023 atoms of any element. Eq. mass of an element
Mass of element in Mass of eleme;nt x 1.008
N 0.0f gram atoms = .
. Atomic mass of the element in grams Mass of hydrogen
Mass of element x 11200
28. Molecular mass: It indicates how many times one =-------------------------------
Volume in mL of hydrogen displaced at NTP
molecule of a substance is heavier in comparison to ~th of
. mass of one atom of carbon-12. Mass of a molecule is equal
= Mass of element x 8
Mass of oxygen
to sum of masses of the atoms present in a molecule.
29. Gram-molecular mass· or Gram molecule: Molecular Mass of element x 35.5
mass expressed in gram. It is the absolute mass in gram of Mass of chlorine
6.02 x 1023 molecules of any substance. . . m· E
35. Metal to metal displacement: _1 =_1
No. of gram molecules ~ E2
Mass of a substance in 36. Double decomposition: AB + CD ~ AD + CB
ppl.
. Molecular mass of the substance in gram
Mass of AB massofB
30. Avogadro's hypothesis: Under similar conditions of Mass of AD
temperature and pressure, equal volumes of all gases contain
same number of molecules. . Atomic mass of an element
:: Eq. mass of 1he element x Valency
 I
BASIC PRINCIPLES 41

37. Dulong and Petit's law: Molecular formula mass

n'=--------
Atomic mass (approximate) = ~A< ·J~;mpirical formula mass
. SpeCIfic heat >(iM Structimi1:'It represents the way in which atoms of
38. Cannizzaro's method: Atomic mass of an element is the various elements are linked with each other.
smallest mass of the element present in the molecular mass 42. Percentage of element:
of anyone of its compounds. Mass of element
Percentage of element = x 100
39. Law of isomorphism: Isomorphous compounds form Molecular mass .
crystals wnicnhave same size and shape and can grow in the 43. Chemical equation: It is a symbolic representation of a
saturated solution of each other. chemical change. The equation becomes balanced when total
Masses of two elements that combine with same mass of number of atoms of various elements are made equal on both
other elements in their respective compounds are in the ratio the sides of equation. Chemical equations are of two types
of their atomic masses. (i) molecular and (ii) ionic. Chemical equation is based on
40. Atomic mass from vapour density of a chloride: law of conservation of mass. '
2 V. D. of a volatile chloride 44. Unit: It is the primary standard chosen to measure any
V aIency 0 f an e1ement = - - - - - - - - - -
Eq. mass + 35.5 physical quantity.
41. Types offormulae:. The seven units of measurement, namely mass, length, time,
(i) Empirical: It represents the simplest relative whole temperature, electric current, luminous intensity and amount
number ratio ofatoms of each element present in the of substance are taken as basic units. All other units can be
molecule of a substance. derived from them and are, therefore, called derived units. SI
(il) Molecular: It represents the actual number of atoms of units are used these days in all branches of science.
each element present in one molecule of a substance. 45. Significant ,figure: It is the total number of certain digits .
plus one doubtfu,l digit. .
Molecular formula =n x Empirical formula.
 5
SOLUTIONS
(General and Colligatlve Properties)

5.1 INTRODUCTION 5.3 TYPES OF SOLU"nONS

When two or more chemically non-reacting substances are AU the three states of matter (gas, liquid or solid) may behave
mixed, they form mixtures. A mixture may be heterogeneous or either as solvent or solute. Depending on the state of solute or
homogeneous. A heterogeneous mixture consists of distinct solvent, mainly there may be the following seven types of binary
phases and the observed properties are just th.e sum of the solutions: .
properties of individual phases. However, a homogeneous [Link]. . Solvent
Solute Example
mixture consists of a single phase'which has properties that may
differ drastically from those ofthe individual components. 1. Gas Gas Air
A homogeneous mixture whose composition can·be varied 2. Gas Liquid Aerated water (C0 2 + H 2 O)
within certain limits is termed a true solution. 3. Gas Solid Hydrogen in palladium
The constituents of a solution cannot be separated by Liquid Liquid Alcohol in water, benzene in
4.
filtration, settling or centrifugal action. All solutions are toluene
characterised by (i) homogeneity, (ii) absence of settling and (iii)
the molecular or ionic state of sub-division of the components. 5. Liquid Solid Mercury in zinc amalgam
When the solution is composed of only two chemical 6. Solid Liquid Sugar in water, common salt
substances, it is termed a binary solution. Similarly, it is called in water
ternary and quaternary if it is composed of three and four Solid Solid Various
. components, respectively. thus; a solution may be regarded as
a single phase containing more than one component. The solution of liquid in' gas or .solid in gas is not possible
because the constituents cannot form a homogeneous mixture.
5.2 SOLVENT AND SOLUTE For a given solution, the amount of the solute dissolved in a
unit volume of solution (or a unit amount of solvent) is termed as
Every solution consists of a solvent and one or more solutes. the concentration of the solute. Solutions containing relatively
Solvent in a solution is its constituent substance which has the high concentration of solute are called concentrated solutions
same state of aggregation as that of the solution. Generally, the while those of relativelY low concentratioll of solute are termed
component present in greater amount than any or all the other as dilute solutions. '
components is called the solvent. For the solubility of solids in
In this chapter, we shall discuss only three types ·of solutions:
liquids, where the liquid is present in large excess over the solid,
(i) Gas in liquid.
there is no ambiguity in these terms, the solid being the solute and
the liquid being the solvent. However, if the solution is such that (ii) Liquid in liquid.
the state of aggregation of the solution is the same as that of a (iii) Solid in liquid.
component present in smaller amount, the latter is called the
solvent For example, in a syrup (liquid solution) containing 60%
5.4 METHODS OF EXPRESSING THE
sugar (a soiid) and 40% wl'lter (a liquid-same aggregation as CONCENTRATION OF A SOLUTION
solution), water is tenned as the solvent. In a solution of alcohol The concentration of a solution can be expressed in a number of
and water, the substance present in a larger proportion by mass is ways. The important methods are:
called the solvent. But if both the liquids have same masses in (i) Mass percentage or Per cent by mass: It is defined as
solution, it becomes difficult to differentiate between solvent and the amount of solute in gram present in 100 gram of the solution.
solute.
 . SOLUTIONS 317

Mass percentage of solute Mass of solute x 100 (vi) Mole fraction: This method is used when the solution
Mass of solution is constituted by mixing two or more components. It is defined as
the ratio of number of moles of one component to the total
Mass of solute
= x 100 number of moles of the solution (i.e., all the components). Taking
Mass of solute + Mass of solvent three components A, Band C.
Mass of solute
=Volume of solution x Density of solution
xlOO Components A B C
Mass (in gram) WI w2
. Mass of solute . . Molecular mass m] m2
The ratio -_.... IS termed as mass fraction.
Mass of solution
No. of g moles
Thus, ml m2
Mass percentage of solute = Mass fraction x 100 Total number of g moles
ml m2 m3
10% solution of sugar means that 10 gram of sugar is present
in 100 gram of the solution, i.e., 10 gram of sugar has been Thus, Mole fraction of A =
dissolved in 90 gram of water. wJ
-+
(ii) Per cent by volume: It is defined as the volume of ml m2 m3
solute in mL present in 100 mL solution.
Volume of solute Mole fraction of B fB
Per cent of solute by volume = x 100
Volume of solution mJ m2
(iii) Per cent mass byvolume: It is defined as the mass of
solute present in 100 mLof solution. Mole fraction of C =
WI
Per cent of solute mass by volume -+
m1 m2 m3
Mass of solute
----xIOO The sum of mole fractions of a solution is equal to 1, i. e~
Volume of solution
fA + IB + .fc '~~'."
(iv) Strength or concentr~tion (Gram per litre): It is In a binary solution,
defined as the amount of the solute in gram present in one litre of
the solution. Mole fraction of solute + Mole fraction of solvent = I
Concentration of solution Let n moles of solute (B) andN moles of solvent (A) be present
Mass of solute in gram in Ii solution.
=
Volume of the solution in litres Mole fraction of solute _11_ ~XB
N+n
Mass of solute in gram
~ x 1000
Volume of the solution in mL Mole fraction of solvent ~= X A
N+n
Concentration in gram per litre is also tenned as strength of
the solution. Let W g of the solute be present in V litre of solution; Thus, X A +XB =I
then Mole fraction is independent of temperature of the solution.
(vii) Molality: It is defined as the number of moles of the
Strength or concentration of the solution ; gL- I solute present in 1 kg of the solvent. It is denoted by m
lNote: V is not the volume of the solvent. V is actually the final Number of moles of solute
volume after dissolving a definite quantity of solute in the Molality (m) = --~--------­
Number of kilo-grams of the solvent
solvent.]
(v) Paris per million (ppm): When the solute is present in Let WB gram of the solute of molecular m~s mB be present in.
trace quantities, it is convenient to express the concentration in WA gram of the ~01vent, then
parts per million (ppm).lt is defmed as the quantity of the solute
in gram present in 106 gram of the solution. Molality (m) = x 1000
mB xW A
Mass of solute 10
opm= x 6 Relation between mole fraction and molality:
• Mass of solution
n N
Atmospheric p0!lution in cities is also expressed in ppm by X B =--andX A =
. N+n N+n
volume. It refers to the voluT.e of the pollutant in 106 units of
volume. 10 ppm of S02 in air means 10 mL of S02 is present in Moles of solute
- - - - - - =: --"'---'-=-

106 mL of air. Moles of solvent mB X WA

318 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

x 1000 WB X 1000 Molarity of mixing: Let there be three samples of solution

--''---- : :;: : :;: m
X A xm A mB XWA (containing same solvent and solute) with their molarity
M t ,M 2 ,M3 and volumes V!,V2 ,v3 respectively. These
or m solutions are mixed; molarity of mixed solution may be given as:
MIVt +M2V2 +M3 V3 :::;:: MR (VI +V2 +V3 )
Note: (i) Molality is the most convenient method to express the where, M R Resultant molarity
concentration because it involves the mass of liquids rather
than their volumes. It is also independent of the variation in VI + V2 + V3 : :;: Resultant volume after mixing
temperature. Note: Molarity is dependent on volume; therefore, it depends on
(ii) Molality and solubility are related by the following relation: temperature.
Solubility x 10 1M Molar solution, i. e, molarity is I
Molality :x: - - - - - - - - - - - O.5Mor MI2 Semimolar
Molecular mass of the solute
0.1 M or MilO Decimolar
Mass of solute in gram x 100] 0.01 M or Mil 00 Centimolar
[ Solubility 0.001 M or Mil 000 Millimolar
Mass of solvent in gram
Relationship between molality and molarity:
(viii) Molarity (Molar concentration): It is defined as the 1 p mB
-=----
number of moles of the solute per litre or per dm 3 of the solution, m M 1000
i.e.,
where, p density of solution
Number of moles of solute
Molarity (M) :::;:: - - - - - - - - - m= molality
• Number of Htres of solution
"M molarity
or Molarity x Number of litres of solution
mB :::;:: molar mass of solute
: :;: Number of moles of solute
Relation between molarity 'M' and mole fraction:
Let wB g ofthe solute of molecular mass mB be dissolved in V
Let M be the molarity of solution, and x A , X B be mole'
litre of solution.
fractions of solvent and solute, respectively.
Molarity of the solution:::;:: --=-- Suppose n A and nB moles of solvent and solute are mixed to
mB xV form solution.
or Molarity x mB Strength of the solution Mass of solution : :;: nAmA + nBmB ... (i)
V
where, m A and mB are molar masses of solvent and solute,
If V is taken in mL (cm 3 ), then respectively. '
Molarity of the solution:::;:: x 1000 Volume of solution:::;:: Mass : :;: (n Am A + n BmB )
mB xV Density d
The unit of molarity is [Link] -lor mol dm -3. Nuinber of moles of solute x _ _ _10,-0_0_ __
Molarity
Molarity (second method): Let d = density of solution in Volume of solution
glmL and let it contains x% solute by mass. 1000xd
M nB x
Then, mass of I litre solution (1000 x d ) g (nAmA +,nBmB)

Mass of solute in 1 litre : :;: ~ x (1000 x d ) g Dividing both numerator and denominator by (n A + nB ),
100
1000x d
:::;:: (xx d x lO)g M x------------
nB
Number of moles of solute in I litre --'-'-- x mA + x mB
nA+nB nA+nB
Massof solute in gram x x d x 10
xlOOOxd
Gram molecular mass of solute mB M
xAm A +xBmB
,where mB molecular mass of s,olute
(ix) Normality: It is defined as the number of gram
M:::;:: xxdx 10 equivalents of solute present per litre of solution. It is denoted by
mB 'N'.
Molarity of dilution: Number of gram equivalents of solute
Normality (N)
Before dilution After dilution Number of litres of the solution
MtVt M 2V2 or Normality x Number. of lit res of the solution
Number of gram equivalents ofthe solute
 SOLUTIONS

Let wagram of the solute of equivalent mass E a be present in

V litre of the so lution, then,
: :: :::I_$OME SOLVED EXAMPLES\I::::: :
. walEa wa
Normabty = = -....=::....-- Example 1. Calculate the masses of cane sugar and water
V Ea xV required to prepare 250 g of25% cane suga~ solution.

Normality x Equivalent mass =W B Solution: Mass percentage of cane spgar 25

V We know that,
Strength of the solution in gIL
Mass of solute
Solutions are expressed as:
Mass percentage =Mass of solution
x 100
N N N N
1N 2 N - - - - - etc. Mass of cane sugar
, '2'10'100'1000' So, 25 --:------- X 100
250
Like molarity, normality is also dependent on volume,
2Sx 250
therefore, it depends on temperature. or Mass of cane sugar = = 62.5 g
100
Normality of solution may be represented as,
Mass of water (250 62.5) ::;; 187.5 g
1N Normal solution, i.e., normality is 1
Example 2. Calculate the molarity of the following
N solutions:
0.5 Nor Seminormal
2 (a) 4 g of caustic soda is dissolved in 200 mL of the solution.
N (b) 5.3 g of anhydrous sodium carbonate is dissolved in 100
0.1 Nor- Decinormal
10 mL of solution.
(c) 0.365 g ofpure HCI gas is dissolved in 50 mL ofsolution.
0.Q1 Nor N Centinormal
100 Solution: (a) Molecular mass ofNaOH 40

0.001 Nor N Millinormal No. of gram moles in 4 g of NaOH = =0.1

1000 , 40
Relationship between normality and molarity: We know
that, Volume of solution in litre = 200 0.2
1000
Molarity x Molecular mass Strength of the solution (gIL) · No. of moles of solute
MoIanty ::;; - - - - - - - - - - .2:.!. 0.5 M
. Volume of solution in litre 0.2
Similarly,
(b) Molecular mass of anhydrous Na2C03 = 106
Normality x Equivalent mass =Strength of the solution (gIL) No. of gram moles in 5.3 g of anhydrous Na2C03
Hence, 5.3 ::: 0.05
Molarity x Molecular mass Normality x Equivalent mass 106

Normality Volume of solution in litre = 100 =0.1

Molecular mass 1000
or ------=n
Molarity Equivalent mass No. of gram moles of solute
Molarity = - - - - - - - - - -
So, Normality =n x Molarity VQlume of solution in litre

[N9mlidity (second method): Let 'd' is the density of = 0.05 0.5M

solution in glmL and x is the percentage ofthe solute by mass. 0.1
Then, (c) Molecular mass of HCI =36.5
N= xxdxlO ] No. of gram mol~s in 0.365 g of pure HCI = 0.365
Equivalent mass of soitl;te 36.5
(x) Formality: It is the number of formula mass in gram Volume of solution in litre = 50
present per litre of solution. In case, formula mass is equal to 1000
molec1.!!~r mass, formality is equal to molarity. Like molarity and No. of gram moles of solute
normality, the lVrmality is also dependent on temperature. It is Molarity =- - - - - - - - - -
Volume of solution in litre
used for ionic COtupt:1mds in which there is no existence of a
molecule. Mole of ionic compounds is called formole and 0.365 1000
=--x 0.2M
molarity as formaHty. 36.5 50
320 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

Example 3. The density of a solution containing 13% by · 0 fsolutlOn

V = vo Iume ' . I' 250
In ltre = - - 0.25
mass of sulphuric acid is 1.09 g/mL. Calculate the molarity and 1000
normality of the solution.
Molarity = 1
Solution: Volume of 100 g of the solution 10
= 100 100 mL Hence,
1 w
d 1.09 10 106 x 0. 25
100
----litre 106 x 0.25 = 2.65
1.09 x 1000 or w
10 g
1
---litre Example 6. 214.2 g of sugar syrup contains 34.2 g of
1.09xJO sugar. Calculate (i) molality of the solution and {ii) mole fraction
13 ofsugar in the syrup.
Number of moles of H 2 S04 in 100 g of the solution
98 Solution: (i) Mass of sugar=. 34.2 g
· No. of moles of H? S0 4 13 1.09 x 10 34.2 34.2
M o1anty = - = x--- No. of moles of sugar ----= 0.1
Volume of soln. in litre 98 Mol. mass 342

1.445M Mass of water (214.2 - 34.2)

[Note: In solving such numericals, the following fonnula can be 180 k
applied:
= 180 g 1000 g
% strength of soln. x density of soln. x 10
Molarity = ----~--------­ No. of moles of water 180 = 10
Mol. mass 18
Similarly, No. of moles of sugar = 0.1 x 1000
of soln. x density'of sola. x10 .; Molality =- ------
Mass of water in kg 180
" Nor~~ity
Eq. mass
0.555m
We know that,
(ii) Total number of moles = 10.0 + 0.1 = 10.1
Normality = Molarity x n

= 1.445 x 2 I n = Mol. mass = 98 = 2J ,"

,.~.
. No. of moles of sugar
Mole fraction of sugar = - - - - - - - -
l Eq. mass 49 Total number of moles
=2.89N = 0.1 = 0.0099
Example 4. Calculate the molarity of pure water 10.1
(d=lg/mL). Example 7. A solution contains 410.3 g ofH 2 SO4 per litre
Solution: Consider 1000 mL of water. of solution at 20°C. If the density is 1.243 g/mL. what will be its
Mass of 1000 mLofwater ~ 1000 x 1 = 1000 g molarity and molality?
1000 Solution: Mol. mass of H 2 S0 4 98
No. of moles of water = - - 55.5
18 410.3
No. of moles of water No. of moles of H 2S04 = - - = 4.186
Molarity 98
Volume in litre
· fH SO I' [Link]? S 04
55.5 Mo1artty 0 2 4 so utlOn = -
55.5M Volume of soIn. in litre
. 4.186 = 4.186M
Example 5. Calculate the quantity of sodium carbonate 1
(anhydrous) required to prepare 250mL M solution.
10
Mass of 1 litre H2 SO 4 solution =1000 x 1.243 =1243 g
Solution: We know that, Mass of water = (1243 - 410.3) 832.7 g = ~: kg
w
Molarity No. of moles of H 2 S04
MxV Molality of solution
Mass of water in kg
where, w= mass ofNa2C03 in g,
4.186 x 1000
M = molecular mass ofNa2C03 in gram 106 832.7
= 5.027m
 SOLUTIONS 321

Example 8. The density ofa 2.03 M sQlution ofacetic acid V&' No. of moles of S20~- ions::: No. of moles of Na2S203
(molecular mass 60) in water is 1.017 glmL. Calculate the .
molality of the solution. =3
Solution: Strength of the solution MolalityofS20~- ions: 3 x1OO0=3.86m
Molarity x mol. mass 776
== 2.03 x 60 121.8 gl L Example 10. A solution is prepared by dissolVing 5.64 g of
Density ofsolution = 1.017 gl mL glucose in 60 g of water. Calculate the following:
Mass of 1 litre of solution = 1000 mL x 1.017 gl mL (i) mass per cent ofeach ofglucose and water;
"" 1017 g (ii) molality of the solution,
895.2 (iii) mole fraction of each ofglucose and water.
Mass·of water ::=1017 -121.8 = 895.2 g = kg
1000 Solution: (i) Total mass of solution
Molality = 2.03 x 1000 ::: 2.267 m ::: 5.64 + 60.= 65.64 g
895.2
Mass per cent of glucose = 5.64 x 100 = 8.59%
, Example 9. The density of a 3 M sodium thiosulphate 65.64
solution (Na2S 203 ) is 1.25 glmL. Calculate (i) the percentage by
Mass per cent of water::: (100 - Mass per cent of glucose'
mass of sodium thiosulphate, (ii) the mole fraction of
sodium thiosulphate and (iii) molalities ofNa + and SzO;- ions. :;: (100 8.59)=91.41%

Solution: (i) Mass of 1000 mL ofNa zS 2 0 3 solution (ii) No. of mores of glucose = 5.64
180
1.25 x 1000= 1250 g . 60
Mass of water in kg = - -
Mass ofNa z Sz 0 3 in 1000 mL of3 Msolution . 1000
3 x Mol. mass of NazSz03 Mo11 '
a lty 5.64 x -
=-- 1000
- : 05'
. 22 m
180 60
= 3x 158= 474 g
Mass percentage ofNazS203 in solution (iii) No. of moles of glucose = 5.64 :;;;; 0.0313
180
474 x 100 37~92 . 60
No. of moles of water:;;;; - :;;;; 3.333
1250 18
Alternatively, M :::: x x d x 10 Molefraction of glucose; 0.0313 =.0.0093
mA 3.333 + 0.Q313
3 xX 1.25 x 10 Mole fraction of water = 3.333 :::: 0.9907
158 3.333 + 0.0313
x= 37.92 Example 11. What would be the molality of a solution
made by mixing equal volumes of 30.0% by mass of H 2 S04
(ii) No. of moles of Na 2S2 0 3 :;: 474 =3 (density 1.218g cm- 3 ) and 70% by mass of H 2 S0 4 (density
158
1.61Og cm-3 )?
Mass of water =(1250 - 474)::: 776 g
Solution: Let 100 mL of one solution be mixed with 100 mL
776
No. of moles of water =- : 43.1 of the other solution.
18 Mass of 100 mL of 30% H 2 S04 100 x 1.218 :::: 121.8 g
Mole fraction of Na2S203 = .3 . =_3_=0.065 Mass of H 2 S04 in 12L8 g of 30% H2 S0 4
43.1 +3 46.1
30
:::: - X 121.8 g 36.54 g
(iii) No. of moles of Na+ ions 100
2 x No. of moles of Na2S203
. . " Mass of water = (1.21.8 - 36.54) :::: 85.26 g
=2x3 6
MassofloomLof70%H2 S04 100x1.6l 161.0g
· fN + . No. of moles of Na + ions !\1ass of H2S04 in 161.0 g of 70% H 2 S04
Mo1a1lty 0 a Ions - . - - - - - - -
Mass of water: in kg 70
=- x 161.0 g = 112.7 g
6 100
=-xlOOO
776 Mass of water.::: (161.0 -112.7)
..
=48.30 g
= 7.73-m Total H 2 S04 in solution = 36.54 + 112.7: 149.24 g
322 , A.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

149.24 Example 15. Reaction,

No. of moles of H 2 S04
98 [Link]- (aq) + Cl z (aq) ---? 2Cl(aq) + Br2 (aq)
Total mass of water in solution =(85.26 + 48.30) is used for commercial preparation of bromine from its salts.
= 133.56 g
133.56 kg Suppose we' have. 50 mL of a 0.06 M solution of NaBr. What
1000 volume of a 0.05 M solution of Clz is needed to react completely
with the Br-? '
· No. of moles of Hz SO 4 149.24 1000
II
MoaIty= =--x-- Solution: 2Br- (aq) + Clz(aq) ---? 2Cl-(aq) + Br2 (aq)
Mass of water in kg 98, 133.56
M1V1 (Br- ) = M 2Vz (C1 2 )
=11.4 m
Example 12. The moleft-action ofCH3 0H in an aqueous
nl nz
solution is 0. 02 and its density is 0. 994 g cm-3. Determine' its where, nl and n 2 are corresponding coefficients.
- 0.06 x 50 = 0.05 X Vz
molarity and molality.
Solution: Let x mole of CH3 0H and y mole of water be 2 1
present in solution.
Example 16. Calculate the molarity, molality and mole
Mole fraction of CH3 OH =_x_ = 0.02
, x+ y fraction of ethyl alcohol in a solution of total volume 95 mL
. y x 1 prepared by adding 50 mL ofethyl alcohol (density = 0.789 mel)
So, - = 49 or - = to 50 mL water (density = 1.00 g m/:,-l ).
,x y 49
. x - 1000 Solution:
Molahty = - - x 1000= - - = 1.13 m Vol. x density
18xy 18x49 No. of moles of ethyl alcohol = - - - - -
. Total mass Mol. mass
Volume of solutIOn = mL
density = 50x 0.789 = 0.8576
- 46
32x+18y
' I'ltre=------~
32x+ ll'tre
0.994 x 1000 994' Vol. x density 50 x I
No. of moles of water =------ =
Mol. mass 18
Molarity --x--x994
32x+ 18y =2.7777
\
994 · ' No. of moles 1000
__9_94_ _ = 1.0875 M MoIartty = x
32+ 18xyl x 32+18x49 VoL of sol. in mL
, ,Example 13. Calculate the concentration of NaOH 0.8576 x 1000 = 9.0~~ 1f
solution in g/mL, whic:i has the same normality as that of a 95
solution ofHCI of concentration 0.04 g/mL. .
Molality = No. of moles of .ute x 1000
Solution: N Ws x 1000 0.04 x 1000 = 1.095 Mass of solvent "ams
HC1
Es xV 36.5x 1
== 0.8576 xIOOO= 52m
NNaOH ""N Rcl 50
1.095 = ws x 1000 · ==
MoI e f ractIOn 0.8576 0.8576 0236'
== - - = .
40x I 0.8576+ 2.7777 3.6353

Ws 0.0438g/mL
5.5' SOLUTIONS- OF GASES IN LIQUIDS
"Example 14. How many Na+ ions are present in 50mL of , (Solubility of Gases)
a 0. 5 M solution ofNaCl?
, MV All gases are soluble in water as well as in other liquids to a
Solution: Number of moles ofNaCI = - - greater or lesser extent. Solutions of gases in water play an
1000
important role in our daily life. The common examples are
0.5 x 50 = 0.025 carbo rated beverages, i.e., soft drinks, household cleaners
1000 containing aqueous solutions of ammonia, formalin-an aqueous
NaCI---? Na + + Cl- solution of , formaldehyde, etc. The natural waters contain
Number of moles of Na + = Number of moles of NaCI dissolved; 02 which is vital for the existence of aquatic life in sea,
! 0.025 ' . rivers and lakes.
The solubility of a gas in a liqui4 is expressed in terms of
'Number of ions of Na + 0.025 x 6.023 X 10 23
absorption coefficient. It is defined as the volume of the gas in
1.505 X 10 z2 mL that can be dissolved by 1 mL of a liquid solvent at the
 15
STOICH IOMETRY
(Chemical Formulae and Equations)

In the discovery of a new chemical compound, the first question (i) Calculations based on mole-mole relationship
to answer is, what is the formula of the compound? The answer In such calculations, number of moles of reactants are given
begins with stoichiometric calculation and analysis of the and those of products required. Conversely, if number of moles
compound. of products are given, then number of moles of reactants--ar.e----
The percentage composition of a compound leads directly to required.
its empirical formula. An empiricaiformula or simplest formula
for a compound is the formula of a substance written with the ::: :::I_SOME SOLVED EXAMPLES\ I::::: : .
smallest integer (whole number) subscripts. Example 1. Oxygen is prepared by catalytic
The molecular formula of a compound is a multiple of its decomposition of potassium chlorate (KCI0 3 ). Decomposition
empirical formula. ofpotassium chlorate gives potassium .chloride (KCI) and oxygen·
Molecular mass = n x empirical formula mass. (0 2 ), How many moles and how many grams of KClO 3 are
required to produce 2.4 mole 0 2? .
The calculations of empirical and molecular formulae are Solution: Decomposition of KCI0 3 takes place as,
dealt in the very first chapter of this book.
2KCI0 3(s) ------7 2KCl(s) + 302 (g)
Stoichiometry: Quantitative Relations in Chemical
2 mole of KCI0 3 == 3 mole of 02
Reactions
Stoichiometry is the calculation of the quantities of reactants . . 3 mole 02 formed by 2 mole KCI0 3

.. 2.4 mole 02 will be formed by (~ x 2.4) mole KCI0 3

and products involved zn a chemical reaction.
It is based on the chemical equation and on the relationship
between mass and moles.
A chemical equation can be interpreted as follows: = 1.6 mole of KCI0 3

N2 (g) + 3H 2(g) ------7 2NH3 (g) Mass of KCI0 3 = Number of moles x Molar mass
1 molecule N2 + 3 molecules H2 ------72 molecules NH3 =1.6x ~22.5=196g

(Molecular interpretation) .tll~STVrT'oRs· O~~8JtCTIVE QUlSTIONS

1 mol N2 + 3 mol H2 ------72 mol NH3 (Molar interpretation) 1. One mole of calcium phosphide on reaction with excess of·
28 g N 2 + 6. g H2 ------734 g NH3 (Mass interpretation) . water gives:
(a) three moles of phosphine
1 vol. N2 + 3 vol. H2 ------72 vol. NH3 (Volume interpretation)
- . (b) one mole of phosphoric acid
Thus; calculations based on chemical equations are' divided (c) two moles of phosphine
. c I
mto lOur types:. . (d) one mole ofP20 s
(i) Calculations based on mole-6tokrelationship. ~ns. (c)]
(ii) Calculations based on mass-mass [Link]. [Hint: Ca3P2 + 6H 20 ~ 3Ca(OHh + 2PH3
(iii) Calculations based on mass-volume relationship. I mole of Ca3P2 '= 2 mole of PH 3]
(iv) Calculations based on volume-volume relationship.
 STOICHIOMETRY 947
2. Mg(OHh in the form of milk ofmagnesia is used to neutralize
excess stomach acid. How many moles of stomach acid can be
:: :::::_SOME SOLVED EXAMPLES\:::::::
neutralized by 1 g of Mg(OHh? (Molar mass of Mg(OHh Example 2. Calculate the mass of (CaO) that can be
= 58.33) prepared by heating 200 kg of limestone CaC0 3 which is 95%
(a) 0.0 171 (b) 0.0343 (c) 0.686 (d) 1.25 pure.
fAns. (b)] 95
[HInt: Mg(OHh + 2HCl ---7 MgCl z + 2H 2 0 Solution: Amount of pure CaC03 - x 200= 190kg
100
Number of moles of stomach acid neutralized
= 190000 g
2 x number of moles of Mg(OH) 2
CaC0 3 (s) CaO(s) + CO 2(g)
1
2x == 0.0343] 1 mole CaC0 3 1 mole CaO
58.33
100 g CaC0 3 56 g CaO
3. When a mixture of 10 moles of S02 and 16 moles of 02 were
100 g CaC0 3 give 56 g CaO
passed over a catalyst, 8 moles of S03 were formed at
equilibrium. The number of inoles of S02 and O2 remaining 56
. . 190000 g CaC0 3 will x 190000 g CaO
unreacted were: 100
(a) 2,12 (b) 12,.2 (c)J,lO (d) 10,3
== 106400 g = 106.4kg ---
fAns. (a)] - - - - -- - -- --

[Hint: 2S0 2 (g) + 02(g) ~ 2S0 3 (g) Example 3. Chlorine is prepared in the laborat01Y by ..
t=0 10 16 0 treating manganese dioxide (Mn02) with aqueous hydrochlnr'c
t eq . (10 2x) (16 x) 2x acid according to the reaction,
2x 8, i.e., x 4 Mn02 + 4HCl MnCl z + Cl2 + 2H20
Remaining S02 == 10 8 =2 mol How many grams ofHCl will react with 5 g Mn02?
Remaining 02 16 - 4 12 mol] Solutiou: 1 mole of Mn02 reacts with 4 mole of HCI
4. Calcium carbonate decomposes on heating according to the or 87 g Mn02 reacts with 146 g HCI
following equation:
.. 5 g Mn02 will react with 146 x 5 g HCI = 8.39 g HCl
CaO(s) + CO 2 (g) 87
How many moles of CO 2 will be obtained by decomposition Example 4. How many grams of oxygen are required to
of 50 gCaC0 3 ? burn completely 570 g of octane?
5 I Solution: Balanced equation,
Ca)3 (b) (c) - (d) I
2 2 2
2C sH l8 + 2502 16C0 2 + 18H 20
fAns. (c)] 2 mol 25 mol
mint: 2x114 25x32
Number of moles of CO 2 Number of moles of CaC0 3
First method: For burning 2 x 114 g of octane, oxygen
Mass =~=~] required
Molar mass 100 2
25 x 32g
5. Sulphur trioxide is prepared by the following two reactions: . 1 f . 25 x 32
S8{S)+ 80 2 (g) ---78S0 2 (g) F or burnmg g 0 octane, oxygen reqUIred = - - - g
2x 114 ~
2S0 2(g) + 02(g) ---72S03 (g)
How many grams of S03 are produced from I mole of S8 ? Thus, for burning 570 g of octane, oxygen required
(a) 1280 (b) 640 (c) 960 (d) 320 25 x 32 x 570 = 2000
fAns. (b)] 2xll4 g g
mint: From the given reaction, it is clear that I mole of S8 will Mole method: Number of moles of octane in 570 grams
give 8 moles of S03~ 570
Mass of S03 formed Numblif of moles x Molar mass 5.0
114
8 x 80 = 640 g]
For burning 2.0 moles of octane, oxygen required
(ii) Calculations based on mass-mass relationship 25 mol 25x 32g
In making necessary calculations, following steps are
For burning 5 moles of octane, oxygen required
followed:
(a) Write down the balanced chemical equation. 25 x 32 x 5.0 g == 2000 g
(b) Write down the theoretical amount of reactants and 2.0
products involved in the reaction. Proportion method: Let x g of oxygen be required for
(c) Calculate the unknown amount of substance using unitary burning 570.0 g of octane. It is known that 2.x 114 g of the octane
method. require 25 x 32 g of oxygen; then, the proportion,
948 G.R. B. PHYSICAL CHEMISTRY FOR COMPETITIONS

25 x 32 g oxygen x 100 g CaC0 3 give 44 g COz

2 x 114 g octane 570.0 g octane
.. 20 g CaC0 3 will give 44 x 20 g CO 2 : 8.8 g COz
25 x 32 x 570 = 2000 100
x
2x 114 g Let He1 be completely consumed.
. . 73 g HCl give 44 g CO 2
Example 5. Calculate the number of grams of magnesium
chloride that could be obtained from 17.0 g of HCI when HCI is " 20 g HCl wfll give 44 x 20 g CO 2 12;054 g CO 2
reacted with an excess of magnesium oxide. 73 .
Solution: Balanced equation, Since, CaC0 3 gives least amount of product CO 2 , hence,
MgO+ 2HCl ---? MgC1 2 + H 2 0 CaC0 3 is limiting reactant. Amount of CO 2 fonned will be 8.8 g.
I mol 2 mol I mol I mol Example 8. 100 g sample of calcium carbonate is reacted
(2x36.5)g (24+7l)g
= 73g = 95g
with 70 g of orthophoGphoric acid. Calculate:
(a) the number of grams of calcium phosphate that could be
73 g ofHCl produce MgCl 2 95 g produced.
95 (b) the number of grams of excess reagent that will remain
1 g of HCI produce MgCl 2
73 g unreacted.
95 Sorutioii:-~ ~ii) TlieoiilancedeqWifionTs:
17 g of HC1 will produce MgCl 2 x 17 g = 22.12g
73 3CaC0 3 + 2H3 P0 4 Ca 3 (P0 4 )z + 3CO:r +3H 2 0
3 mol 2 mol I mol
Example 6. How many kilograms ofpure H 2 SO4 could be
obtained from 1kg of iron pyrites (FeS 2) according to the 3(40+12+48) 2(3+31+64) .(3x40+2x95)
following reactions? = 300g = 1969 310g

4FeS 2 + 1102 ---? 2Fe 20 3 + 8S0~ 300 g ofCaC0 3 produce Ca 3 (P0 4 h =310 g or 1 mol
2S02 + 02 ---? 2S03 100 g ofCaC0 3 would produce
S03 + H 20 ---?H 2 S0 4
Solution: Final balanced equation, Ca 3(P0 4 )2 310 x 100
300
4FeS 2 + 1502 + 8H z 0---? 2Fe203 + 8H 2S0 4
4 mol 8 mol = 103 g
4x120g 8x98g
0.33 mol
4 x 120gofFeS 2 yield H 2 S04 = 8 x 98 g
196 g ofH 3 P0 4 produce Ca3(P04)z =310 gor 1 mol
1000 g ofFeS.) will yield H 2 S04 = 8 x 98 x 1000
- 4 x 120 70 g ofH 3 P0 4 would produce Ca3{P04)2 =-310 x 70
196
1.63 kg
Limiting reagent: Limiting reactant or reagent is the .= 110.7 g or 0.356 mol
reactant that is entirely consumed when a reaction goes to 'The above. values suggest that CaC0 3 is the limiting reagent.
completion. Other reactants which are not completely consumed Hence, calcium phosphate fonned is 103 [Link] 0.33 mole.
in the reaction are called excess reactants. (b) For producing 103 g of Ca3 (PO 4) 2' H 3 PO 4 required will
OR be
The reactant which gives least amount of product on beints
completely consumed is called limiting reactant. 196 x 103 65.12
310 g
Example 7. /f20g ofCaC03 is treated with 20gof HC/,
how mUIlY grams 'of CO 2 can be generated according to the Mass ofreinaining H 3 P0 4 =(70 -65.12) 4.88 g
followil;!~ equation?
, .. Example 9. 1g of Mg is' burnt ill a closed vessel which
CaCO (s) + 2HCI(aq. )---?CaCI2 (aq.)+ H 2 °(l) + CO 2 (g) contains 0.5g of02:
Solution: " (i) Which reactant is left in excess?
(if) Find the mass of the excess reactant.
Ca0 3 (s) + 2HCI(aq.) ~ CaC1 2 (aq.) + Hz0(l)+ CO 2 (g) Solution: (i) The balanced equation is:
1 ' )1 2 mol 1 mol
I' g 73g 44g
2Mg + O 2 ---? 2MgO
2 x 24 2 x'l6 2(24 + 16)
L •. CaC0 3(s) be completely consumed in the reaction. =48g ~32g =80g

(
48 g ofMg require oxygen = 32 g
 STOICHIOMETRY 949

I g of Mg requires oxygen
32
48
0.66g

But only 0.5 g oxygen is available. Hence, O 2 is a limiting

Thus, Na3P04 will be limiting and actual amount of product will
be 0.1 mole.]
7. In the following reaction:
-.
agent and a part of magnesium will not burn. 4NH 3 (g) + 502 (g) ---7 4NO(g) + 6H 2 0(l)
.. Magnesium will be left in excess. when I mole ammonia and I mole of 0 0 are mixed then the
(ii) 32 g of 02 react with magnesium = 48 g number of moles of NO formed will be:" '
(a) 0:8 (b) 0.7 (c) 0.6 (d) 0.5
0.5 g of0 2 will react with magnesium = 48 x 0.5 = 0.75 g [Ans. (a)]
32
Hence, the mass of excess magnesium [Hint: 1 mole ofNH3 (on complete reaction) I mole NO.

= (1.0 0.75) 0.25 g Similarly, 1 mole of O 2 (on complete reaction)

~);alPple
10. The reaction, mole NO. Thus, O 2 will be limiting reactant and actual amount of
2 C(s) + O2 (g) ~ 2 CO(g) NO formed in the reaction will be 0.8 mole.]
is carried out by taking 24 g of carbon and 96 g O 2 , Find out: 8, 30 g Mg and 30 g O 2 are reacted and the residual mixture
(a) Which-reactantis left in excess? contains:
----flr)HowmuckvfiHneft?--:------ ---- -- ---:-~~--- (a) 60g ofMgOonly- -
(c) How many moles of co an for/ned? (b) 40 g ofMgO and 20 g of O 2
(d) How many grams of other reactant should be taken so (c) 45 g ofMgO and 15 g of O 2
that nothing is left at the end of the reaction? (d) 50 g ofMgO and 10 g of O 2
[Ans. (d)J
Solution: 2C(s) + °2 (g) ~ 2CO(g)
2 mol I mol [Hint: 2Mg(s) + 02(g)~ 2MgO(g)
24g 32g 2 mol I mol 2 mol
2 x 24 g 1 X 32 g 2 x 40 g
Let carbon be completely consumed.
24 g carbon give 56 g CO 30 g Mg gives !~ x 30Jg MgO on complete reaction, _
Let 02 .is completely consumed.
32 g 02 give 56 g CO i.e. , 30 g Mg == 50 g MgO

., 96 g 02 will give 56 x 96 g CO 168 g CO

1
80 x 30 g MgO on complete reaction,
32 ) -
32
Since, carbon gives least amount of product, i. e. ,56 g CO or 2 i.e. , 30 g O2 == 75 g MgO
mole CO, hence carbon will be the limiting reactant. :. Mg is limiting reactant and MgO formed in the reaction will be
,. Excess reactant is ° 50 g.
2,
Amount of O 2 used 56 24 = 32 g Unreacted amount of O 2 = 30 - 10 = 109
Amount of 02 left 96 32 64 g .', Mixture contains 50 g MgO and 10 g 02-J
32 g 02 react with 24 g carbon 9. 254 g of iodine and 142 g of chlorine are made to react
completely to give a mixture of ICI and ICI 3 • :c~ow many
" 96 g 02 will react with 72 g carbon.
moles of each are formed?
Thus, carbon should be taken 72 g so that nothing is left at the
(a) O. I mole ofICl and 0.1 mole ofICI 3
end of the reaction.
(b) I mole ofICI and I mole ofICI 3
(c) 0.5 mole ofICI and 0.1 mole ofICl 3
(d) 0.5 mole of lCI and I mole of ICI 3
6. 0.5 mole BaCl z is mixed with 0.2 mole Na 3P04 ; the
[Ans. (b)]
maximum number of moles of Ba3(P04h that can be formed
[Hint: Both reactants are completely consumed, hence, both
is:
are limiting.
(a) 0.7 (b) 0.5 (c) 0.2 (d) 0.1
12 + 2Clz ~ ICI + ICI 3
[Ans. (d)]
[Hint: 3BaCI 2 + 2Na3P04 254 g or I mole 12 and 142 g or 2 mole CI, will react to give 1
mole ICI and 1 mole ICI 3 .J - r'
Number of moles ofBa3(P04h formed by BaCl 2 10. Magnesium hydroxide, Mg(OH)2 is the white milky ><ubstance
1
x 0.5 = 0.l66 in milk of magnesia. What mass of Mg(OH)0 is formed when
3 15 mL of 0.18 M NaOH are combined with mL of 6.14 M12
Number of moles ofBa3(P04h formed by 0.2 mole Na 3P0 4 MgCl z? The molar mass of Mg(OHh is 58.3 g mol-I.
1 (a) 0.079 g (b) 0.097 g (c) 0.16 g·(d) 0.31 g
x 0.2 0.1
2 [Ans. (a)J
950 G. R.s. PHYSICAL CHEMISTRY FOR COMPETITIONS

[Hint: MV == 12 x 0.14 == l.68 x lO-3 Thus, when 109 of Mg are used,

lOOO lOOO 87
the mass of the pure Mn02 required is - x 10= 36.25 g
15 x 0.18 == 2.7 x lO-3 24
1000
So, 45.31 g of pyrolusite contain Mn02 (pure) 36.25 g
NaOH will be limiting reagent because on c'omplete consumption,
NaOH gives least amount of Mg(OHh .. 100 g of pyrolusite contain Mn02 (pure)

Mass of Mg(OHh == 1 x 2.7 x 10-3 x 58.3 == V.V /9 g] = 36.25 x 100 80.00 g

2 45.31
Calculations involving per cent yield .. Percentage of purity 80.00
In general, when a reaction is carried out in the laboratory we
do not obtain actually the theoretical amount of the product. The .QUESllONS
amount of the product that is actually obtained is called the actual
yield. Knowing the actual yield and theoretical yield the per cent n. C7 H6 0 3 + C 4 H6 0 3 ----7 C9H804 + C 2 H40 2
Salicylic acid Acetic anhydride Aspirin Acetic acid
yield can be calculated by the given formula: (138,12gmol- 1 ) (102,09gm~I-1 ) (180,15gmol- i ) (60,05gmol- i )
. Actual yield
Per ctmtYleld =: - - - - - - What is the percentageyieldifO.,85 g of aspirin.fol111edinthe---
Theoretical rea~tion _Qf~_g--'Ji_salicylic_acid_withexcessJ)f acetic

Example 11. For the reaction, anhydride?

(a) 65% (b) 77% (c) 85% (d) 91%
CaO + 2HCI----,>CaC/2 + H 2 0
[Ans. (a)]
1.23 g ofCaO is reacted with excess ofhydrochloric acid and 1.85 [Hint: Mass of aspirin (theoretical) formed from 1 g salicylic
g ofCaCl 2 isformed. What is the per cent yield? ·d_180.15 1304
Solution: The balanced equation is; aCI - 138.12 . g
CaO + 2HCl----'> CaCl 2 + H 20 'Id = Actual amount of
I mol I mol
01
/oyle x 100
56 g III g
Theoretical amount of product

56 g of CaO produce CaCI 2 == III. g 0.85 x 100", 65%]

1.304
III
1.23 g ofCaO produce CaC1 2 == 56 x 1.23 = 2.43 g 12. A sample of impure silver (1.5 g) is heated with sulphur to
fOl111 Ag 2 S. The mass of Ag 2 S fOl111ed was 0.124 g. What was
Thus, Theoretical yield 2.43 g the percentage yield of silver sulphide?
Actual yield = 1.85 g (a) 6.41% (b) 7.20% (c) 8.27% (d) 10.8%
[Ans. (b)]
Per cent yield = 1.85 x 100 = 76.1
2.43 [Hint: 2 Ag +S
2 mol
Calculations involving per cent purity 2x 108= 216g 248g

Depending upon the mass of the product, the equivalent

Amount of Ag 2S that can be formed from 1.5 g silver
amount of the reactant present can be determined with the help of
a chemical equation. Knowing the actual amount of the reactant 248
x 1.5 1.722 g
taken aM the amount calculated with the help of a chemical 216
, .
equation the percentage purity can be determined.
Example 12. Chlorine evolved by the reaction of 45.31g
01
(0
' d f
Ylel 0.124
0 Ag 2 S = - , - x 100 =7.2
1.722
]

of pyrolusite (impure) and excess of HCI is found to combine 13. Magnetite, Fe 30 4, can be converted into metallic iron by
completely with the hydrogen produced by the reaction of 10 g of heating with carbon monoxide as re~resented by this equation:
magnesium and excess of dilute hydrochloric acid. Find the
percentage ofpurity ofMn02 in the given pyrolusite. Fe304 + 4CO 3Fe + 4CG 2
How many kilogram ofFe304 must be processed in thip way
Solution: Mg + 2HCI ----'> MgCl 2 + H2
24g (2x36.5)g 2g
to obtain 5 kg iron; if the process is 85% effieient?
(Molar mass ofFe304 is 232 g mol-I.)
Mn02 + 4HCl-----'> MnC1 2 + Cl 2 +'2H 20 (a) 6.92 kg (b) 8.12 kg (c) 20.8 kg (d) 24.4 kg
87g' 7lg ,
[Ans. (b)]
H2 + Cl 2 2HCI
2g 71 g [Hint: 1 mole Fe304 (232 g) = 3 mole Fe (168 g)
2 g of hydrogen obtained by using 24 g of Mg will combine Amount of Fep 4 required for 5 kg iron == 232 x 5 kg
completely with 71 g of chlorine produced from 87 g of pure 168
Mn02' 6.904 kg
 I
STOICHIOMETRY 951

Since, efficiency of the reaction is 85%, hence, the actual required the mixture is calculated. It is equated with the data given and the
amount of Fe 3° 4 will be unknown factors are, thus, worked out.
100 X 6.904 k '
85 g, I.e.,
8.12 kg] ::: :::[Link] SOLVED EXAMPLES\ I::::: :
14. Iodobenzene is prepared from aniline (C6~NH2) in a two step .Example 13. A solid mixture (5.0 g) consisting of lead
process as shown here: nitrate and sodium nitrate was heated below 600 0 C until the
C6~NH2 + HN0 2 + HCI ~ C6~N~Cl- + 2HiO mass of the residue was constant. If the loss in mass is 28.0 per
cent, find the amount of lead nitrate and sodium nitrate in the
C6~~CI- + KI C6~I + N2 + KCI mixture. (lIT 1990)
In an actual preparation, 9.30 g of aniline was converted to Solution: Let the amount of NaN0 3 in the mixture be =X g
12.32 g of iodobenzene. The percentage yield of iodobenzene
is: .. The amount ofPb(N0 3 h in the mixture = (5.0':'~) g
(a) 8%· (b) 50% Heat
2NaN0 3 -----7 2NaN0 2 + O 2
(c) 75% (d) 80% (2 x 85) g 32 g
[Ans. (d))
Heat
[Hint: 1 mole Of~61-1sNH2 (123 g) 1mole ofC6HsI (204 g) 2Pb(N0 3 h -----7 2PbO + 4N0 2
(2 x 331) g
9 3 gam'1'mewr'11'·
..... 204J\
-gtve-=--123 t'
3) . d0 benzepe------
x 7~gtO 662g

= 15.424 giodobenzene 170 g ofNaN0 3 evolve oxygen = 32 g

32
Actual amount of product
- - - - - - - - - - - x 100
x g of NaN0 3 evolve oxygen = - x x g
% yield . 170
Calculated amount of product
662 g of Pb(N0 3 h evolve gases = 216 g
= 12.32 x~OO '" ~O~) . . ' 216
15.424 (50 x) g ofPb(N0 3 h evolve gases x (5.0 - x) g
662
15. Benzamide can be prepared by the action of concentrated
ammonia upon benzoyl chloride. _32 216
Total loss = xx+-x(5.0 x)
C6~COCI + 2NH3 ~ C6~CONH2 + NH4CI 170 662
Loss given in the ~roblem = 28 x 5
Benzoyl chloride Benzamide
In one. such experiment, 65 cc of concentrated ammonia (in 1.4 g
100
excess) was re!lcted with 15 g of benzoyl chloride to give
ll.l g of pure benzamide. Molar masses: benzoyl chloride .E.x+ 216 (5.0-x) 1.4.
(141); benzamide (121). The percentage yield of benzamide 170 662
is: On solving, x 1.676 g
11.
(a) Il.l x 100 (b ) -'------'- x 100 Thus, Mass of NaN0 3 = 1:676 g
15 IS
Mass of Pb(N0 3 ) 2 = (5.0 -1.676) g == 3.324 g
(c) 11.1 x 100 (d) @ ><.100
65 141 Example 14. 3.68 g ofa mixture ofcalcium carbonate and
magnesium carbonate when heated· strongly leaves ' .92 g of a
(e) 11.1 x 141 x 100
121 xiS white residue: Find the percentage composition ofthe mixture.
Solution: Let x g of CaC0 3 be present in the mixture.
[Ans. (e))
[Hint: Amount of benzamide froin 15 g benzoyl chloride The mass of MgC0 3 in the mixture = (3.68 x) g.
Heat .
. =!.3.!. x 15 CaC0 3 -----7 CaO + CO 2
141 g IOOg 56g·
Actual amount of benzamide fonned = 11.1 g Heat
MgC0 3 -----7 MgO + CO 2
Actual amount of product 84g 40g
% yield = x 100
Calculated amount of
56x x 40x
= 11.1 x 100 = ILl x 141 x 100]
+ ----'----'- == 1.92
100 84
12IXI5) 12lxl5
( 141 On solving, x= 2
. 2
Analysis of mixtures: In such problems, one of the Percentage of CaC0 3 == - - x 100 54.35% .
components is supposed to be x g and the other will be the 3.68
difference from the total. Balanced chemical equations for the Percentage of MgCO J 100 54.35 = 45.65%
reactions of both the components are now written and the total
amount of the common product produced by the components of
952 G R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

Example 15. 0.5 g of a mixture of K 2CD3 qnd Li 2 CD3 Solution: The balanced equation is:
required 30 mL of0.25 N HCI solution for neutralization. What is CuQ + H2 -7CU + H 2 O.
the percentage composition ofthe'mixture? I mol 1 mol
79.5 g 22.4 litre at NTP
Solution: Let the amount ofK2~Q3 be' x' g.
Amount of Li2CQ3 (0.5 - x) g 22.4 litre of hydrogen at NTP reduce CuQ == 79.5 g
2.80 litre of hydrogen at NTP will reduce CuQ
Numberofequivalents= x + (0.5 x) ... (i)
138/2 74/2 = 79.5 x 2.80 g = 9.95 g
22.4
Number of equivalents of HCI used Example 18. Calculate the volume of carbon dioxide at
NTP evolved by strong heating of20 g calcium carbonate.
NV = 0.25 x 30 7.5 X 10-3 ... (ii) Solution: The balanced equation is:
1000 1000
CaCQ 3 CaQ+ Co. 2
Comparingeqs. (i) and (ii), we get I mol I mol
IOOg = 22.4 litre at NTP .
x = 0.48 g
LOO g 0fCaCQ3 .evolve carbon dioxide == 22.4litre
" . ~Mass,ofK2C03=OA~Lg- 0'
20ogGaGQrwmoev01veearoon-di0'xide--~-··o.. ~

Mass of Li2CQ3 = 0.02 g = 22.4 x 20 4.481itre

100
% K 2C03 = 0.48 x 100 = 96 Example 19. Calculate the volume of hydrogen liberated
0.5 at 27° C and 760 mm pressure by treating 1.2 g of magnesium
with excess ofhydrochloric acid.
Solution: The balanced equation is:
Mg + 2HCl MgC1 2 + H2
(iii) Calculations based on mass-volume relationship 1 mol I mol
24g 22.4 litre at NTP
In such calculations, masses of reactants are given and volume
of the product is required and vice-versa. . 24 g of Mg liberate hydrogen 22.4 litre
1 mole of a gas occupies 22.4 litre volume at STP mass of a
gas can be related to volume according to the following gas 1.2 g Mg will liberate hydrogen 22.4 x 1.2 = 1.12 litre
equation: 24
PV nRT Volume of hydrogen under given condition can be calculated
by applying
PV= w RT
m P2V2
Example 16. What volume of NH 3 (g) at 27° C and 1 atm T2
pressure will be obtained by thermal decomposition of 26.25 g PI 760mm P2 == 760mm
NH 4 CI?
Tl ==273K T2 (27 + 273) = 300 K
Solution: . Ammqnium chloride undergoes decomposition
as; ¥j 1.121itre V2 == ?
NH 4 CI(s) - 7 NH 3 (g) + HCl(g) - 760 x 1.12 X
V2- 300 -123081'Itre
--.
1 mol I mol 273 760
53.5g 1 mol
Example 20. A solid mixture (5 g) consisting of lead
.. 53.5gNH4Clgive 1 molNH 3 nitrate and sodium nitrate was heated below 600° C until the
.. 26.25 g NH 4 Cl will give _1_ x 26.25 mole NH 3' weight ofthe residue is constant. If the loss in weight is 28%, find
53.5 . the amount of lead nitrate and sodium nitrate in the mixture.
= 0.5 mole .: (HT 199(J)
Solution: Loss in weight is due to formation ofNQ 2 and 0. 2
PV==nRT
1 x V = 0.5 x 0.0821 x 300 gases (weight loss = ~ x 28 == 1.4 g~
100
V == 12.315 litre Pb( NQ 3 h - 7 PbQ + NQ 2 + 0. 2
Example 17. What quantity of copper(JI) oxide will react xg (x y) g '----v----'
yg
with 2.80 litre of hydrogen at NTP?
NaNQ 3 - 7 NaNQ 2 + X Q2
(5-x) (3,6 x+ y) (1.4- y)

•
 STOICHIOMETRY I 953
Number of moles ofPb(N0 3 h Number of moles ofPbO Volume of0 2 at NTP = 83.33 x 22.4 litre = 1866.592 litre
x (x- y) .. 21 litre 02 is present in 100 litre air
k •• (i)
,.:",331 223 .. 1866.592 litre 02 will be present in 100 x 1866.592 litre 02
21
M.w. Pb(Ng~h.:::;::331, M.~. PbO:::: 223
- .... _.- '-- - :::: 8888.51itre 8.8885 x 10 3 litre
Number of moles of~aN03 ,'Number ofmoles.ofNaN0 2
Example 23. What volume of oxygen gas at NTP is
-5-\- 3.6-x+ y _ necessary for complete combustion of 20 litre of propane
- ... (ii)
85..; 69 measured at 27° C and 760mm pressure?
Solving eqs. (i) and (ii), we get· Solution: The balanced equation is:
Mass of Pb(NO}h = x:::: 3.3246 g . CjHs + 502 ~ 3C0 2 + 4H 2 0
1 vol. 5 vol.
Mass ofNaN0 3 5 3.3246= 1.6754 g 1 litre 5 litre

(iv) Calculations based on volume-volume relationship I litre of propane requires:::: 5 litre of oxygen
20 litre of propane will require = 5 x [Link] 100 litre of oxygen
These calculations are based on two laws: at 760 mm pressure and 27° C. . ________ ,___
(i) Avogadro's law (ii) Gay-Lussac's law _ . This...Yolume_wilLbe_con.[Link].
---Por-example: - - - - - - - - - - --~------ --------------Giveu:-conditions NTP conditions

N2(g) + 3H2(g) 2NH3(g) (Avogadro's law) Pj :::: 760mm P2 = 760mm

I mol 3 mol 2 mol VI 100 litre V2 = ?
Ix22.4L 3x22.4L 2x22.4L TI 27+273=300K T =273
2
(under similar conditions of temperature and pressure, equal :::: P2V2
Applying
moles of gases occupy equal volumes) Tl T2
2NH} (g) .V :::: PIVI X
2
I vel. 3 vol. 2 vol. TI
under similar conditions, ratio of coefficients by mole is equal to :::: 160 x 100 x 273 = 91.0 litre
ratio of coefficient by volume. 300 760
Example 21. 1 litre mixture of co and CO 2 . is taken. This Example 24. One litre of oxygen at NTP is allowed to
is passed through a tube containing red hot charcoal. The volume react with three times of carbon monoxide at NT? Calculate the
now becomes 1.6 litre. The volumes are measured under the same volume of each gas found after thereactiolJ.
conditions. Find the composition ofmixture by volume. Solution: The desired'equation is:
Solution: Let there be x mL CO in the mixture, hence, there 2CO + O 2 ~ 2C0 2
will be (1000 - x) mL CO 2, The reaction of CO 2 with red hot 2 vol. J voJ.· . 2 vol.
charcoal may be given as,
1 vol. of0 2 reacts with:2 voL of CO
CO 2 (g) + C(s) 2CO(g)
I vol. 2 vol. or I litre of 02 reacts with 2 litre of CO
(iOOO - x) 2(1000 - x) Thus, I litre of CO remains unreacted. .
Total volume of the gas becomes:::: x + 2(1000 x) I vol. of 02 produces CO 2 = 2 vol.
x+ 2000- 2x= 1600 or . . I litre of 02 will produce CO 2 2 litre
x=400mL Thus, gaseous mixture after the reaction consists
:. Volume of CO = 400 mL and volume of CO 2 600 mL Volume of CO 1 litre
Example 22. What volume of air containing 21 % oxygen Volume of CO 2 2 litre
by volume is reqUired to completely burn I kg of carbon AII11c:,..,r~ QU£mONS
containing 100% combustible substances?
Solution: Combustion of carbon may be given as, 16. 10 litre of 02 gas is reacted with 30 litre of CO gas at STP, The
C(s) +02(g) volumes of each gas present at the end of reaction are:
I mol I mol [CMC (Vcilore) 2008)
12g_ 1 mol
(a) CO (10 litre), CO2 (20 litre)
.. 12 g carbon requires I mole 02 for complete combustion (b) O2 (10 litre), CO (30 litre)
.. 1000 g carbon will require ~ x 1000 mole 02 for (c) CO (20 litre), CO2 (10 litre)
12 (d) 02 (10 litre), CO2 (20 litre)
combustion, i. e. , 83.33 mole 02 (e) O2,(10 litre), CO (10 litre)
954 I' G.R.S. PHYSICAL CHEMISTRY FOR COMPETITIONS

[Ans. (a)]
9 gm CaC0 3 will give 22.4 x 9) litre of CO 2, i. e., 2.016 litre
1 100
[Hint: CO(g) + 02(g)
·2 of CO 2 .]
t = 0 30 L 10 L 0 18. 100 mL ofPH 3 on heating forms P4 and H2 , volume changes in
After reaction (30 20)L 0 20L] the reaction is: (DPMT 2009)
17. When 10 g of 90% pure limestone is heated, the volume of . (a) an increase of 50 mL (b) an increase of 100 mL.
CO 2 (in litre) liberated at STP is: [JEE (WB) 20071
(c) an increase of 150 mL (d) a decrease of 50 mL
(a) 22.4 litre (b)2.24 litre
[Ans. (a)]
(c) 20.16 litre (d) 2.016 litre
[Ans. (d)] [Hint: 4PH3(g)~ P4 (s) + 6H 2 (g)
4 mol 6 mol
. 4mL 6mL
[Hint: Mass ofCaC0 3 in the sample J0 x .90 9 g
100 .
volume ofH2 produced by 100 mL PH 3 ='64 x 100 150 mL
CaC03(s) ----7 CaO(s) + CO 2 (g)
I mol 1 mol' Thus, there is increase of 50 mL.]
100g 22.4 L

Example 1. . Calculate the weight of CaO required to ,Example 3. An impure sample. of calcium carbonate
remove the hardness of1000000 litre of water containing 1.62g contains 80%pure calcium carbonate. 25 g of the impure sample
ofCaC0 3 per litre. -~" reac{edwlth'excess ofhydrocfilorzciicid: Cii[culatethevoluin-e::--:1~­
Solution: Mass ofCa(HC0 3 ) 2 in the water carbon dioxide at NTP obtained from this <sample.
Solution: 100 g of impure calcium carbonate contain
1.62 x 1000000
= 80 g pure calci'O.m carbonate
1620000 g 1620 kg
Reaction involved in the removal ofhardnes$ may be given as, 25 g of impure calcium carbonate sample contain
Ca(HC0 3 )2 + CaO 2CaC0 3 + H 2 0 =.!2.. x 25
162 kg 56 kg 100
.. 162 kg Ca(HC03hrequire 56 kg CaO. = 20 g pure calcium carbonate
.. 1620 kg Ca(HC03)2 will require 560 kg CaO.
The desired equation is:
Example 2. A mixture in which the mole ratio of H 2 and
02 is 2: 1 is used to prepare water by the reaction.
1 mol 22.4 litre
2H2 (g) + 02(g) 2H 20(g) , 100g at NTP <

The total pressure in the container is 0.8. atm at 20° C before

the reaction. Determine the final pressure at 120 0 C after reaction 100 gpure CaC03 liberate = 22.4 litre CO 2
assuming 80%yield of water. . (lIT 1999) 20g pure CaC0 3 liberate 22.4 x 20
100
Solution: p 2 x 0.8 0.533atm 4.48 litre CO 2
Hz 3
, Example 4. The weight of 1 litre sample of ozonised
Po . = 1 x 0.8 =0.266 atm oxygen at NTP was found to be 1.5 g. When 100 mLofthis mixture
.23
at NTP were treated with turpentine oil, the volume was reduced
fa 90 mL. Hence, calculate the molecular weight of ozone.
1=0 0.533 0.266 0 Solution: Volume of ozone
After the reaction
0.533 x 20 x
0.266 20 0.533 x 80
volume absorbed in turpentine oil
100 100 100 .
lOmL
0.1 066 0.0533 0.4264
Volume of oxygen = 90 mL
Total pressure 0.1066 + 0.0533 + 0.4264 = 0.5863 atm
Mass of 100 mL mixture = ~xM+ 90 x'32 0.15
Using Gay-Lussac's law, 22400
Tl On solving, we get M = 48
:. Molecular mass of ozone = 48
293 393
P2 0.7864 atm
 .:.\....
STOICHIOMETRY 955
, '....

Example 5. A mixture of NaHC0 3 and Na 2C0 3 weighed x=18.2·

1.0235 g. The dissolved mixture was reacted with excess of Hence, mole fraction of ethane = 18.2 x 100 = 66.66
Ba(OH)z toform 2.1028g BaC0 3 , by the following reactions: . 27.3
Na 2C0 3 + Ba(OH)z -----t BaC0 3 + 2NaOH Mole fraction of ethene = 33.34
NaHC0 3 + Ba(OH)z -----t BaC0 3 + NaOH + H 20 Example 7. Amixture of HCOOH and H 2C 2 0 4 is heated
What was the percentage ofNaHC0 3 in the original mixture? wi~h concentrated H 2 SO 4' The gas produced is collected and on
Solution: Let x g of NaHC0 3 be present in the mixture. treating with KOH solution, the volume of the gas decreases by
II 6th. Calculate the molar ratio of the two acids in the original
Mass ofNa 2C0 3 in the mixture = (1.0235 - x) g mixture. (lIT 1990)
x Cone. H 2 S0 4'
Number of moles of NaHC0 3 = - .Solution: HCOOH ) CO + H 20
84 1 mol· Heat I mol ,"
. (1.0235 - x) Cone. H 2 S0 4
Number of moles of Na2C03 = - - - - - H 2C 20 4 - - - - - - - 7 ) CO + CO 2 + H 20
106 1 mol Heat I mol 1 mol
Number of moles of BaC0 3 Let a moles ofHCOOH and b moles ofH 2C 20 4 be present in
= Number of moles ofNaHC0 3 the original mixture.
~---.------- . - - +Numoeiof-moTeso-fNii;-C0 Moles ofCGformed = u +b
3
2.1028 x (1.0235-x) Moles of CO 2 formed = b
- - - = - + -'------'- Total moles of gases =a + b + b = a + 2b
197 84 106
CO 2 is absorbed by KOH and the volume reduces by 1/6th.
x=0.4122 a+ 2b
Moles of CO 2 = - -
AmountofNaHC0 3 ==_OAlng . 6 .'
0.4122 b=a+2b
Percentage of NaHC0 3 = - - x 100 = 40.27 or
1.0235 6
Example 6. A mixture of ethane and ethene occupies 40 or a=4b.
litre at 1.00 atm and at 400 K. The mixture reacts completely with
130 g of O2 to produce CO 2 and H 2O.. Assuming ideal gas or'. ~=4
b
behaviour, calculate the mole fractions ofC 2H 6 'and C2H4 in the
mixture. (lIT 1995) or a:b=4:1
Solution: Volume of the mixture at NTP Example 8. 3.6 'g mixture of sodium chloride and
potassium chloride is dissolved in water. The solution is treated
= 40 x I x 273 = 27.3 litre
with excess of silver nitrate solution: 7.74 gof silver chloride is
400 I
obtained. Find the percentage of sodium chloride and potassium
chloride in the mixture.
Let the volume of ethane = x litre Solution: The balanced equation between NaCI and AgN0 3
IS:
Volume of ethene = (273 - x) litre
NaCI + AgN0 3 -----tAgCI + NaN0 3
Balanced equations: 1 mol . I mol
58.5g 143.5g
C 2H 6 +7/2° 2 -----t2C0 2 +3H 20
~ voL 712 voL
Let x g of N aCI be present in the mixture.
C 2H4 + 302 -----t 2C0 2 + 2H2
1 voL 3 voL
° 58.5 g NaCI produce = 143.5 g AgCl
x g NaCl will produce = 143.5 x x gAgCI
Total volume of oxygen required for complete combustion of 58.5
the mixture is: The balanced equation between KCI and AgN0 3 is:
[~x+ (27.3-x)x 3] litre KCI + AgN0 3 -----t AgCl + KN0 3
I mol 1 mol
74.5 g 143.5 g
or [7X +·(27.~ -'- x) x 6] litre
KCI present in the mixture = (3.60 - x) g
74.5 g of CI produce = 143.5 g of AgCl
7X+(27.3-X)X6] 32
M ass 0 f oxygen =
[
x -- (3.6 - x) g of KCI will produce = 143.5 x (3.6 - x) g of AgCl
2 22.4 . ~.5 .
16 Thus, 143.5 x + 143.5 (3.6 - x) = 7.74
130= (x + 163.8) x -
22.4 58.5 74.5
956 G. RB. PHYSICAL CHEMISTRY FOR COMPETITIONS

x = 1.54 0.1468 litre of oxygen will be evolved = 245 x 0.1468

154 67.2
% of NaCl = -'- x 100 = 42.7
3.60 = 0.5352 g of KCl0 3
% of KCl (3.60 -1.54) x 100 57.3 Hence, KCI0 3 left for eq. (ii) reaction,
3.60 .'
(1.00- 0.5352) = 0.4648 g
Example 9. 5 g of K 2S04 were dissolved in 250 mL of
245 g KCt0 3 will yield KCI = 149 g
solution. How many mL of this solution should be used so that
1.2 g ofBaSO4 may be preCipitated from BaCl2 solution? 0.5352 g KCI0 3 will yield KCl ~:~ x 0.5352 g 0.3254 g
Solution: The desired equation is:
BaCl 2 + K 2S04 ~ BaS04 +2KCl Considering eq. (ii),
2 x 39 + 32 + 64 137 -;: 32 + 64
= 174g =233g 4KCI0 3 ~ 3KCI0 4 + KCI
4(39 + 35.5 + 48) 3(39 + 35.5 + 64) (39 + 35.5)
233 g of BaS04 obtained from 174 gofK 2 S0 4 490g 415.5g 74.5g

1.2 g of BaS04 will be obtained from *:>< 1.2

490 g of KCl0 3 yi~ld 415.5 g of KCl0 4

-0~464Kgof-KClO.,-will-yield=-415 .5xOA648
~ 490'
= 0.8961 g of K 2 S0 4
5 g of K2 S04 are present in 250 mL of solution = 0.3941 g of KCI0 4
490 g KCl0 3 yield = 74.5 g of KCl
So, 0.8961 g ofK 2 S04 will be present in 250 x 0.8961
. 5
0.4648 g of KCI0 3 _will yield = 74.5 x 0.4648
= 44.8 mL of solution 490
Example 10. A 2.00 g of sample containing Na2C03 and =.0.0707 g of KCl
NaHC0 3 loses 0.248 g when heated to 300 0 C, the temperature at
Total mass of residue = 0.3254 + 0.3941 + 0.0707
which NaHC0 3 decomposes into Na zC0 3 , CO 2 and steam. What
is the percentage ofNa z C03 in the mixture? 0.7902 g
Solution: 2NaHC03 ~Na2C03 +CO z +HzO % KCI0 4 = 0,3941 x 100 = 49.8
168g 44 18 0.7902
g
. Example 12. A mixture of FeO and Fe304 when heated in
The loss comes due to evolution of CO 2 and steam. air to a constant weight gains 5% in its mass. Find the
62 g loss occurs when the quantity of NaHC0 3 is 168 g. composition of the initial mixture.
Soluth~n: Letthe % of FeO in the mixture be x
0.248 g loss will occur when the quantity of NaHC0 3 .
168 . So, % ofFe3 04 in the mixture = (100 x)
x 0.248 = 0.672 g FeO on hea~ing is converted into Fe203'
62
QuantityofNa2C03 in the sample (2.0-0.672) l.328g 4FeO+ 0z ~ 2Fe203
288g 320g
% of Na 2C0 3 = 1.328 x 100 = 66.4 288 g ofFeO yield = 320 g ofFe 20 3
2
,.Exampie 11. A 1.00g sample ofKCI03 was heated under x g of FeO will yield = 320 x g of Fe203
288
.such conditions that a part ofit was decomposed according to the
equation,
2KC10 3 ~ 2KCI + 302 ... (i)
and the remaining underwent change according to the equation, 464 g of Fe304 yield = 480 g of Fe2 0 3
4KClO3 ~ 3KClO4 + KCI ... (li) (100-x)g of Fe 2 0 3 will yield = 480 (100 x) of Fe203
464
If the amount of oxygen evolved was 146.8 mL at STp,
calculate the percentage by mass of KCIO 4 in the residue. Total Fe203 320 x + 480 (100 - x)
Solution: 2KCI0 3 ~ 2KCI + 302 288 464
2(39 + 35.5 + 48) 2(39 + 35.5) 3 x 22.4 litre According to the question,
245 g 149 g 67.2 litre
320 x + 480 (100 - x) 105
67.2 litre of oxygen evolved from 245 g of KCI0 3 288 464
 STOICHIOMETRY 957

x = 20.2 x == 0.8 n
So, percentage of FeO = 20.2 After thereaction,
and percentage of Fe304 79.8
Nurpber of moles of H2 =211 ..:.. 2 x 0.8n = OAn
Example 13. A mixture in which the mole ratio ofH 2 and
O2 is 2: I , is used to prepare water by the reaction: Number ofmole~ of O 2 . = 0.211

2H2(g)+ O 2 (g)~2H20(g) Number of moles of H2 0= 1.6n

The total pressure in the container is 0.8 atm 'at 20° C before Total moles = 0.4n+ 0.211 + 1.611 = 2.211
the reaction. Determine the final pressure at 120° C after the
Initial sta:te: PV nRT
reaction, assuming 80% yield of water. (UT 1999)
Solution: The given reaction is: . 0.8 x V 3n x R x 293 ... (i)
2H 2 (g) + 02(g) ~ 2H 20(g) After the reaction, P x V = 2.2n x R x 393 ... (ii) .
Initial moles 2n n o Solving eqs. (i) and (ii), we get
Final moles (2n 2x) (n - x) 2x
P= 0.787atm
% yield =80
2xx 100 80
2n

1. 500 mL of 0.25 M Na2S04 solution is added to an aqueous 12. What weight of zinc will react with diL. sulphuric acid to
solution of 15 g of BaCl 2 resulting in the formation of a white liberate 1000 mL o~hydrogen at 27°C and 750 mm pressure?
precipitate of insoluble BaS04' How many moles and how 13. 1.2 g sample of Na2C03 and K 2C03 was dissolved in water to
many grams ofBaS04 are formed? fOffillOO mL solution. 20 inL of this solution required 40 mL
2. Zinc and hydrochloric acid react according to the reaction: of 0.1 N HCI for complete neutralization. Calculate the weight
Zn(s) + 2HCI(aq.) ~ ZnCI 2 (aq.) + H2 (g) . ofNa2C03 in the mi~ture. If another 20 mL of this solution is
If 0.3 mole Zn are added to hydrochloric acid containing 0.52 treated with excess of BaCl z, what will be the weight of the
mole HCI, how many moles of H2 are produced? precipitate? (lIT 1997)
3. Calcium carbonate reacts with aqueous HCI to give CaCI 2 and 14. Calculate the volume of air containing 21 % by volume of
CO2 according to the reaction:. oxygen· at NTP required to convert 294 mL of S02 into S03
CaC03 (s) + 2HCI(aq.) ~ CaCl 2 (aq.) + H20 + CO 2 (g) under the same [Link].
15. 4 g of an impure s..;mple of CaCO, on treatment with excess
What mass of CaC03 is required to react completely with 25
mL of 0.75 MHCI? HCI produce 0.88 g CO2 , What is the percent purity ofCaC~
4. Calculate the mass of iron which will. be converted into its sample?
oxide by the action of 18 g of steam. (MLNR 1996j 16. What weight of AgCl will be precipitated when a solution
5. How. much potassium chlorate is needed to obtain 204 litre j-" containing 4.77 g qf NaCI is add~d to a solution of 5.77 g 'of
oxygen at NTP? ,AgN03 ?
6. at
Calculate the volume of carbon dioxide obtained NTP by lHint: AgN0 3 is a lirclting rea·geht in this problem.]
heating 8.4 g of sodium bicarbonate. 17. LO g of an alloy of aluminium and magnesium is treated with
7. Calculate the volume of air needed for the combustion of I kg excess of dil. HCI. The evolved hydrogen :collected over
of carbon. mercury at O°C has a volum~ of 1.20 litre at 0.29 atm pressure.
CalCulate the percentage composition of the alloy.
pint: 100 parts of air contain 21 parts of oxygen by volume.]
18. How much iron can be theoretically obtained by the reduction
8. How many grams of oxygen will be formed by the action of 12
of 1.0 kg of Fe203 ? (At. wt. of Fe 56)
. g ofsodium peroxide on water? Calculate also the volume of
the gas at NTP. . 19.. 34 g of pure H2 0 2 is decomposed. Calculate the mass and
.9. A gaseous compound of carbon;md nitrogen containing volume at NiP of oxygen that will be evolved.
53.8% by weight of nitrogen was found to have a vapour . 20. Find the percentage composition of iron and magnesium, 5.0
density of 25.8. What is the molecular formula of. the g, which when dissolved in acid, gave 2.81 litre of H2 at NTP.
compound? 21. Equal weights of Hg and iodine are allowed to react
10. C<1i,;<'l~te the weight of lime (CaO) that can be obtained by . completely to form a mixture of mercurous iodide and
heating "'or, leg of limestone which is 93% pure. mercuric iodide. Calculate the ratio of the masses of
11. How many mole~ of impure potassium chlorate of 75% purity mercurous and mercuric iodides formed. (Hg = 201, I =: 117)
are required to proc!~lce 4~g of oxygen? pint: Hg + ----? HgI 2 ;
201 g . 455 g