1

BASIC PRINCIPLES'

1..1' CHEMISTRY AND ITS SCOPE (2) Inorganic chemistry: It deals with the study of all
known elements and their compounds except organic
Chemistry is a branch of physical science which deals with the compounds. It is concerned with the materials obtained from
study ofmatter, its physical and chemicalproperties, its chemical minerals, air, sea and soil.
composition, the physical and chemical changes which it (3) Physical chemistry: It is concerned with the physical
undergoes and the energy changes that accompany these properties and constitution of matter, the laws of chemical
processes. combination and theories go.verning reactions. The effect of
All objects in this universe are composed of matter. Most of temperature, pressure, light, concentration, etc., on reactions
these objects are visible (solids and liquids) but some are come under the scope of physical chemistry.
invisible. Chemistry is termed as a material science because it is (4) Analytical chemistry: It deals with various methods of
concerned with all material substances such as air, water, rocks, analysis of chemical substances both qualitative and quantitative.
minerals, plants, animals including man, the earth on which we It includes chemical and physical methods of analysis.
all live, and other planets. According to one of the famous A number of specialised branches have been introduced as to
scientists of twentieth century, Linus Pauling, Chemistry is the
cope with the extraordinary expansion in the subject of
science of substances, their properties, their structure and their
chemistry. Some of the specialised branches are:
transformations.
(i) Biochemistry: It comprises the studies of the substances
Chemistry is a very interesting subject which touches almost
related to living organisms and life processes.
every aspect of our lives, our culture and our environment. It has
(ii) Medicinal chemistry: It deals with the application of
changed our civilization to a great extent. The present day
chemical substances for the prevention and cure of various
chemistry .has provided man with more comforts for a healthier
diseases in living 'beings.
and happier life. A large number ormaterials which we use these
days were unknown at the turn of the century. A few decades (iii) Soil and agriculture chemistry: It deals with the:
back, our clothes and footwears were exclusively of natural analysis and treatment of soils so as to increase its fertility for the'
origin such as vegetable fibres, wool, hair, skin of animals, etc., better yields of crops. It is concerned with the chemicals used as
but, now the synthetic fibres produced in chemical factories have fertilizers, insecticides, germicides, herbicides, etc.
largely replaced them. Modem chemistry has given man new (iv) Geochemistry: It includes the study of natural
plastics, fuels, metal alloys, fertilizers, building materials, drugs, substances like ores and minerals, coal, petroleum, etc.
energy sources, etc. (v) Industrial chemistry: It deals -with the study of
During the last few decades, the expansion of chemistry has chemical processes for the production of useful chemicals on a
been tremendous. The field has become wide and complex. For large scale at relatively low costs.
convenience and better understanding of the subject, it has been (vi) Nuclear chemistry: It is the most recent branch. It
divided into various branches. The four main branches of includes the study of nuclear reactions, the' production of
chemistry are: radioactive isotopes and their applications in various fields.
(1) Organic chemistry; (2) Inorganic chemistry; (vii) Structural chemistry: It deals with various
(3) Physical chemistry; (4) Analytical chemistry. techniques used for elucidation of the structure of chemical
(1) Organic chemistry: It is concerned with the study of substances. It is concerned with the properties of substances in
compounds of carbon except carbonates, bicarbonates, cyanides, terms of their structure.
isocyanides, carbides and oxides of carbon. It is actually the (viii) Polymer chemistry: It includes the study of chemical
study of hydrocarbons and their derivatives. substances of very high molecular masses of the order of 100,000
or greater, called polymers-natural or artificial. This branch is
 2 G.R.B. PHYSICAL CHEMISTRy.fDR COMPETITIONS

gaining popularity as the use of plastics, rubber, synthetic fibres, Pri~~tley and Carl Scheele. Priestley was a very conservative
silicones, etc., is on the increase thes~ days. scientist. Even after his discovery of oxygen, he still believed in
(ix) Limnochemistry: It deals with the study of chemistry phlogiston theory.
involved in the river water or water reservoirs. (v) Modern period: Lavoisier (1743-1793), a French
(x) Phytochemistry: It includes the study of chemistry of plants. chemist, is regarded as the father of modern chemistry. He
Thus, it can be said iliat theteisno othel'bfaQ,c1(ofscience presented the exact explanation of combustion by proposing that
~4ichis so wide in its<scope as cheniistty;" . " . oXY8¢I1 is necessary for combustion. This concept was largely
responsible for the overthrow of the phlogiston theory. Among
t~2 aRIEFHISTORY OF CHEMISTRY his other contributions, he showed that water is composed of
hydrogen and oxygen, proposed the theory of indestructibility of
It is difficult to specify the date when science of chemistry came fl\atter, presented a clear defmition of an element and proposed a
into existence; however, its 'groWtli must have gone side by side system of chemical nomenclature.
with the growth of civilization. Broadly, the history of chemistry Another major step towards modem chemistry was taken in
can be studied under five periodS of its development. the first decade of the nineteenth century when the English
(i) Ancient period up to 350 A.D.: In ancient times, many chemist, John Dalton, postulate~ that all elements are made up
chemical operations such as souring of milk, conversion of sweet of atoms. He pictured atoms as tiny, indestructible units that
juices into wines, the conversion of wines into vinegar, etc., were could combine to form compound atoms or molecules. Dalton
known: Around3000,RC'" techniques of making glass, pottery, proposed that each element has its own kind of atom,s and the
pigments, dyes, perfuines and extraction of metals especially atoms of different elements differ in essentially nothing but their
gold* and silver were known in China, India, Egypt and Greece. masses. He determined the relative fl\asses of atoms of many
The beginning of chemistry as a science could probably be set elements. Thus, a new era had begun. The other important
about 400 B.c., when the theory was proposed that everything is chemists of this period are:
cOlllPosed of four elements: earth, air, fire and water. The first (a) Richter-Law of Reciprocal Proportions (1794)
.. bQOkof chemistry was written in Egypt around 300 A.D. The
(b) Proust-Law of Definite Proportions (1799)
terril chemistry meant the Egyptian art.
(c) Gay-Lussac-Law of Combining Volumes of Gases
(ii) The aicli"emicai period (350-1500): During this (1808)
period, scientists called alchemists tried to discover two things:
(d) Avogadro-Avogadro Hypothesis (1811)
an elixir of life which could make m:an eternally young and a
(e) Berzelius-Introduced the Modem Symbols for
philospher's stone which could transmute base metals like zinc,
Elements (1813)
copper, iron, etc., into gold. The alchemists failed in their efforts
because no philospher's stone and elixir of life actually existed (f) Faraday-Laws of Electrolysis (1833)
but we are indebted to them for designing new types ofapparatus (g) Thomas Graham""':"'Law of Gaseous Diffusion (1861)
and for discovering new chemical operations such as distillation, (h) Mendeleev-Periodic Law and Periodic Table (1869)
sublimation, e~traction of gold by amalgamation process and (i) Arrhenius-TheoryofIonization (1887)
preparation of caustic alkalies from ashes of plants., (j) Henry Becquerel-Discovery of Radioactivity (1896)
(iii) tlatro chemistry period (i500~1650): . During this (k) Madam Curie-Discovered Radium and Polonium
era, chemists paid their attention towards medico-chemical (1898)
problems. They believed tllat the primary object Of c4emistry was The twentieth century is' regarded as an active era of
to prepare medicines and not to make gold from base metals. chemistry. During this period, chemistry has fl\ade many
DUring this period, the study of gases was begun and quantitative contributions to human knowledge and civilization. Now, we live
experiments were undertaken for the first time. Robert Boyle in a world of synthetic fl\aterials. Chemistry of today is actually
(1627-1691) found that when it metal is heated in air, the mass· helping in solving major problems of our present day civilization
increases. He also established the relationship between volume such as population explosion, food and diseases, depletion of
and pressure of a gas. In 1661, Boyle wrote. the book 'The sources of energy, depletion of natural sources and environmental
Skeptical Chyrnist' in which he criticised' the hasic ideas of pollution ..
alchemy.
(iv) The phlogiston period (1650-1774): The phlogiston 1::~, MATTER AND ENERGY
theory was proposed by Ernst Stahl (1660-1734). Phlogiston
Besides life, matter a~denergy are regarded the two fundamental
was described as a substance in a combustible fl\aterial which is
entities with which whole of the universe is composed of. Matter
given off when the material bun:J.s. This theory persisted for about,
is anything that has mass and occupies space. All bodies in the
100 years arid was a centre of much controversy. During the end
universe conform to this definition. Mass is the quantity of matter
of the eighteenth century, much work was done with gases,
in a particular sample of matter. Mass ofa body is constant and
especially by Joseph Black, Henry Cavendish, Josepth
does not change regardless of where it is measured. The mass of a
-",. ~ . '

*Gold was probably the ftrst metal to be used because it occurred as a free metal in the earth. :
t Iatro is a Greek word m~aning a physician.
 BASIC PRINCIPLES 3

body would be the same on the moon as it is on the earth. Our structure and are very near to one another. This form of matter is
senses of sight and touch usually tell us that an object occupies associated with minimum amount of energy.
space except in the case of colourless, odourless and tasteless in liquid state, substances have no definite shape but possess a
gases where some other evidence is required to satisfy the fixed volume. There is slight effect of pressure and temperature
definition of matter. on their volumes. They have the ~perty of flowing. The
The term weight should not be used in place of mass as it has a particles are nearer to one another than in a gas and this form of
different meaning. The term weight refers to the force with which matter is associated with energy more than solids.
an object is attracted towards earth. An object resting on earth In a gaseous state, substances have no definite shape and
experiences a force called its weight, W, that is equal to its mass volume. Gases fill completely any vessel in which they are
m, mUltiplied by the acceleration due to gravity g, thatis, confined and thus occupy the whole space available to them.
W=mg There is a large effect of pressur-eand temperature on their
The weight of an object thus depends on the value of' g' which volumes. The particles are far apart from one another and move
varies from place to place. However, the mass of an object is with very high speeds in all possible directions. This form of
determined by comparing the weights of two objects, one of matter is associated with maximum amount of energy.
known mass, the other of unknown mass in the same location on Sublimation
earth as both experience the same gravitational acceleration.
Solidification
Matter is indestructible, i, e., it can -neither be -created, nor
destroyed, but it can change its form; thus, the total quantity of Solid Liquid , Gas
matter of the universe is constant. ' .~~
Energy is defined as the capacity of doing work. Freezing Condensation
Anything which has the capacity to push the matter from one place
to another possesses energy. There are various forms of energy + energy + energy
such as heat, light, etc. Energy is neither created, nor destroyed, but Solid '~ Liquid ~ Gas
-energy . ,- energy
can only be transformed from one form of energy to another.
AbsorPtion 'of energy
The world became aware of the fact that matter can be
converted into energy with the discovery of nuclear reactions, Release of energy
especially nuclear fission and nuclear fusion. The relationship Depending on temperature and pressure, a substance can exist
between mass and energy was given by Einstein. The. famous in anyone of the three forms of matter.
relation is: ... ' (ii) Chemical classification: Matter exists in nature in the
2
E =mc form of chemical substances. A pure substa~ce is defined as a
where, E = energy, m = mass and c = velocity of light. variety of matter, all samples of which have same composition
and properties. Pure substances are divided into elements and
On account of this equation, the 'above two 'laws are
compounds. Most of the materials found in nature are in the. form
amalgamated into a single statement:
of mixtures consisting of tWo or more substances. There are two
"The total amount of matter and energy available in the types of mixtures-Homogeneous and Heterogeneous. Both
universe is fIXed." types of mixtures can be separated into their components (pure
Example 1. Calcula(e the amount of energy released in substances) by mechaniCal and physical methods. Th~
ergs, calories and in joules when 0.001 kg ofmass disappears. classification can be summarized in the following way:
[Given, Velocity of light = 3 X 108 ms-1 ]
Matter
Solution: According to Einstein equation, E lne
2
I '
m=0.00Ikg=lxlO- kg;c=3xI0 ms-
E
3 8

(1 x 10-3 )(3 X 108 )2 = 9x 1013 J

1
I
Physical classification Chemical classification
7

9xlO13 J
lJ = 10 erg = 0.24 cal
9xlO 13 xl0 7 erg=9x10 13 x 0.24 cal
1 1 . r Physical Pure,
1
Solids Liquids Gases Mixtures
= 9 x 1020 erg me.~ods substances
2.16 x 1013 cal
I
ClaSSification of Matter I
Homogeneous
1'
Heterogeneous
(i) Physical classification:, Matter can exist in anyone of
three forms, (a) solid, (b) liquid and (c) gas: Chemical
In the solid state, substances are rigid. They have a definite Compounds Elements
methods
shape and fixed volume. There is negligible effect of changes in
pressure and temperature on their volumes. The individual
particles that make up a solid occupy definite positions in the Inorganic Organic
 4 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

Properties of Matter: Properties are the characteristic (iii) or from names of the elements in other languages such as
qualities with the help of which different kinds of matter can be Latin, German, etc.
commonly recognised. In chemistry, substances are distinguished Na-Sodium (Latin name Natrium)
by two types of properties, viz (i) Chemical properties and (ii) Cu-Copper (Latin name Cuprum)
Physical properties.
Fe---Iron (Latin name Ferrum)
The chemical properties of substances are those in which they
undergo change in composition either alone or by interactions with Ag-Silver (Latin name Argentum)
other substances, i. e., to form new substances having different Pb-Lead (Latin name Plumbum)
compositions from the substances which undergo change. Au-Gold (Latin name Aurum)
The properties of substances which are observed in absence of K-Potassium (Latin name Kalium)
any change in composition under specific physical s~ate are
Hg-Mercury (Latin name Hydragyrum)
termed physical properties. Colour, density, melting point,
boiling point, hardness, refractive index, thermal conductivity, W-Tungsten (German name Wolfram)
electrical conductivity, malleability, ductility, etc., are some Out of 117 elements known, 88 have been isolated from
examples of the physical properties. The properties of matter can natural sources and the remaining have been prepared by
be further classified into two: (i) Intensive properties and (ii) artificial means. The man made elements are:
Extensive properties. The intensive properties are those which
S.No. Name Symbol S.No. Name Symbol
do not depend upon the quantity of matter, e.g. , colour, density,
melting point, boiling point, refractive index, etc. These 1. Neptunium Np 16. Hassium or Hs or
properties are same irrespective of the quantity of the substance. Unniloctium Uno
Chemical properties are also intensive properties. The extensive 2. 17. Meitnerium or
Plutonium Pu Mtor
properties of matter depend on the quantity of matter. Volume, Unnilennium Une
mass, weight, energy, etc., are the extensive properties.
3. Americium Am 18. Ununnilium Uun
:1;4 ELEMENTS AND COMPOUNDS 4. Curium Cm 19. Unununium Uuu
Elements are pure substances that cannot be decomposed into 5. Berkelium Bk 20. Ununbium Uub
simpler substances by chemical changes. The smallest particles 6. 21.
Californium Cf Ununtrium Uut
of an element possess the same properties as the bigger particles.
An element can also be defined as a pure substance which 7. Einsteinium Es 22. Ununquadium Uuq
consists of only one type of atoms. Due to discovery of isotopes, 8. Fermium Fm 23. Ununpentium Uup
this definition does not seem to be correct. The modem definition
9. Mendelevium Md 24. Ununhexium Uuh
of an element is that it is a simple individual which has a definite
atomic number (see atomic structure) and has a defmite position in 10. Nobelium No 25. Ununoctium Uuo
the periodic table. It carmot be decomposed in a chemical change. 11. Lawrencium Lr 26. Technetium Tc
In chemistry, the elements are the chemical alphabet and
compounds are the words, i. e. , combinations of elements. 12. Kurchatovium Ku 27 Promethium Pm
There are presently 117 different elements known. Every 13. Hahnium Ha 1 28.• Astatine At
element has been given a definite name and for convenience a 14. Seaborgium or Sg or \29. Francium Fr
nick name which in· chemical language is called a symbol. Unnilhexium Unh
Symbol is a small abbreviation to represent a full and lengthy
name of the element. Symbols have been derived: 15. Nielsbohrium or Bhor
Uns
(i) either by taking the first letter of the name of the element Unnilseptium I
which is capitalized: The elements from S. No. 1 to 25 are called transuranic
O-Oxygen N-Nitrogen F- Fluorine elements. The credit for the discovery of most of the transuranic
C-Carbon H-Hydrogen U- Uranium elements goes to the scientist G.T. Seaborg. The first artificially
P-Phosphorus S-Sulphur 1- Iodine produced element was technetium. It was synthesised in 1937 by
scientists at the University of California at Berkley.
(ii) or by taking the first letter and one more letter from the Most of the earth's crust is made up of a small number of
name of the element. The first letter is always capitalized. elements. Only ten of the naturally occurring elements make up
Ca-Calcium Ni-Nickel AI-Aluminium 99% mass of the earth's crust, oceans and atmosphere. The
Mg-Magnesium Co-Cobalt Bi-Bismuth following table shows the abundance of highly abundant
CI-Chlorine Br-Bromine Sa-Barium elements in nature:

Note: Among the naturally occurring elements, lH is lightest and 2~~ U is the heaviest atom.

l
 BASIC PRINCIPLES I' 5

Abundance of Elements (Earth's Crust, Oceans and generally (i) brittle, (ii) non-lustrous, (iii) having low melting
Atmosphere) and boiling points, (iv) non-conductors of heat, (v) capable of
Oxygen 49.5% Chlorine 0.19% forming acidic oxides or neutral oxides, (vi) not capable of
evolving hydrogen from acids, and (vii) capable of forming
Silicon 25.7% Phosphorus 0.12%
volatile hydrides.
Aluminium 7.5% Manganese 0.09% There are some elements which do not fit completely into
Iron 4.7% Carbon 0.08% either the metal or non-metal class. Elements which have some
Calcium 3.4% N'$. Sulpur 0.06% '$. properties of both metals and non-metals are called semi:metals
t'-
Sodium 2.6% 0\ 0\ Barium 0.04% d or metalloids. The semi-metals are silicon, germanium, arsenic,
antimony and tellurium. .
Potassium 2.4% Chromium 0.033%
The above classification of elements is a rough one as certain
Magnesium 1.9% Nitrogen 0.030%
metals. like lithium, sodium, potassium possess low density;
Hydrogen 0.87% Fluorine 0.027% certain non-metals like hydrogen and graphite (a form of carbon)
Titanium 0.58% Zirconium 0.023% are good conductors of electricity. Metals rarely combine with
one another while non-metals combine with one another to form
If the entire universe is considered, then 90% of matter is
compounds. Metals and non-metals commonly combine with .
hydrogen. Helium is the second most abundant element
each other to form compounds.
amounting to 9% and the remaining elements make up only 1%
of the universe with oxygen, neon, carbon and nitrogen next in
Compounds
order of decreasing abundance.
The commercial use of an element depends not only upon its Compounds are also pure substances that are composed of
abundance but also upon its accessibility. Some of the common two or more different elements in a fixed proportion by mass.
elements such as copper, zinc, tin and lead are not abundant but Compounds containing more than four elements are rare. The
are found in nature in rich deposits from which these can be properties of a compound are altogether different from the
easily extracted. On the other hand, the elements such as titanium properties of the elements from which it has been constituted.
and zirconium which are found in abundance in nature are not The compound water has a definite composition, i. e., 11.2%
widely used because their ores are not rich and their extraction is hydrogen and 88.8% oxygen, Thus, the two are present in the
difficult and expensive. ratio of 1 : 8 by mass. The properties of water are totally different
from the properties of hydrogen and oxygen both. Hydrogen and
Metals, Non-metals and Metalloids oxygen are in gaseous state while water is in liquid state under
ordinary atmospheric conditions. Oxygen supports combustion
All the elements may be classified into two groups, metals while hydrogen is combustible but water is normally used for
and non-metals. The division is based on both physical and extinguishing fire. Component elements in compounds can be
chemical properties. separated only by chemical means and not by physical methods.
Metals are regarded as those elements which possess the Compounds are classified into two types:
following properties:
(i) Organic compounds: The' compounds obtained from
(i) They are generally solids at ordinary conditions. Mercury living sources are termed organic compounds. The term organic
is an exception which is in liquid state. is now applied to hydrocarbons (compounds of carbon and
(ii) They are lustrous in nature. hydrogen) and their derivatives.
(iii) They possess high density. (ii) Inorganic compounds: .! The compounds obtained from
(iv) They are good conductors of electricity and heat. non-living sources such as roc~ and minerals are termed
(v) They are malleable and ductile. inorganic compounds. The compounds of all elements except
(vi) They possess generally high melting and boiling points. hydrocarbons and their derivatives are included in this category.
(vii) They react with mineral acids liberating hydrogen. The number of organic compounds is very large in comparison to
(viii) They form basic oxides. inorganic compounds.
(ix) They form non-volatile hydrides if combine with Some Specific Properties of Substances: Some specific
hydrogen. properties of substances are given below:
(i) Deliquescence: The property of certain compounds of
(x) They have molecules usually mono-atomic in the vapour
taking up the moisture present in atmosphere and becoming wet
state. when exposed, is knpwn as deliquescence. These compounds are'
Sodium, calcium, aluminium, copper, silver, zinc, iron, nickel, known as deliquescent. Sodium hydroxlde, potassium hydroxide,
gold, mercury, etc., are the examples of metals. anhydrous calcium chloride, anhydro;us magnesium chloride,
The non-metals do not show the above properties. Six of the anhydrous ferric chloride, etc., are the hamples of deliquescent
non-metals, carbon, boron, phosphorus, sulphur, selenium and compounds. Sodium chloride is noti deliquescent but when
iodine, are solids. Bromine is the only liquid non-metal at room common salt is placed in atmosphere it becomes wet due to
temperature and normal pressure. The remaining non-metals; presence of an impurity of magnesium chloride.
nitrogen, oxygen, fluorine, chlorine, hydrogen, helium, argon, (ii) Hygroscopicity: Certain compounds combine with the
neon, krypton, xenon and radon are gases. Non-metals are moisture of atmosphere and are converted into hydroxides or
 6 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

hydrates. Such substances are called hygroscopic. Anhydrous microscppic .~evel. Tlle, c~mponeIits cm,m,ot, ~e s~en"by pak~ ~~
copper sulphate, quick lime (CaO), anhydrous sodium carbonate, a
or with the' heIp of microscope. The mixture is, uniform,
etc., are of hygroscopic nature. throughout having a single phase*. The homogeneous ri:riXttire is
(iii). Emorescence: The property of some crystalline isotropic in nature, i. e" every portion of it has the same
substances of losing their water of crystallisation on exposure composition and properties. '
, and becoming powdery on the surface is called efflorescence. Alloys such as brass, steel, 22-carat gold; solutions such as
Such salts are known as efflorescent. The examples are: common salt dissolved in water, sugar dissolved in water, iodine
Ferrous sulphate (F eSO4' 7H2 0), sodium carbonate dissolved in carbon tetrachloride, benzene in toluene, methyl
(Na2C03·lOH20), sodium sulphate (Na2 S04,lOH20) , potash alcohol in water; gasoline (a mixture of hydrocarbons), air, etc.,
alum [K 2S04 'Al2 (S04)3 ·24H 2 0] , etc: are some of the examples of homogeneous mixtures.
(iv) Malleability: This property is shown by metals. When A heterogeneous mixture is not uniform. It can have two or
the solid is beaten and does not break but is converted into a thin more phases. The components can be seen by naked eye or with
sheet, it is said to possess the property of malleability. Copper, the help of a microscope. It has anisotropic properties, i.e.,
gold, silver, aluminium, lead, etc"can be easily hammered into properties are not uniform throughout the mixture. Soil, a
sheets. Gold is the most malleable metal. mixture of sulphur and sand, a mixture of iron filings and sand,
(v) Ductility: The property of a metal to be drawn into smoke, etc., are the examples of heterogeneous mixtures.
wires is termed ductility, Copper, silver, gold, aluminium, iron, The components of a mixture differ in many of their physical
et<;:., are ductile in nature. Platinum is the most ductile metal. and chemical properties. The advantage of this difference is taken
(vi) Elasticity: When the stress is small" the ;solid:, in the separation of a mixture. The method of separation
completely regains its original shape, size or volume after the employed should not bring about the destruction of anyone of the
deforming force is removed. The solid is then said to be elastic. components. Some preliminary techniques based on physical
Steel, glass, ivory, etc., are elastic bodies. properties are described here in brief.
(vii) Plasticity: When stress is increased on a metal, a limit , (i) Filtration: This method is useful when one of the
is reached beyond which, if the stress is removed, the solid does components is an insoluble solid in a solvent. The insoluble solid
not come back to its original shape Or size. It acquires a permanent is obtained by filtration of the suspension through filter-paper.
deformation. Such materials can be given any shape without any For example, common salt containing sand is separated by
difficulty. filtration. The mixture is mixed with water. It is shaken so as to
(viii) Brittleness: The solid materials which, break into dissolve common salt. The sand remains insoluble. The
small pieces on hammering are called brittle. The solids of suspension is put to filtration. ,The sand cplleqts ,on the,
non-metals are generally brittle in nature. filter-paper. It is taken in a baSin and 'dried hy heating. The filtrate .
(ix) Hardness: A material is said to be harder than the other is taken in evaporating dish and heated till whole of the water is
if it can scratch it. The hardness is measured on Mho's scale. For evaporated. Solid common salt is thus obtained in the dish.
this purpose, ten minerals have been selected which have been Sugar containing charcoal, potassium nitrate containing saw
assigned hardness from 1 to 10. dust or mixtures having insoluble components can be separated
Hardness Mineral by filtration.
Hardness Mineral
(b) Sublimation: It is a process in which a solid'substance is
Talc 6 Orthoclase directly converted into its vapours by ~lication of heat and vapour is
2 Gypsum 7 Quartz reconverted into solid by subsequent cooling. The method is used
Calcite Topaz when one of the components undergoes sublimation and other
3 8
components are not decomposed by heating. For example, naphtha-
4 Fluorite 9 Corundum lene can be separated from common salt by sublimation. Similarly, a
5 Apatite 10 Diamond mixture of ammomwn chloride and potassiwn chloride can be
separated by sublimation as ammoniwn chloride sublimes on heating.
On Mho's scale, hardness of diamond is maximum and that of
(iii) Distillation: It is a process of converting a liquid into
talc is ri1inimum. If a material can scratch topaz but cannot
its vapour by heating and then condensing the vapours again into
scratch corundum it possesses hardness equal to 8.
the same liquid by cooling. Thus, distillati()n involves
vaporisation and condensation both.
1'.5 MIXTURES
Distillation =Vaporisation + Condensation
A mixture is a material containing two or more substances either This method is employed to separate liquids which have
/ elements or compounds or both in any proportion. Substances different boiling points or a liquid from non-volatile solid or
which form a mixture are milled components. Components are solids either in solution or suspension. The mixture of copper
present in the,mixtQre without loss of their identity. There are two sulphate and water or mixture of water (b.p. 100°C) and methyl
types of mixtures-:-homogeneous, and heterogeneous. In a alcohol (b.p. 4SOC) can be separated by this method.
homogeneous mixture, the components are mixed uniformly to
* Phase is defiried. as part ora system which hasunifonn properties and composition. A solution or mixture of sugar and water is a one phase system.
Every drop of the solution has same properties and sartte cdmpOsition.
 BASIC PRINCIPLES . I
(Iv) Magnetic separati(ln: If one of the components of a Mixture
.--_ _ _ _...II_A_m....,agnet is moved in the mixture
mixture has magnetic properties, it can be separated by using Ii
magnet. Iron is separated from a mixture of iron filings and
Iron filings attracted Residue
sulphur by moving a magnet through the mixture. by magnet . 1Heated
(v) Solvent extraction: This method is based on the
preferential solubility of one of the components ofthe rnixture in
a particular solvent (usually a low-boiling organic solvent) which Vapours Residue
1
forms a distinctly separate layer with the other liquid if present in (Common salt + sand)
the mixture. For example, iodine present in water can be .
1Cooled
Shaken with
recovered with the help· of ether or carbon disulphide. For this Naphthalene water and filtered
method, a separating funilel is utilized. The aqueous solution of
iodine is taken in separating funnel to which ether is added. The

I
Filtrate Residue
funnel is shaken. Two layers are formed. The upper layer which
is dark brown consists of ether and iodine and the colourless Ewpo""",,
lower layer consists of only water. The lower layer is taken out.
to dryness .IDriOO ,.

The coloured layer is then poured out and ether is removed Common salt Sand
cautiously by distillation when iodine is left behind.
Two immiscible liquids such as water and oil can also· be (c) (i) Ammonium chloride sublimes on heating,
separated by the use of a separating funnel. (ii) Potassium chloride is soluble in water,
(iii) Powder~d glass is insoluble in water.
Example 2. How will you separate the following mixtures?
(a) Sulphur, potassium nitrate and charcoal, 1.6· ALLOYS
(b) Sand, common salt, iron filings and naphthalene, When two or more elements are melted together and resulting
liquid is allowed to solidify, the product so obtained'is called an '
(c) Powdered glass, ammonium chloride and potassium alloy ifit possesses metallic properties. An liiloymay consist of a
chloride. mixture of a metal with another metal, a metal with a non-metal·
Solution: or a metal with both metal and non-metal.
(a) (i) Sulphur is soluble in carbon disulphide, Alloys are prepared because they have properties more
(ii) Potassium nitrate is soluble in water, suitable,for certain applications than do the simple metals. Alloys
(iii) Charcoal is insoluble in carbon disulphide as are used because they are harder and stronger, have desirable
casting properties, special physical properties such as magnetic "
well as in water.
properties and resistance to corrosion in certain environments.
Mixture Meltingipoint of an alloy is normally lower than the melting point .
Stirred with CSz and filtered of eith¢r of the pure components. Thcnt}al and' .. 'electrical. - .
r------------L------~ ~ conduct~vities are n~n:nally reduced in alloys'. ... .. .... . c- -.' ...

I
Filtrate (soln. of sulphur is CS0 Residue
An fllloy contammg one component mercury IS called .
amalgam. Most of the metals form amalgams. Iron, platininn,
tungsten, etc., are few metals which do not form amalgams.
1Evaporated Alloys are mainly classified into two distinct types, namely
ferrous 'and non-ferrous. Ferrous alloys always contain iron,
Sulphur carbon and one or two of the other elem~nts such as manganese,
Filtrate Residue nickel, chromium, copper, vanadium, molybdenum, tungsten,
etc. When the percentage of carbon in the alloy is below 0.1, the
1Dried·
I Evaporated to
dryness

Potassium nitrate Charcoal

alloy is termed the iron alloy and if it is above 0.1, the alloys are
called steels. When iron is not present in the alloy, it is termed a
non~ferrous alloy. Some ofthe important alloys have been listed
below:· .
Alloy·. CompoSition Main uses'
(b) (i) Iron filings are separated by. a magnet,
(ii) Naphthalene sublimes on heating, 1. Brass Cu 60-;-80%, Utensils, COIJlOellser
(iii) Sand is insoluble in water. Zn 2()..-40% electrical goods, cartridge
shell .
2. Bronze Cli 75:-90%, Coins, statues, utensils.
Sn 10-25%
8 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

3. Gennan Cu 56%, Zn 24%, Utensils, resistance coils (i) Combination: Two or more substances react to form one
silver Ni20% product. When a compound is obtained by the direct reaction
4. Gun metal Cu87%, Machine parts, guns between elements, it is termed direct union or synthesis.
Sn 10%,Zn3%
2HCI C+O z
S. Rolled gold Cu 95%,Al5% Artificial j ewellery
6. Magnalium AI94%,Mg6% Balance beams, light 2Mg + O 2 = 2MgO
instruments
7. Electron Mg95%, Zn 5% Construction of aircraft (ii) Decomposition: When a compound is broken down
into two or more simple constituents, the change is called
8. Duralumin Al 95%, Cu 4%, Making aeroplanes
decomposition. Often heat is utilised for the decomposition. Such
Mn 0.5%, Mg 0.5%
decomposition is termed thermal decomposition.
9. Type metal Pb 82%, Sb 15%, Making printing types
Sn3% 2HgO = 2Hg + O 2 ; 2KCI03 = 2KCI + 30 2
10. Solder Pb 50-70%, Soldering CaC0 3 = CaO+ CO2; 2NaHC0 3 = Na 2C0 3 + H 20+ CO2
Sn 30-50% (iii) Substitution: When one element enters .into a
11. Britannia Sn 93%, Tableware compound by the replacement of the other element, the change is
Sb5%,Cu2% termed substitution.
12. Wood's metal Bi 50%, Pb 25%, Electric fuses and other
CuS04 + Zn Cu + ZnS0 4 ; C 2H 6 + Cl 2 = C 2H s CI + HCI
Sn 12.5%, Cd 12.5% safety devices
13. Nichrome Ni 60%, Cr 15%, Electrical resistances 2KI + Cl 2 = 2KCI + 12 Zn + 2HCI = ZnCl 2 + H2
Fe 25% (iv) Addition: Something is added to a chemical substance
14. Constantan Ni 40%, Cu 60% Electrical resistances without elimination.
15. Monel metal Ni 70%, Cu 30% Chemical plants KI+I2 = KI3
16. lnvar Ni 35%, Steel 65% Surveying instruments,
C2H 4 + HBr = C2HsBr
pendulums, chronometers
OH
17. Stainless Fe 89.4%, Cr 10%, Utensils, ornamental
steel Mn 0.35%, C 0.25% pieces. CH3CHO+ HCN = CH3CH<
CN
1.7 PHYSICAL AND CHEMICAL CHANGES (v) Internal rearrangement: When nothing is added or
nothing is eliminated from a chemical substance but due to
Matter undergoes two types of changes; physical and chemical. A
rearrangement of the various atoms present in a molecule, a new
physical change is one in which a substance changes its physical
compound comes into existence. When ammonium cyanate is
state but keeps its chemical identity. In physical change, a new
heated, a new substance urea is formed.
substance does not come into existence. Mass remains the same.
Physical properties are altered. This is a temporary change. For NH 4 CNO= NH2CONH 2
example, water shows all of its chemical properties whether it is
The chemical change is termed isomerisation, when one
in the form of ice or water or steam. Ice melts to form water and
isomer is converted into another.
water can be converted again into ice by placing it in a freezer.
CH 3
When 10 g of ice melts, 10 g of water is obtained. Melting,
- evaporation, condensation, frc()zing, sublimation, distillation,
CH 2 -CH 2-CH3 AlU3iHCI) CH -bH-CH
passing of electric current through metallic conductor, making of 3 3
n-Butane 300"C 2-Methyl propane
magnet from an iron piece, are some examples of physical
changes. (vi) Polymerization: Two or more molecules of a
In a chemical change, a new substance or substances come substance combine to form a giant molecule,
into existence. The starting materials called reactants, are used up 3C2 H 2 - C6 H 6
and new substances called products, are formed. The Acetylene Benzene
composition of the new substances is different from that of the nHCHO (HCHO)n
starting materials. It is a permanent change as it is not easy to Fonnaldehyde Para fonnaldehyde
obtain the starting materials again from the products.
(vii) Double decomposition: An exchange of partners
Energy is always released or absorbed when chemical or occurs between two compounds.
physical changes occur. Energy is required to melt ice and energy I I
is required to boil water. Conversely, the condensation of steam AB+CD= AD+CB
to form liquid water always liberates energy, as does the freezing L.....J
. of liquid water to form ice. Chemical changes either release I I
energy (exothermic) or adsorb energy (endothermic). BaCI 2 + Na 2 S04
L-.....J
= BaS04 + 2NaCI
Chemical changes are of various types. The important ones
are: I I
KOH + HCl = KCl + H 20
L--J
 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 1:3:2 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 is.otope 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 =ll.Ox 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~atomic.mass orgram.atomof = 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 composed.of. 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 PRIN.CIPLES 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 substance:::: 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 O.Olx 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 present.in 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]
=O.lx 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 second:::: 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
=-x8:::9
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 + 35.Sx
(iii) The law of isomorphism: Isomorphous substances
form crystals which have same shape and size and can grow in = A + 35.Sx
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 + 35.Sx
 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%]
%ofoxy.gen ~-- x tOO= 53.7 (93 + 28)
'., 35.60
13. Which pair of species has same percentage of carbon?
Exa~ple 34. Hydrogen. and o.xygim 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 Emp.mass 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 4::: 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 r.eaction 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 5:::: 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 = 193.93:::: 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 of.CaO.
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) analytical.It 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, ni.etal 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: change.mllo 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 element.to 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.
42 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

Questions
1. Match the following, choosing one item from Column-X and 2. Matrix Matching Problems:
the appropriate related item from Column-Y. (According to the new pattern of lIT Screening)
[A] [A] Match the Column-X and Column-Y:
Column-X Column-Y Column-X Column-Y
( a) Efflorescence (i) Homogeneous mixture (a) Vapour density (i) Unitless
(b) Malleability (ii) Heterogeneous mixture (b) Mole (ii) I mol electrons
(c) Alloy (ii9 Mole (c) 12 g carbon (iii) Collection of 6.023 x 1023
(d) "1 amu (iv) (l/12)th mass of atoms
carbon-l 2 1
(d) 96500 C . (iv) Molecular mass x -
2
(e) Sulphurandsand (v) Tendency to lose water of
crystallisation [B] Match the Column-X and Column-Y:
(f) Amount of substance (vi) Property ofmetalbeiilg .... -Column-X .Column-Y
hammered into thin sheets
(a) 1.6 g CH4 (i) 0.1 mol
[B]
(b) 1.7 gNH) (ii) 6.023 x 1023 electrons
Column-X Column-Y
(c) HCHO (iii) 40% carbon
. (a) Equal volumes of all (i) Dalton's atomic theory (d) C6H 120 6 (iv) Vapour density =15
gases contain equal
[C] Match the Column-X and Column-Y:
number of molecules at
NTP. Column-X Column-Y
(b) The atom is indestruc- (ii) Law of conservation of (a) 1 amu (i) Heaviest particle of atom
tible. mass (b) Proton (ii) 1.66 x 10-27 kg
(c) All pure samples of the (iii) Avogadro's law
same compound contain (c) Neutron (iii) 931.5 MeV
the same elements (d) a-particle (iv) Positively charged
combined in the same
[D] Match the Column-X with Column-Yfor the reaction:
proportion by mass.
A +B2 ~AB2
(4) Total mass before and (iv) Dulong and Petit's law
after the chemical Column-X Column-Y
reaction is same.
(a) 300 atoms of A + 200 (P) B2 is limiting reagent
(e) Atomic mass (v) Gay-Lussac's law molecules of B2
6.4
(b) 100 atoms of A + 100 (q) A is limiting reagent
Specific heat molecules of B2
(f) Gases react in simple (vi) Law of constant (c) 5 mol of A +2.5 mol (r) None of the reactant is in
ratio of their volumes. proportions ofB2 excess
[C] . (d) 2.5 mol of A + 5 mol (s) 200 molecules of A B2 will
ofB2 be formed
Column-X Column-Y
(a) Most abundant element (i) Platinum
(b) Most abundant metal (ii) Diamond
(c) Liquid at room temp. (iii) Aluminium
"
(d) Hardest substance (iv) Plutonium
(e) Most ductile metal (v) Mercury
(f) Transuranic element (vi) Oxygen
 · BASIC PRINCIPLES 43

1. [A] (a-v); (b-vi); (c-i); (d-iv); (e-il); (f-iii) 2. [A] (a-i, iv); (b-iii); (c-iii); (d-ii)
[B] (a-iii); (b-i); (c-vi); (d-ii); (e-iv); (f-v) [B] (a-i, ii); (b-i, ii); (c-iii, iv); (d-iii)
[C] (a-vi); (b-iii); (c-v); (d-ii); (e-i); (f-iv). [C] (a-ii, iii); (b-ii, iv); (c-i); (d-iv)
[D] (a-p, s); (b-r); (c-p); (d-q).

1. The density of mercury is 13.6 glmL. Calculate the diameter [Ans. 9.41 x 1023 CH 4 molecules, 9.41 x IOz3 carbon atoms and
of an atom of mercury assuming that each atom of mercury is 37.64 X 1023 hydrogen atoms.]
occupying a cube of edge-length equal to the diameter of
mercury atom. [Hint: No. of moles of methane = 25.0
(Atomic mass of mercury 200) 16.0
[Ans. 2.9 x 10-8 cm] One molecule of methane contains one carbon atom and four
2. A metal M of atomic mass 54.94 has a density of 7.42 g/cc. hydrogen atoms.]
Calculate the apparent volume occupied by one atom of the 12. How much sugar (C1 zH 22 0 11 ) will be required if each person
metal.
[Ans. 1.23 x 10-23 cc] on the earth is given 100 molecules of sugar? The popUlation
o(the earth is 3 x 1010.
3. Find the charge of I g ion ofN 3- in coulomb.
[Ans. 2.894 x 105 coulomb] [Ans. 170.43 X 10- 11 g]
13. A mixture of hydrogen and oxygen contains 20% by mass of
4. Calculate the volume at NTP occupied by 6.25 g of nitrogen.
hydrogen. What is the total number of molecules present per
[Ans. 5.0 litre] gram of the mixture?
5. 10 mL of hydrogen contains 2 x 103 molecules of hydrogen at [Ans. 7.528 x 1022]
certain pressure and temperature. Calculate the }lumber of [Hint: In I gram of the mixture, 0.2 g of hydrogen and 0.8 g of
molecules of oxygen whose volume is 200 mL at the same
temperature and pressure. oxygen are present. Moles of Hz = 0.2 = 0.1, moles of oxygen
2
4
[Ans. 4 x 10 molecules]
= 0.8 = 0.025. Calculate the number of molecules of hydrogen
6. The masses of equal volumes of a gas and hydrogen are 25.6 g 32 .
and 0.8 g respectively under same conditions of temperature and oxygen and then add.]
and pressure. Find the molecular mass of the gas. 14•. How many electrons ate present in 18 mL of water?
(MLNR 1995)
[Hint: Y.D. of the gas 25.6 32.0
0.8 [Hint: 18 mL water = 18 g water:::: I mole water 6.02 x 1023
Molecular mass 2 V.D. 2 x 32.0= 64.0] molecules, each molecule consists 10 electrons (8 electrons per
oxygen atom, 2 electrons for two hydrogen atoms). Total
7. One litre of a gas at NTP weighs 1.97 g. Find the molecular electrons = 10 x 6.02 X 1023 = 6.02 X 1024]
mass of gas.
15. Sulphur molecule is known to be composed ofS atoms of the
[Ans. 44.128]
element. In a sample of 192 g of pure sulphur, calculate (i)
8. How many moles of water are present in one litre of water? number of g-atoms of sulphur; (il) number of atoms of
[Ans. 55.5 moles] sulphur; (iii) number of moles of sulphur; (iv) number of
9. Calculate the mass of 6.02 x 1021 molecules of nitrogen. molecules of sulphur.
[Ans. 0.28 gJ [Ans. g-atoms = 6; No. of atoms 6 x 6.02 x 1023 ; No. of
10. 1.5276 g ofCdCl 2 was found to contain 0.9367 g of cadmium. moles = 0.75; No. of molecules =4.52 x 1023]
Calculate the atomic mas~ of cadmium.
[Ans. 112.54] [Hint: The atomic mass of sulphur is 32.]

Mass of Cd x 35.5 16. The vapour density of a mixture containing N02 and N 20 4 is
[Hint: Equivalent mass of cadmium
Mass of CI 38.3 at 27°C. Calculate the moles of NO z in 100 g of the
mixture. (MLNR 1993)
= 0.9367 x 35.5= 56.27
0.5909 [Hint: Mol. mass of mixture 2 x 38.3 76.6
Atomic mass Equivalent mass x Valency]
11. Calculate how. many methane molecules and how many No. of moles in 100 g of mixture = 100
76.6
hydrogen and carbon atoms are there in 25.0 g of methane?
(MLNR 1990; Dhanbad 1992) Let a g ofN02 is present in mixture.
44 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

Moles ofN0 2 + Moles ofN 20 4 Moles of mixture 23. Use the data given inthe following table to calculate the molar
a 100 a 100 mass of naturally occurring argon: . , ..
-+_._-=-- or a= 20.10 g
46 92 76.6 Isotope Isotopic molar mass Abundance
MoiesofN02 in mixture 20.10:= 0.437] 36Ar 35.96755 g mol- I 0.337%
46
38 Ar 37.96272 g mor l
0.063%
17. Calculate the number of oxygen atoms in 88 CO 2 , What g
would be the mass of CO having the same number of oxygen 4°Ar 39.9624 gmor l 99.6%
atoms? (BITS 1990)
[Ans. 39.947]
[Hint: 88 g CO 2 = 2 moles of CO 2 , One molecule consists of 2
24. Density of oxygen atNTP is 1.429 g/litre.' Calculate the
oxygen atoms. standard molar volume of the gas.
No. of oxygen atoms = 2 x 2 x 6.02 x 1023 = 24.08 x 1023 [Ans. 22.39 litre mol-I]
25. How many iron atoms are present in a stainless steel ball
CO molecule has one oxygen atom.
bearing having a radius of 0.254 cm? The stainless steel
Mass of CO containing 24.08 x 1023 oxygen atoms contains 85.6% Fe by weight and has density of7.75 glcm 3 .
__2_8---,;:;:- x 24.08 x 1023 112 g) [Ans. 4.91 x 1021 ]
26.. The nucleus of an atom. X is supposed to be a sphere with a
18. Density of water at room temperature is 1.0 g cm-3. How many radius of 5 x 10- 13 cm. Find the density of the matter in the
molecules are there in one drop of water if its volume is 0.1 atomic nucleus if the atomic weight of X is 19.
cm3? [Ans. 6.02 x 1013 glmL]
[Ans. 3.34 x 1021 molecules] 27. Calculate the number of atoms of each element present in
[Hint: Mass of one drop:= Vol. x d 0.1 xl = 0.1 g 122.5 g ofKC10 3 .
[Ans. Number of atoms of'K' = 1 x 6.023 X 1023
No. of moles = 0.1; No. of molecules 6.02 x 1023 x 0.1 ]
Number of atoms of 'Cl' = 1 x 6.023 X 1023
=0

18 . ·18
19. Naturally occurring bqron consists of two isotopes, whose Number of atoms of '0' 3 x 6.023 x 1023 ]
atomic masses are 10.01 and 11.01. The atomic mass of
28. In an experiment, 1.0 g CaC03 on heating evolved 224 mL of
natural boron is 10.81. Calculate the percentage of each
isotope in natural boron. (MLNR 1994) CO2 at NTP. What mass of Cao (calcium oxide) is formed?
[Ans. % of isotope with atomic mass 10.01 20; % of isotope [Ans. Mass ofCaO = 0.56 g]
with atomic mass 11.01 = 80] [Hint: Mass of 224 mL of CO 2 =44 x 224 0.44 g)
[Hint: Let x be the percentage of the isotope with atomic mass 22400
10.01. 29. What mass of potassium chlorate (KCI03 ) on heating gives
1.491 g of potassium chloride (KCl) and 0.6721itres of oxygen
IO.Olxx+l1.01(l00-x)~1O.81 or x=20]
atNTP?
100 100
[Ans, Mass ofKCI0 3 = 2.451 g]
20. Chlorine has isotopes 3sCI and 37 Cl. There are three 35CI
[Hint: Mass of 22.4 litre of oxygen at NTP = 32 g)
isotopes for every 37 CI isotope in a sample of chlorine.
30. A compound AB completely decomposes into A and B on
Calculate the atomic mass of chlorine.
heating. 50 g of AB, on strong heating, gave 40 g of A. How
[Ans. A = 3 x 35 + 37 x 1 == 35.5 ] much quantity of AB should· be decomposed by heating to
4 obtain 2.5 g of B? How much quantity of A will be produced
21. Natural hydrogen gas is a mixtUre of IH and 2H in the ratio of in the process?
5000 : 1. Calculate the atomic mass of the hydrogen: [Ans. 12.5 g AB is to be decomposed, 10.0 g of A will be
[Ans. 1.000199] produced.]
22. Chromium has tne following isotopic composition: [Hint: AB...-? A + B)
50g 4()g 109
. FractioDai
Mass number Isotopic mass 31. If 12.6 g of NaHC0 3 is added to 20.0 g ofHCI solution, the
abundance
residue solution is found to weigh 24.0 g. What is the mass and
50 49.9461 x volume of CO2 released at NTP in the reaction?
52 51.9405 0.8379 [Ans. 8.6 g CO 2 released. Volume at NTP = 22.4 x 8.6 = 4.378
53 52.9407 0.0950 44
litre]
54 I 53.9389 0.0236 32. (i) 5.06 g of pure cupric oxide (CUO), on complete reduction
Calculate the value of x. by heating in a current of hydrogen, gave 4.04 g of
[Ans. 0.0435] metallic copper.
 BASIC PRINCIPLES 45

(ii) 1.3 g of pure metallic copper was completely dissolved 39. Phosphorus and chlorine form two compounds. The first
in nitric acid and the resultant solution was carefully contains 22.54% by mass of phosphorus and the second
dried and ignited. .1.63 g CuO was produced in the j4.88% of phosphorus. Show that these data are consistent'
process. Show that these results illustrate th~ law of with law of multiple proportions.
constant proportions. (Hint: The ratio of the masses of chlorine which combines with
(Ans. In both cases, the ratio of copper and oxygen is 1 : 0.25. a fixed mass of phosphorus in two compounds is 3 : 5 which is a
Hence, the law of constant proportions is illustrated.] simple whole number ratio. Thus, the data illustrate law of
33. Metal M and chlorine combine in different proportions to multiple proportions.]
form two compounds A and B. The mass ratio M : CI is 40. A and B are two hydrocarbons. A and B are heated separately
0.895: I in A and 1.791 : 1 in B. What law of chenrical in excess of oxygen when 0.028 g of A gave 44.8 mL CO2 and
combination is illustrated?' 0.044 g of B gave 67.2 mL CO2 at NTP. Show that the results
[Ans. Masses of metal which combine with 1 part of chlorine are in' agreement witlt law of multiple proportions.
are in the ratio of 1 : 2, which is a simple ratio. Hence, law of [Hint: Determine the masses of CO2 at NTP and then masses of
multiple proportions is illustrated.] .
carbon.
34. 2.8 g of calcium oxide (CaO) prepared by heating limestone . 44
were found to contain 0.8 g of oxygen. When one gram of (A) Mass of CO 2 = 22400 x 41.8 == 0.088 g,
oxygen was treated with calcium, 3.5 g of calcium oxide was
'Mass of carbon == 0.024 g, mass of hydrogen 0.004 g.
obtained. Show that the results illustrate the law of definite
44
proportions. (B) Mass of CO 2 == - .-x 67.2 == O.l32g,
22400
35. By means of the given analytical results show that law of
Mass of carbon = 0.036 g, mass of hydrogen == 0.008 g.
multiple proportions is true:
Thus, the masses of carbon combining with same mass of
Mercurous chloride Mercuric chloride hydrogen are in the ratio of 4 : 3 which is a simple ratio. Hence,
Mercury = '84:92 % Mercury = 73.80% law of multiple proportions is followed.]
41. Aluminium oxide contains 52.9% aluminium' and carbon
Chlorine 15.08% Chlorine = 2620% dioxide contains 27.27% carbon. Assuming the validity of the
[Ans. The masses of mercury which combine with I part of law of reciprocal proportions, calculate the percentage of
chlorine are in the 'ratio of 2 : I, which is a simple ratio. Hence, aluminium in aluminium carbide.
law of multiple proportions is illustrated.] [Hint: From the data, it is observed that the ratio of masses of
36. 1 g of a metal, having no variable valency, produces 1.67 g of aluminium and carbon in aluminium carbide should be 3 : 1 or its
its oxide when heated in air. Its carbonate contains 28.57% of simple mu1tiple. Hence, percentage of aluminium iIi aluminium
the metaL How much oxide will be obtained by heating 1 g of carbide = 2.4 x 100. = 75.0]
the carbonate?
[Ans. 0.477 g] 42. Two volumes of ammonia, on dissociation gave one volume of
nitrogen and three volumes of hydrogen. How much hydrogen
Mass of metal Mass of metal in 1g of carbonate
[Hint: will be obtained from dissociation of 40 mL ofNH) ?
Mass of oxygen x
[Ans. 60 mLl
i.e., x == 0.1914 g of oxygen 43, The following results were obtained by heating different
oxides oflead in a current of hydrogen:
Mass of oxide = 0.2857 + 0.1914 = 0.4771 g] . (a) 1.393 g oflitharge gave 1.29~ g oflead.
37. 0.36 g of Mg cbmbines with chlorine to produce 1.425 g of (b) 2.173 g of lead peroxide gave 1.882 g oflead.
magnesium chloride. 9.50 g of anothefsample of anhydrous (c) 1.721 g of red lead gave 1.552 g oflead.
magnesium chloride gave, on electrolysis 2.24 litre of chlorine Show that these results ar.e in accordance with the law of
at NTP. Show that these data agree with the law of constant multiple proportions .
.proportions. .(Ans. Masses of lead that combine with same mas~Mf oxygen
(Hint: Mass of 2.24 litre of chlorine at NIP == ~ x 2.24 are in the ratio of 4 : 2 : 3 which is a simple ratio. So, 'the results
22.4 are in accordance with the law of multiple proportions.}
== 7.1 g. In both cases, the ratio of masses ofMg and CI is 1 : 3. 44.. Calculate the number of g-moles of CaO that could be
Hence, law of constant proportions is followed.] obtained from 42.54 g of CaC03 and convert. the number of
g-moles to grams.
38. Carbon dioxide contains 27.27% carbon, carbon disulphide
contains 15.97% carbon and sulphur dioxide contains 50% .42.54
[No. of g-moles =: == 0.4254,
sulphur. Show that these figures illustrate the law of reciprocal . 100
proportions. Mass of CaO 0.4254 x 56 == 23.8 !II
[Hint: The masses of oxygen and sulphur which combine with 45. I g of a metal M which has specific heat of 0.06 combines
1 part of carbon are in the ratio of 2.667 : 5.25, i.e., 1 : 2. In with oxygen to form 1.08 g of oxide. What i~ the atomic mass
sulphur dioxide, the masses of sulphur and oxygen are in the ratio ofM? . '
of 1 :. 1 which is a simple multiple of first. Hence, law of
reciprocal proportions is illustrated.]
46 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

. . . 6.4 51. If the equivalent mass of a metal (M) is x and the formula of its
[Hint: A pproxunate atOIll1C mass = = 106.6
0.06
oxide is M m On' then show that the atomic mass of Mis 2xn
m
Equivalent mass of M = I x8 100
[Hint: m atoms of M combine with n atoms of oxygen.
0.08
106.6 1 atom of M combines with!!.. atoms of oxygen.
Valency = - - "" 1 m
100
· 2n
Exact atomic mass = I 00 x I =100 ] Hence, Vaency
I =-
m
,-'
A compound .contains 28% of nitrogen and 72% metal by
mass. 3 atoms of the metal combine with 2 atoms of the Atomic mass = Equivalent mass x Valency
nitrogen. Find the atomic mass of the metal. 2n 2nx]
xx
[Hint: Valency of metal = 2 and valency of nitrogen 3 m m
52. Two oxides of metals A and B are isomorphoUS. The metal A
. I f0 ' . mass of metal 72
EqUlva ent mass nItrogen =-14 ; whose atomic mass is 5,2, forms a chloride whose vapour
. 3 14/3 28 density is 79. The oxide of the metal B contains 47.1%
Equivalent mass of metal = 12 '. oxygen. Calculate the atomic mass of B.
[Hint: Let the valency of A be x. The formula of chloride
Atomic mass of metal == 12 x 2 =24]
= ACl"
47. The chloride of a solid metallic element contains 57.89% by
2 V.D. A + x x 35.5 or x",3
mass of the element. The specific heat of the element is 0.0324
cal deg -1 g -I. Calculate the exact atomic mass of the element. As the two oxides are isomorphous, the valency of B is also 3.
-: Ient mass 0 f B =--
EqUiva 52.9 x 8 = 8.99 atomic mass of
[Hint: Equivalent mass of the element = 57:89 x 355:::: 48.8 -, 47.1'
, . 42.11
B = ~.99 x 3 26.97]
Approximate atomic mass 200 53. A mixture of 1.65 x 1021 molecules of X and 185x ler l
0.0324
molecules ofY weighs 0.6.88 g. If molecular mass ofY is 187,
200 what is the molecular mass of X ?
Val ency =-""4 21 21
.. 48.8 [Hint: A x 1.65 X 10 + 187 x 1.85 x 10 =0.688 A 4135]
23
Exact atomic mass = 48.8 x 4 195.2] 6.02 x 6.02 x 10 '

54. The equivalent mass of a metal is 29.73 and the vapour density
48. Two oxides ofametal contain 63.2% and 69.62% of the metal.
of its chloride is BOA. Find out the atomic mass of the metal.
The specific. heat of the metal is 0.117. What are the formulae
of the two oxides? [Ans. Atomic mass 118.92]
[Ans. M0 2 andM20 3]
2 x V.D. 2 x (BOA)
49. White vitriol (hydrated zinc sulphate) is isomorphous with [Hint: Valency
Eq. mass + 35.5 = (29.73 + 35.5) "" 4]
MgS04 ·7H2 0. White vitriol contains 22.95% zinc and 43.9%
of water of crystallisation. Find the atomic mass of zinc. 55. Calculate the percentage of aluminium, sulphate radical and
water in potash alum.
[Hint: The formula of white vitriol should be znS0 4· 7HP as it
[Ans. Al = 5.6<)010; SO!- 40.51%; Water = 45.57%]
is isomorphous to MgS0 4 ·7H20, i.e., 7 water molecules are
56. Carbohydrates are represented by the general formula
associated with one zinc atom. 7HP = 7 x.18 126. Mass of Zn
with which 126 parts of water by mass ate associated Cm (H2 0)". On heating, in absence of air, they decompose into
22.95 x I 26 = 65. 87. Atomic mass of. zinc.] steam (HP) and carbon. 3.1 g of a carbohydrate,\on complete
= decomposition by heating in absence of air, leave a residue of
.j. 43.~0 .,
1.24 g of carbon. If the molecular mass of the carbohydrate be
50. li\.. solid element. burns in oxygen without a~y change in
J 80, find its molecular formula.
volwne (of gas) under similar conditions 01 temperature and
pressure. If the vapour density of pure gaseous product is 32, [Hint: Determine % of carbon in carbohydrate. It is 40%. Water
what is the equivalent mass of the element? is 60%. Empirical formula == CHzO. Molecular formula
[Hint: One vol. of oxide contains 1 vol. of 02' = 6 x CHP CJI1206']
57. A gaseous hydrocarbon contains 85.7% carbon and 14.3%
One mole of oxide contains one mole of 02' hydrogen. 1 litre of the hydrocarbon weighs 1.26 g at NTP.
Mol. mass of oxide = A + 32 = 2 V.D. 64 Determine the molecular formula of th~ hydrocarbon.
[Ans. C2H4]
So, A = 32 58. Equal masses of oxygen, hydiogen and methane are taken in a
contairier under identical conditions. Find the ratio of their
32 parts of element combine with'32 parts of oxygen.
volumes.
Equivalent mass of element = 32 x 8 8]
[Ans. 1: 16: 2]
So,
32
 BASIC PRINCIPLES 47
59. How many moles are there in 1 m 3 of any gas at NTP? [Hint: Formula of divalent hydrated metal sulphate will he
[Ans. 44.6 moles] MS0 4 ·xH20
60. A hydrated chloride of metal contains 18.26% metal and
Molecular mass of salt = 65.4 + 96 + 18x
32.42% chloride ion by mass. The specific heat of metal is
0.16. What is hydrated chloride? = (161.4 + 18x) .
[Ans. CaCI 2 ·6H20] 18x
% of water = x 100 = 43.85
61. 1.878 gof MBrx when heated in a stream of HCl gas was 161.4 + 18x
completely converted to chloride MCl x which weighed 1.0 g. On solving, x=7
The specific heat of metal is 0.14 cal g-l. Calculate .the
.'. Molecular formula of hydrated salt = MS0 4 •7H 20 ]
molecular masses of metal bromide and metal chloride.
70. A person with fever has a temperature of 102.SOF. What is the
[Ans. Mol. mass of metal bromide = 285.54;
temperature in degree celsius?
Mol. mass of metal chloride = 1522]
[Hint: Use C= 5(F- 32)]
62. An au~omobile antifreeze consists of 38.7% C; 9.7% H and . 9
remaining oxygen by weight. When 0.93 g of it are vaporised
71. An ornamental ring contains 275 carats of diamond. How
at 200°C and 1 atm pressure, 582 mL of vapour are formed.
many grams diamond does it have?
Find the molecular formula of the antifreeze.
[Hint: 1 carat = 200 mg
[Ans. C;Ift;02]
:. Mass of diamond = 275 x 200 x 10-3 g]
63. A mineral contained MgO = 31.88 %; Si02 = 63.37% and
H20 = 4.75%. Show that the simplest formula for the mineral
72. 1 volume of a gaseous compound consisting C, H, °
on
complete combustion in presence of 2.5 volume of O2 gives 2
is H2Mg3Si4012.
°
(H = 1; Mg= 24; Si = 28; = 16)
vol. of steam and 2 vol. of CO 2. What is the formula of the
compound if all measurements are made at NTP?
64. How m~ny moles of NH3 are there in 250 cm 3 of a 30%
[Ans. C2H40]
solution, the specific gravity of which is 0.90?
73. 60 mL of a mixture of nitrous oxide and nitric oxide was
[Ans. 3.97 moles]
exploded with excess of hydrogen. If 38 mL of N2 was
65. Haemoglobin contains 0.25% iron by mass. The molecular formed, calculate the volume of each gas in the mixture.
mass of haemoglobin is 89600. Calculate the number of iron
[Ans. NO = 44 mL and N20 = 16 mL]
atoms per molecule of haemoglobin.
[Atomic mass of Fe = 56] 74. For a precious stone, 'carat' is used for specifying its mass. If 1
[Ans. 4 atoms] carat = 3.168 grains (a unit of mass) and 1 gram = 15.4 grains,
find the total mass in kilogram of the ring that contains 0.5
66. A sample of potato-starch was ground to give a starch like
carat diamond and 7 gram gold.
molecule. The product analysed 0.086% phosphorus. If each
molecule is assumed to contain one atom of phosphorus, what [Ans. 7.1 x 10-3 kg]
is the average molecular mass of the material? 75. The density of a gaseous element is 5 times that of oxygen
[Ans. 36000 amu] under -similar conditions. If the molecule of the element is
triatomic, what will be its atomic mass?
67. Insulin contains 3.4% sulphur. Calculate minimum molecular
mass of the insulin. [Ans. 53.33]
[Ans. 941.176 amu] 76. Calculate the number of electrons, protons and neutrons in 1
mole of 18 0 2- ions.
[Hint: For minimum molecular mass, one molecule of insulin
must have atleast orie sulphur atom:] [Ans. Electrons = 10 x 6.023 X 1023
68. Calculate the number of carbon, hydrogen and oxygen atoms Protons = 8 x 6.023 X 1023
in 18 g of glucose. .
Neutrons = 8 x 6.023 x 1023 ]
[Ans. 3.61 x 1023 carbon atoms, 7:22 x 1023 hydrogen atoms,
3.61 x 1023 oxygen atoms] 77. 600 mL of a mixture of 02 and D3 weighs 1 gm at NTP.
69. Hydrated sulphate of a divalent metal of atomic weight 65.4 Calculate the volume of ozone in the mixture.
loses 43.85% of its weight on dehydration. Find the number of [Ans. 200 mL]
molecules of water of crystallisation in the formula of
hydrated salt. [JEE (West Bengal) 2005]
I .'

48 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

..;p:OBJECTIVE QUESTIONS
S~t·1: Questions with single correct answer
15. One sample of air is found to have 0.03% carbon dioxide and
1. The father of modetn chemistry is: another sample 0.02%. This illustrates that:
(a) Priestley (b) Lavoisier (a) aids a compound
(c) Dalton (d) Mendeleev (b) air is an element
2. A pure substance can only be: (cr'air does not follow the law of constant proportions
(a) a compound (d) air is a mixture
(b) an element 16. Which one of the following is not a mixture?
(c) an element or a compound (a) Distilled water
(d) a heterogeneous mixture (b) Sugar dissolved in water
3. A pure substance which contains only one type of atoms is (c) Liquefied Petroleum Gas (LPG)
called: . (d) Gasoline
(a) an element (b) a compound 17. Which of the following is a charactelistic property of both
( c) a solid (d) a liquid mixtures and compounds?
4. Which one of the phrases would be incorrect to use? . (a) Their properties are same as those of their components
(a) A mole of an element (b) A mole ofacompound (b) Energy is released when they are formed
(c) Their masses me equal to the sum of the masses of theil'
(c) An atom of an element (d) An atom of a compound
components .
5. A symbol not only represents the name of the element but also
(d) They contain the components in fixed proportions
its:
. 18. Name the scientist who stated that matter can be converted
(a) atomic mass (b) atomic number
into energy:
(c) atomicity (d) atomic volume
(a) Boyle (b) Lavoisier (c) Avogadro (d) Einstein
6. The credit for the discovery of transuranic elements goes to:
19. Which one of the following is not an intensive property?
(a) Hahn (b) Rutherford
(a) Weight (b) Pensity
(c) Seaborg (d) Curie
(c) Refractive index (d) Melting point
7. The most abundant metal in'earth's crust is:
20. The metalloid among the following group of elements is:
(a) iron (b) magnesium
(CPMT 1993)
(c) calcium (d) aluminium
(a) P (b) As (c) Al (d) Po
8. The most abundant element in earth's crust is:
21. Which of the following ailoys does contain Cu andZn?
(a) hydrogen (b) oxygen (e) nitrogen (9) silicon
(lIT 1993)
9. Which one of the elements is not found in nature? (a) Bronze (b) Bras~
(a) Radium (b) Technetium . (c) Type metal (d) Rolled gold
(e) Polonium (d) Helium 22. Which metal is present in german silver?
Ill. Which one of the following is not a compound? (a) Copper (b) Iron (c) Silver (d) . Zinc
(a) Marble' (b) Ozone 23. Which of the following processes results in the formation of a
(c) Carborundum (d) Quicklime neW compound? .
11. Which one of the following is not an element? (a) Dissolving common salt in water
(a) Diamond (b) Ozone (c) Silica (d) Graphite (b) Heating water
12. The direct change from solid to gaseous state is referred to as: (c) Heating platinum rod
(a) dissociation (b) decomposition (d) Heating iron rod
(c) sublimation (d) deliquescence 24. Which one of the following is not a chemical change?
13. Sulphur burns in oxygen to form sulphur dioxide. The (a) Sublimation (b) Combustion
properties of sulphur dioxide are: (c) Electrolysis (d) Rusting
(a) totally different from sulphur and oxygen 25. The law of mUltiple proportions is illustrated by the pair of
(b) similar to'sulphur compounds:
, (c) similar to oxygen (a) sodium chloride and sodium bromide
(d) more similar to sulphur than oxygen (b) water and heavy water
14. Which one of the following statements is incorrect? (c) sulphur dioxide and sulphur trioxide
(a) All elements are homogeneous (d) magnesium hydroxide and magnesium oxide
,(b) Compounds always contain two or more different elements 26. In compound A, 1.0 g nitrogen combines with 0.57 g oxygen,
(c) A mixture is not always heterogeneous In compound B, 2.0 g nitrogen unite with 2.24 g oxygen and in
(d) Air is a heterogeneous mixture compound C, 3.0 g nitrogen combine with 5.11 g oxygen.
These results obey the law of:
 I
BASIC PRINCIPLES 49

(a) multiple proportions (b) constant proportions 36. Hydn;,gen combines with .chlorine to iornl HCl. It also
(c) reciprucai proportions (d) none of these combines with sodium to form NaH. If sodium and chlorine
27., Which one is the best example oflaw of conservation of mass? also combine with each other, they will do so in the ratio of
(a) 6 g of carbon is heated in vacuum, there is no change in ·their masses as:
mass (a) 23: 35.5 (b) 35.5 : 23
(b) 6 g of carbon combines with 16 g of oxygen to form 22 g (c) 1 : 1 (d) 23: 1
of CO2 37. Zinc sulphate contains 22.65% Zn and 43.9% H20. If the law
(c) 6 g water is completely converted into steam Of constant proportions is true, then the maSs of zinc required
(d) A sample. of air is heated at constant pressure when its to give 40g crystal!) will be: . .
volume increases'but there is no change in mass (a) 90.6 g (b) 9.06 g (c) 0.906 g (d) 906 g
28. A chemical equation: is balanced according to the law of: 38. 3 g of a hydrocarbon on combustion in excess of oxygen .
(a) multiple proportions (b) constant proportions produces 8.8 g ofCO2 and 5.4 g ofH,20. The data illustrates
(c) reciprocal proportions (d). conservation of mass the law of:
29. S02 gas was prepared by (i) burning sulphur in oxygen, (a) conservation of mass (b)· mUltiple proportions
(ii)· reacting sodium sulphite with dilute H2S04 and (iii) (c) constant proportions. (d) reCiprocal proportions
heating copper with conc. H2 S04 , It was found that in each
case sulphur and oxygen combined in the ratio of 1 : 1. The [Hint: Mass of carbon in 8.8 g CO2 '= ~ x 8.8 2Ag;
44
data illustrates the law of:
(a) conservation of mass (b) multiple proportions Mass of hydrogen in 5.4 g Hp = 2 x 5.4 0.6 g.
(c) constant proportions (d) reciprgcal proportions 18
30. A sample of CaC03 has Ca = 40%, C d 12% and 0= 48%. If Total mass of(e + 1I) = 2.4+ 0.6= 3.0 g]
is
the law of constant proportions true, then the mass of Ca in 39. In the reaction, N2 + 3H2 ~ 2NH3, the .ratio of volllmes of
nitrogen, hydrogenimd ammonia is 1 : 3 : 2. These. figures
5 g of Cac03 from another source will be:
(a) 2.0 g (b) 0.2 g ( c ) 0.02 g (d) 20.0 g illustrate the law of:
31. Potassium combines with two isotopes of chlprine (a) constant proportions (b) Gay-Lussac
. eSCI and 37CI) respectively to form two samples of KCI. (c) multiple proportions (d) reciprocal proportions
40. Two volumes of anllllonia, on dissociation gave Qne volume of
Their formation follows the law of:
nitrogen and three volumes of hydrogen. How much hydrogen
(a) constant proportions (b) multiple proportions
will be obtained from the dissociation of 10 litre ofNH3?
(c) reciprocal proportions (d)" none of these
(a) 30 litre (b) 10 litre (c) 15 litre (d) 2Q litre
32. Different proportions of oxygen in the various oxides of
41. If6litre ofH2 and 5.6 litre ofCl 2 are mixed and exploded in
nitrogen, prove the law of:
an eudiometer, the volume of HCI formed is:
(a) reciprocal proportions (b) multiple proportions
(a) 6.0 litre (b) 5.6 litre (c) 11.2litre (d) 11.6litre
(c) constant proportions (d) conserv~tion of mass
42. The law of constant proportions was enunciated by:
33. One part of an element A combines with two p<!l'ts of B
(a) Dalton (b) Berthelot (c) Avogadro (a) Proust
(another element). Six parts of eleI'llelit C combine wjth four
43. An important postulate ofDalton:s atomic theory is:
parts of element B. If A and C combine together, the ratio of
(a) an atom contains electrons, protons and neutrons
their masses will be governed by~
(a) law of definite proportions (b) atom can neither be created nor destroyed nor divisible
(c) all the atoms. of an elemeht are not -identical
(b) law of multiple proportions
(d) all the elements are available in nature in the form of
(c) law of reciprocal proportions
atoms
(d) law of conservation of mass
44. The atomic masses of the elements are usually fractional because: .,:'.
34. H2S contains 5.88% hydrogen, H20 ~ontains 11.11 % hydrogen
(a) elements consist of impurities
. while S02 contains 50% sulphur. These figures jllustrate the
(b) these are mixtures of allotropes"
law of:
(e) these are mixtures ofisobars
(a) conservation of mass (b) constant proportions
(d) these are mixtureS of isotopes
(c) multiple proportions (d) reciprocal proportions
35. Number.of atoms in"4.25 g ofNH3 is: (AFMC 2010)
of
·45. The chemical formula a particular compound represents:
3 (a) the size of its molecule
(a) 6.023xl023 . (b) 4x6.023xl02
(b) the sQ.ape of its molecule
(c) l. 7 X 1024 (d) 4.5 x 6.023 x 1023 (c) the total number of atoms in a molecule
. w (d) the number of different types of atomS in a molecule
[Hint: Number of molecules ofNH 3 =- x 6.023 X 1023
. M . 46. Which one of the following properties of an element is not
= 4.25 x 6.023 x 1023 variable?
17 (a) Valency (b) Atomic mass
Number of atom = 4 x 4.25 x6.023xto2, (c) Equivalent mass (d) All of these
17
= 6.023 x 102']
 50 GR B. PHYSICAL CH~MISrIW FOR COMPI::TITIONS

41. 1 amu is equal to: 57. 74.5 g of a metallic chloride contains 35.5 g of chlorine. The
(a) 1.00758 g (b) 0.000549 g equivalent mass of the metal is:
(c) l66xlO-24 g (d) 6.02 X 10-23 g (a) 19.5 (b) 35.5 (c) 39.0 . (d) 78.0
48. Which one of the following relationships is correct? 58. The product of atomic mass and specific heat of any element is
a constant, approximately 6.4. This is known as:
(a) At. mass = 6.4 x Sp. heat.
(a) Dalton's law (b) Avogadro's law
(b) At. mass x Sp. heat = 6.4
(c) Gay-Lussac law (d) Dulong Petit's law
(e) At. mass x 6.4 = Sp. heat
(d) At. mass x Sp. heat x 6.4 = 1
59. The molecular mass of chloride, MCl, is 74.5. The equivalent
mass of the metal M will be:
49. A I g of an element gives A2 g of its oxide. The equivalent mass
(a) 39.0 (b) 74.5
of the element is:
(c) 110.0 (d) 35.5
(a) A2 - Al X 8
[Hint: Mol. mass = At. mass + 35.5 = Eq. mass x valency +35.5,
Al
Valency of M from the formula Mel is 1]
(c) Al X 8 60. 1 g of hydrogen is found to combine with 80 g of bromine. 1 g
A2 - Al
. ".
50. Al g of an element gives A2 g of its chloride; the equivalent
of calcium combines with 4 g of bromine. The equivalent mass
of calcium is:
mass of the element is: (a) 10 (b) 20 (c) 40 (d) 80
(a) _A---,I~ x 35.5 (b) A2 x 35.5 61. 2.8 g of iron displaces 3.2 g of copper from a solution of
A2 - Al A2 - Al copper sulphate. If the equivalent mass of iron is 28, the
equivalent mass of copper will be:
(c) A2 - Al x 35.5 (d) A2 - Al x 35.5
(a) 16 (b) 32 (c) 48 (d) 64
Al A2
62. The specific heat of a metal of atomic mass 32 is likely to be:
51. Which one of the relationship is wrong? (a) 0.25 (b) 0.24 (c) 0.20 (d) 0.15' .
(a) 2 Y.D. = Mol. mass
63. The equivalent mass of an element is 4. Its chloride has a
(b) At. mass = Eq. mass x Valency
vapour density 59.25. The valency of the element will be:
6.4
(c) At. mass = - - - (a) 4 (b) 3 (c) 2 (d) 1
Sp. heat 64. The equivalent mass of iron in the reaction,
H I ' Mol. mass
(d) va ency = - - - - 3Fe + 4H20 = Fe 30 4 + 4H2 would be:
Eq. mass (a) 21 (b) 56 (c) 42 (d) 10
52. In ml g of a metal A displaces rnzg of another metal B from its 65. The specific heat ofa bivalent metal is 0.16. The approximate
salt solution and if their equivalent masses are EI and E2 equivalent mass of the metal will be:
respectively, then the equivalent mass of A can be expressed (a) 40 (b) 20 (c) 80 (d) 10
as: 66. A sample of pure calcium weighing 1.35g was quantitatively
converted to 1.88 g of pure calcium oxide. Atomic mass of
(a) EI = rnz x E2
ml calcium would be:
(a) 20 (b) 40 (c) 16 (d) 35S
(c) EI = ml ;2 rnz (d) EI = ~: x E2 67. A metal oxide is reduced by heating it in a stream of hydrogen.
It is found that after complete reduction, 3.15 g of the oxide
53. When the specific heat of a metallic element is 0.214 cal g -I , have yielded 1.05 g of the metal. We may conclude that:
the atomic mass will be closest to which one ofthe following? (MLNR 1991)
(a) 1 (b) 12 (c) 30 (d) 66' (a) atomic mass of the metal is 4
S<l. Approximate atomic mass of an element is 26.89. If its (b) atomic mass of the metal is 8
equivalent mass is 8.9, the exact atomic mass ofthe element is: (c) equivalent mass of the metal is 4
(a) 26.89 (b) 8.9 (c) 17.8 (d) 26.7 (d) equivalent mass of the metal is 8
55. When an element forms an oxide in which oxygen is 20% of 68. Compounds with identical crystal structure and analogous
the oxide by mass, the equivalent mass ofthe element will be: chemical formula are called:
(a) 32 (b) AO (c) 60 (d) 128 (a) isomers (b) isotones
56. 0.32 g of a metal gave on treatment with an acid 112 mL of (c) allotropes (d) isomorphous
,/ hydrogen at NIP. Calculate equivalent mass of the metal: 69. Which pair of the following substances is said to be
,. I[AMtJ'(Eilgg.. ) lOlO] isomorphous?
(~) 58 (b 32 (c) 11.2 (d) 24 (a) White vitriol and blue vitriol
[Hint.: Mass of metal that displaces 11200 mL hydrogen at STP (b) Epsom salt and Glauber's salt
wHl b-o it~ equivalent mass. (c) Blue vitriol and Glauber's salt
:. Equi"~Jent mass of metal = 0.32 x 11200 = 32] (d) White vitriol and epsom salt
112
 BASIC PRINCIPLES 51

c mass of chlorine is 35.5. It has two isotopes of atomic (c) 18.1 >.< 1023 molecules of CO2
~5 and 37. The percentage o~}~!#lyier~sotope is: (d) 3 g-atoms of CO2
, (b) 15 (c) 20'" (d) 25 85. Which among the following is the heaviest?
c mass of boron is 10.81. It has two isotopes with 80% IPMT (Kerala) 20061
)% abundance respectively. The atomic mass of the (a) One mole of oxygen
~ having 80% abundance is 11.01. The atomic mass of (b) One molecule of sulphur trioxide
ler isotope is: ( c) 100 amu of uranium
.81 (b) 11.01 (c) 10m (d) 21.82 (d) 10 moles of hydrogen
)f chlorine combines with a metal giving III g of its (e) 44 g of carbon dioxide
Ie. The chloride is isomorphous with MgCl2 . 6H2 0. The 86. The largest number of molecules is in:
; mass of the metal is: • (a) 28 gofCO (b) 46 gofC2H sOl:;l
(b) 30 (e) 40 (d) 69 (c) 36 g ofHzO (d) 54 g ofN2 0 s .
lpour density of a volatile chloride of a metal is 59.5 and 87. Which of the following has the smallest number of molecules?
Lllvalent mass ofthe metal is 24. The atomic mass of the (a) 22.4 x 103 mL of CO2 gas
1t will be:
(b) 22 g of CO2 gas
(b) 48 (c) 24 (d) 12
(c) 11.2 litre of CO2 gas
xide of an element possesses the molecular formula,
(d) 0.1 mole of CO 2 gas
. If the equivalent mass of the metal is 9, the atomic
)f the metal will be: 88. Thetmmber of grams of H2 S04 present in 0.25 mole of H2 S04
(b) 18 (c) 9 (d) 4.5 is:
lolecular mass of a compound having formula MO and (a) 0.245 (b) 2.45 (c) 24.5 (d) 49.0
tlent mass 20 is: 89. Number of molecules in I litre of oxygen at NTP is:
, (b) 40 (c) 28 (d) 20 3 3
(al 6.02 x ItY (b) 6.02x 102
~sity of air is 0.001293 g mL- 1• Its vapour density is: 32 22.4
·3 (b) 14.3 (c) 1.43 (d) 0.143
Divide with the density of hydrogen, i.e., 0.00009 g (c) 32 x 22.4 (d) 32
22.4
90. 4-.6 x I (iI~'atoms of an element weigh 13.8 g. The atomic mass
,f a substance when vaporised occupy a volume of 5.6
ofthe. element is:
. NTP. The molecular mass of the substance will be:
(a) 190 (b) 180 (c) 34.4 (d) 10.4
(b) 2M (c) 3M (d) 4M
apour densities of two gases'are in the ratio of I : 3.
molecular masses are in the ratio.oJ:
.3 (p) I : 2 (c) 2: 3 < (d) 3: 1
ganic compound on analysis was found to contain (c) 3 x 6.02 X 1023 (d) 4 x 6.02 X 1023
Vo of sulphur. The molecular mass of the 'eompound, if its 92. The total number of protons in 109 of calcium carbonate is:
llie contains. two sulphur atoms, is: (CPMT1992)
10 (b) 2000 (a) 3.01 i5x 1024 (b) l5057 x loZ4
1000 (d) 200000 "
tomic mass of an element is p. If valency is 3, the (cl. 2:0478 x. 1024 (4) 4.0956 x loZ4
r density of the volatile chloride will be: '" - 93. 19.7 kg of gold was recovered from a smuggler. The atoms of
,.75 (b) 6.675 (c) 667.5 - (d) 81 gold recovered are: (Au = 197) .
msity of a gas 'A' is three times that of a gas 'B'. If the . (a) 100 (b) 6.02 x 1023
lliar mass of A is M, the molecular mass of B is:
(c) 6.02 X loZ4 (d) 6.02 x loZ5
(b) M/3 - (c).fjM (d) M
94 .. The molecular mass of CO2 is 44 amu and Avogadro's number -
.fj is 6.02 x I oZ3. Therefore, the mass of one molecule of cn, is:
r density of a volatile substance is 4 in comparison to (a) '7.31 x 10-23 (b) 3.65 x 10-23 .-
le (Cl4 1~ Its molecular mass will be:
(b) 2 »(c) 64 (d) 128 (c) lOI X 10-23 (d) 2.01 x 10-23
e the wrong statement: 95. Equal volumes of different gases at any definite temperature
nole means 6.02 x 1023 particles and pressure have:
olar mass is mass of one molecule (a) equal weights (b) equal masses
olar mass is mass of one mole of a substance (c) equal densities (d) equal nlunb(=r of !1]ok.,;
olar mass is molecular mass expressed in grams 96. A gaseous mixture contains oxygen and nitrc)fycil in the ,.,,!iu vf
lIe of CO2 contains: (MLNR 1990; CBSE 1993) I : 4 by mass. Therefore, the ratio of their l:!!miYcr
Vl "'-" 1 n23 ..............-"" ,....c r-" molecules is:
 G.R. B. PHYSICAL CHEMISTRY FOR COMPETITIONS,

m will react with ethyl alcohol to give: 110. A compound of aluminium and chlorine is composed of9.0 g
,of hydrogen (b) one mole of oxygen Al for every 35.5 g of chlorine. The empirical formula of the
'ofNaOH, (d) 1/2 mole of hydrogen compound is:
an atom of carbon is: (a) AICI (b) AICl 3 (c) AICl 2 (d) AICl 4
(b) 1.99 x 10-23 g 111. The haemoglobin from red corpuscles of most marnmels
contain approxImately 0.33% of iron by mass. The molecular
(d) 1.99 x 1023 g
mass of haemoglobin is 67200. The number of iron atoms in
of moles of Hz in 0.224 litre of hydrogen gas at each molecule of haemoglobin is:
'(MLNR 1994) (a) 4 (b) 3 (c) 2 (d) 1
(b) 0.1 (c) 0.01 (d) 0.001 112. The percentage ofP20 s in diarnmonium hydrogen phosphate,
:Jf 1 g helium at NTPin litres is: [(NH4 )2 HP04 ] is: (CPMT 1992)
(b) 0.56 (c) 2.8 (d) 0.28 (a) 23.48 (b) 46.96
24
s to contain 1.0 x 10 particles, the mass of ope (c) 53.78 (d) 71.00
;en is: 113. The percentage of nitrogen in urea (NH2CONH2), is: '
(b) 5.32 g (a) 38.4 (b) 46.6 (c) 59.1 (d) 61.3
(d) 16:0 g 114. The chloride of a metal has the formula MCI 3 . The formula of
)f 1 litre capacity each are separately filled with
°
[e, 02 and 3 , At the same temperature and '
ratio of the number of atoms of th.ese gases
its phosphate is:
(a) M 2P04 ' (b) MP04 (c) M 3P0 4 (d) M(P04 )2
115. 10 g of hydrofluoric acid gas occupies 5.6 litre of volume at
ferent flasks would be:
NTP. If, the empirical formula of the gas is HF, then its
1 (b)2:1:2:3 molecular formula will be: (At., mass ofF = 19)
3 (d) 3 : 2: 2 : 1
(a) HF (b) H3F3
mperatirre and pressure, two flasks of equal
filled with H2 and'SOz separately. Particles which (c) H2F2 (d) H4F4
10
lUmber, in the two flaskes are: [Hint: Molecular mass - x 22.4 =40]
(b) electrons 5.6
:s (d) neutrons 116. Calcium pyrophosphate is represented by the formul.a
a mixture of 6.02x 1023 oxygen atoms and Ca ZP20 7 . The molecular formula of ferric pyrophosphate is:
ydrogen molecules at NTP is: (a) Fe 2P2 0 7 (b) FePZ0 7
(b) 33.6 litre (c) Fe(P20 7 )3 (d) Fe4(PZ07)3
(d) 22.4 litre 117. The percentage of available chlorine in a sample of bleaching
of molecules' present in a drop of water, if its ' powder, CaOClz ·2H2O, is:
)5mL, are: (a) 30 (b) 50 '(c) 43.5 (d) 59.9
,21
(b) 1.66 x102 2
n 8. SI unit of energy is:
~3 (d) 1.66x 1024 (a) kg m 2 S-2 (b) kg m- I S2
was 'found tocolltain nitrogen and oxygen in the (c) kg m 2 S-I (d) kg m 2 8 2
n 28 g and oxygen 80 g, The formula ()f the
119. One ~cro gram is equal to:
(a) 10:3 g , (b) 103 g (c) 106 g (d) 10-6 g
(b) N 2 0 3
(d) N;04 " 120. Significant figures in 0.00051 are:
t formula of a compound cOQ.tain"ing sb% of W5 ~3 002 ~4
At. mass = 10) and 50% of the element.y. (At. 121. ' The number of significant figures in 6.02 xloZ 3 is:
;: {(IIlI" 1994J
(a) 23 (b) 3 (c) 4 (d) 26
(b) X 2Y
(d) X 2Y 3 " , 122. Express 0:006006 into scientific notation in three significant
digits:
til X (At. mass 75) and Y (A!. mass = 16),
ivea compound having 75.8% of X. The f~rmula
(a) 6.01x io-
3 (b) 6.006 x 10-3
lund i s : ( M L N R 1991) (~) 6.00 x 10":3 (d) 6.0 x 10-3
(by X 2 Y 123. The proper value of significant figures in 38:0+ 0.003;5
(d) X 2Y 3
+ 0.00003 is:
a certaincornpound was found to contain iodine
(a) 38 (b) 38.0035
in the ratio of 254': 80. The formula of the
: (At. mass ofl = 127,0 = 16) (c) 38.00353' (d) 38.0
(b) 12 0 124. Which of the following is the correct unit for measuring
nuclear radii?
(d) 120s
(a) Micron " (b) Millimetre
 BASIC PRINCIPLES 53
~r to prepare 1 litre normal solution of KMn0 4, how 137. The density of a liquid is 1:2 glmL. There are 35 drops in 2
~ams of KMn04 are required if the solution is to be mL. The number of molecules in one drop (m.lar mass of
I acid medium for oxidation? (PET (MP) 2002) liquid = 70) is:
8g (b) 31.6 g (c) 62 g (d) 790 g (a) (1.21 NA
.
(b)(~J·
35
2 NA
'
!U1 oxide of a metal is converted to chloride completely . 35)
rields 5 g chloride. The equivalent weight of metal is: L2 .
(c)--z NA (d) 1.2NA
(KCET2002) (35)
.25 (b) 3.325 (c) 12 (d) 20 13lt A sample of PCI 3 contains iA mole;' the substance. How
:rofatoms 558.5 g Fe (At. wt. ofFe= 55.85 g morl) is: many atoms are there in the sample? IeEE (KeraJa) 20.04/
(AlEEE 20.0.2.) (a) 4 (b) 5/ 4'
ice that in 60 g carbon (b) 6.023 x lcY 3 (c) 8.431 X 1023 (d) ,572 x IcY
lfthat of8 g He (d) 558.5 x 6.023 x 1023 (e) 2A09 x lcY4
efix 1018 is: [MEE (Kerala) 2062J . .
139. The eqUivalent weigh
. N OH J;Yi"O ~
. NaH PO + H is:
2 4 2
°
I of ,nosphoric acid H 3P0 4 in the

~a (b) exa (c) kilo (d) nano reaction, a + 4 lBHU (Pre.~ 20051
:ga (b) 49 (c) 25 (d) 9&
mce in density is the basis of: LMEE (Kerala) 20.02) (all? Only one hydrogen ofH 3P04 is replaced, i.e,its basicity
ra filtration (b) molecular sieving ='1
. 1· MoleCular mass
wity separation (d) molecular attraction EqUlva ent mass = 98 = 98]
)mic absorption Ie Ids Basicity I
' 1 , j
:ctlVe of the source, pure sample of water ai:;'en. This is 140. 5.6 g of an organic compound on burning with excess of
-0 mass of oxygen and 11.11 % mass of)\''Kerala) 20.0.21 oxygen gave 17.6 g of CO2 and 7.2 g H20. The organic
led by the law of:
",.anJtrcompos1't'IOn compound is: [PET (Kcrala) 200.61
[lservation of mass .W)constant volume (a) C6H6 (b) C4Hs (c) C3HS (d) CH3 COOH
lItiple proportion (e) CH3CHO
141. The decomposition of a certain mass of CaC03 gave 11.2 dm3
y-Lussac~~l~electron weigh one kilogram? . of CO 2 gas at STP. The mass of KOH required to completely
lanv r [IIT(S.creening) 20.021 neutralise the gas i s : · (KCET 2006)
3 x 1023 (b) 1 x 1031 (a) 56 g (b) 28 g (c) 42 g (d) 20 g
9.108 3 1
[Hint: 11.2 dm of CO 2 at STP - mole CO 2
:3 X 1054 I 2
(d) X 108
9.108 9.1 08 x 6.023 KOH + CO 2 ~ KHC0 3
he numbers: 161 cm; 0.161 cm; 0.0161 cm. The
of significant figure for three numbers is:
~ mole CO2 will be neutrali)'ed by ~ mole KOH, i.e, 28 g KOR]
[AFMC CPune) 200.2l 142. How many moles of magnesium phosphate, Mg 3 (P04 )2' will
,5 (b) 3,3,3 (c) 3,3,4 (d) 3,4,4 contain 0.25 mole of oxygen atoms? (AIEE.E 2006:)
me of the following laws directly explains the law of (a) 0.02 (b) 3.125 x 10-2
Ition of mass? (AFMC 20(2)
(c) 1.25 X 10-2 (d) 2.5 x 10-2
d's rule (b) Dalton's law
[Hint:
gadro's law (d) Berzelius hypothesis .: 8 mole oxygen atoms are present in 1 mole Mg3 (P04 )2
las maximum number of atoms?
[Ill' (S.creening) 20031 :.0.25 mole oxygen atoms will be present in.!. x 0.25 mole
· 8 ·
. C(12) (b) 56 g Fe(56) Mjffi (PO 4}z' i. e., 3.125 x 10-2 mole Mg3 (PO 4hJ
. AI(27) (d) 108 g Ag(l08) 143. An element, X has the following isotopic composition,
lch of sulphur is present in an organic compound, if 200 X: 90%
:>mpound gave 1.158 g ofBaS04 on analysis?
199 X :8%
[PET (Kerala) 20.651
(b) 15% (c) 20% (d) 25% 202X :2%
the weighted average atomic mass of the naturally- occurring
_of H2 and 20 mL of O2 react to form water, what is element 'X' is closest to : ICDSE (Mt'd.) 2007)
e end oftl:!e reaction? (AFMC 2005) (a) 201 amu (b) 202 amu (c) 199 amu (d) 200amu
 G.R:B. PHYSICAL CHEMISTRY FOR COMPETITIONS

age atomic mass of 149. Common salt obtained from sea-water contains 95% NaCI by
8 x 199 ] + [ ~ x 202 ]
mass. The approximate number of molecules present in 109
x 200 ] + [ salt is: (DPMT 2009)
100 100
) amu "" 200 amu] (a) 1021 (b)1022
statement for 14 g CO is : (VMMC2007) ~I~ OOI~
is 2.24 L at NTP [Hint: Mass ofNaCI in 10 g salt:;:: 10 x ~ ::= 9.5 g
1 . 100
pOis to mole of CO
2 Number of molecules ofNael 9.5 x 6.023 x 1023
pondto same mole of CO and N2 58.5
22 23
3
'1" ....nds 3.01 x 102 molecules of CO = 9.78 x 10 "" 10 ]
r of hydi . 150. 109 hydrogen and 64 g oxygen were filled in a steel vessel
) h' h hll;en atoms present III 25.6 g of sucrose
w IC a\ molar mass of 342.3 g, is: and exploded. Amount of water produced in this reaction will
be: [CBSE (PMT) 20091
(VITEEE 2008)
. (a) 3 mol (b) 4 mol
(b\9.91x 1023
(c) 1 mol (d) 2 mol
(d) 44 ,- ..,,23
. 10 64
nber ot mOil;;" vr ~'-""Y"'<;e [Hmt : I1H = - :;:: 5 110 2 - = 2
Mass 4_.
2 2 32
:;:: -----,c.'-
Molar mass 342.3 2H2 + 02 ~ 2HzO
0.075 Case I : If H2 is completely consumed then:
101es of hydrogen atom = 0.075 x 22 nH 0 5 mol
2
toms of hydrogen 0.075 x 22 x 6.023 x 1023 ~''le II: If0 2 is completely consumed then
= 9:?x 1023 ] . htl~ 2
~-:-x2 4 mol
Ipied by one molecule ~f• • (-density = 1 glcm 3) Since, O 2 gives It.~
[CBSE-PMT (Pre.) 2008] hence, it is limiting an!9unt of product on complete consumption
3 cm
3 (b) 5.5 x 10- 23 cm3 equal to 4.] . "'er of moles of water formed will be
3 cm
3
(d) 6.023 x 10- 23 cm 3 151. An organic compound made ot '-.
nitrogen. What will be its molecularYmmd N contains 20%
18 one nitrogen atom in it? ijh£ontains only
iSS of one molecule = . 23 g
. 6.023 x 10 (a) 70 (b) 140 -"Il) 2009]
= 2.98 X 10- 23 g (c) 100 (d) 65
23
M 2.98x 10- [Hint: % N '" Mass of nitrogen x 100
>fie molecule = - - '- = cm 3
Density Molecular mass
"" 3 x 10- 23 cm 3 ] 20 =.!.± x 100
~cn contains as many atoms as in: (KCET 2008)
m=70]
lydrogen (b) 5 g of hydrogen
152. Given that the abundances of isotopes 54 Fe, 56Fe and 57Fe are
Iydrogen (d) I g of hydrogen
5%,90% and 5% respectively, the atomic mass of Fe is:
s consists oruniform cylindrical particles of 1:50A , (IlT 2009)
and 5000A long. The specific volume of virus is
lfthe virus is considered to bea single particle, its (a) 55.85 u (b) 55.95 u
lass is: (c) 55.75 u (d) 56.05 u
)7 g mol-1 (b) 7.90 x 107 g mor I [Hint:AtomicrnassofFe= 5 x54+ 90 x56+ 5 x57
)7 g mol-I (d) 9.70 x 107 g mol-I 100 100 100
55.95 amu]
lme of single virus = n?h 153. The number of atoms in 0.1 mol triatomic gas is:
= 3.14 x (75 x 1O- 8 i x (5000 x 10- 8 ) (N A = 6.02x 1023 mol-I) ICBSE (PMT) 2010]
8.836 x 10- 17
cm 3 (a) 6.026x 1022 (b) 1.806x 1023
. I .' Volmne 8.836 X 10- 17 cm 3 (c) 3.6x 1023 (d) 1.8x 1022
mg e ViruS =
, Specific volmne 0.75 Ig [Hint: No. of atoms = O.lx 3 x6.02x 1023
16
1.178xlO- g :;:: 1. 806 X 1023 ]
ss of virus 1.178 x 10- 16 x 6.023 X 10 23

7.09 X 107 g mol-I J

 BASIC PRINCIP~cS 55

questions given below may have more 4. Select the numbers with same significant figures:
than one correct answers (a) 6.02 x 1023 (b) 0.25
(c) 6.60 x 10- 34 (d) 1.50
'the following relationships are wrong?
3 S, Which are isomorphic to each other?
l"" 0.1 har (b) 1 litre = 1 r.m (a) CuS04·5HP· (b) ZnS04·7HzO
0.239 cal (d) 1 eV;-:1.11 x 10--4 J (c) FeS04·7H20 (d) FeS04·8H20
If the following numbers have same significant 6. 11.2 L of a gas at STP weighs 14 g. The gas could be:
(a) N2 (b) CO
) (b) 0.60 ~c) 6.0 (d) 60 (c) NO z (d) NzO
fthe following }).ive the same mass? 7, 8 g O2 has same number of molecules as that in:
oole of 02 gas (a) 14 g CO (b) 7 g CO
nole of SC?2 gas (c) 11 g CO2 (d) 22 g COz
3 x 1022 molecules of S02 gas
4 x 1023 molecules of0 2 gas

Assertion-Reason TYPE QUESTIONS

e following questions, two st?Nments are given as 6. (A) Empirical formula of glucose is HCHO.
A) and 'Reason' (R). AIlswer the questions by (R) Molecular formula of glucose will also be equal to HCHO.
er codes given bell''' . 7, (A) The volume of 1 mole of an ideal gas at I bar pressure at
Jth (A) aJ'lrl \t<.) are correct and CR) is the correct 25°C is 24.78 litre.
ana~4'1 of (A). ' (R) 1 bar == 0.987 atm.
Ith (A) and (R) are correct but (R) is not the correct 8. (A) Atomic weight ': Specific heat (cal/mol) x 6.4
anation of (A). (R) The formula is valid for metals only.
,) is correct and (R) is wrong. 9. (A) Number of moles of Hz in 0.224 L of H2 is 0.0 I mol.
") is wrong but (R) is correct. (R) 22.4litres ofH2 at STP contains 6.023 x 1023 mol.
lth (A) and (R) are wrong. (AIIMS 1996)
O2 and 1 g'03 have equal number of atoms. 10. (A) The equivalent weight of an element is variable.
;s of 1 mole atom is equal to its gram-atomic mass. (R) The valency of an elemeftt is variable. (!\JlMS 1995)
our density of sulphur vapour relative to oxygen is 2 11. (A) The number of significant figures in 507000 is three.
luse sulphur atom is twice as heavy as that of oxygen (R) In 507000, all the zeros are significant.
n. 12. (A) Law of conservation of mass is invalid for nuclear fission,
lOur density depends upon the molecular state of the fusion and disintegration.
stance in vapour state. (R) The law proposes that mass is neither created nor
vogram is equal to 1 amu. destroyed in a reaction. .
'gram is reciprocal of Avogadro's number. 13. (A) Mas,S spectrometer is used for determination of atomic
ole H2S04 contains same mass of oxygen and sulphur. mass of isotopes.
.ole H2S04 represents 98 g mass. (R) Isotopes are the atoms of same element having same
nole oxygen and N2 have same volume at same atomic number but differeni mass numbers.
perature and pressure.
,ole gas at NTP occupies 22.4 litre volume at STP.
G.R.B. PHYSIC/\" CHEMISTRY FOR COMPETITIONS

e' QUESTIONS :: :
: 1
t

\
3. (a) . 4. (d) 5. (a) 6. (e) 7. (d) 8. (b)
1. (e) 12. (e) 13. (a) \4. (d) 15. (d) 16. (a) \
9. (a) 20. (b) 21. (b) 22. l\l) 23. (d) 24. (a) 1
7. (b) 18. (d) 29. (c) 30. (a) J
31. (d) 32. (b)
5. (a) 36. (a) 37. (b) 38. (a) 39. (b) 40. (e)
3. (b) 44. (d) 45. (d) 46. (ti) 47. (e) 48. (b) \
t
1. (d) 52. (b) . 53. (c) 54. (d) 55. (a) 56. (b) i

9. (a) 60. (b) 61. (b) 62. (e) 63. (b) 64. (a)
7. (e) 68. (d) 69. (d) 70. (d) 71. (e) 72. (e)
5. (a) 76. (b) 77. (d) 78. (a) 79. (d) 80. (a)
3. (b) 84, (a) 85. <e) 86. (e) 87. (d) 88. (e)
1. (d) 92. (a) 93. (d) 94. (a) 95. (d) 96. (e)
9, (e) 100. (a) 101. (a) l'6't,(b) 103. (c) 104. (d)
7. (b) 108. (d) 109. (d) 110. (b) 111..(a) 112. (e)
5. (e) 116. (d) 117. (e) 118. (a) ,"1.Q, (d) l~o.(e)
3. (d) 124. (d) 125. (b) 126. (a) 127. (a) 12K.:(b)
."
L (d) 132. (b) 133. (e) 134. (a) 135. (e) ,"ll.· (d)
). (d) 140. (b) 141. (b) 142. (b) 143.• (d) ·'144. (a)
7. (b) 148. (a) 149. (e) 150. (b) 151 •. (a) 152. (b)

J. (b, «) 4. (a, c, d) 5. (b, e) 6. (a, b) 7. (b, c)

I-REASON TYPE QUESTIONS j

(e) 4. (d) 5. (b) 6. (e) 7. (b) 8. (b)
(e) 12. (b) 13.' (a)
 BASIC PRINCIPLES 57

BRAIN STORMING PROBLEMS /1/1/1

lOBJECTIVE QUESTIONS] for ( lIT ASPIRANTS I
ng questions co~tain single correct option: [Hint: Mass = 18g
the following table: Number of molecules ofHzO in 18 g mass = 6.023 x IO z3
npound Mass of the compound Number of electrons in 18 g water = 6.023 x.l OZ3 x 10
II. mass) r (in grams) taken, = 6.023 x 1024 4
CO2 (44) 4.4 .: Each molecule of water contains 10 electrons.]
NO? (46) 2.3 6. What is the empirical formula of vanadium oxide if 2.74 g of
HzOz (34) metal oxide contains 1.53 g of metal?
S02 (64) 1.6 (a) VZ0 3 (b) VO (c) V20 S (d) ~07
two compounds have least mass of oxygen? tni.... % of V = 1.53 x 100= 55,83
:ular masses of compounds are given in brackets.) ?.74
(EAMCET 2004)
.. %of ° =44.17
nd IV (b) I and III (c) I and II (d) III and IV Element % Atomic ratio Simplest ratio
I. Mass of oxygen present = 4.4 x 32 = 3,2 g 55.83", 1.1 l.l
44 V 55.83
52 1.1
[I. Mass of oxygen present = 2.3 x 32 = 1.6 g 44.17 =.2.76 2.76
44.17 2.5
46
II. Mass of oxygen present = 6.8 x 32 = 6.4 g
° 16 1.1
34 V:0=2:5

V. Mass of oxygen present = ~ x 32 = 0.8 g

Thus, empirical fomlUla = VzO s]
64 7. Number of moles of electrons in 4.2 g ofN 3 - ion (nitride ion)
I IV have leaSt mass of oxygen.] is:
osphateofacertain metal M is M 3 (P04 h. The correct (a) 3 (b) 2 (c) 1.5 (d) 4.2
a of metal sulphate would be: 8. The ratio of volumes occupied by 1 mole 02 and I mole CO2
(S04 h (b) MS04 under identical conditions of temperature and pressure is:
(S04 h (d) M 2 S04 (a)l:1 (b)l:2 (c)J.:3 (d)2:1
rcentage of Se in peroxidase enzyme is 0.5% by mass 9. The maximum amount of BaS0 4 that can be obtained on
~ mass of Se 78.4 amu). Then, the minimum mixing 0.5 mole BaCl z with I mole H 2S0 4 is:
lIar mass of enzyme which contains not more than one (a) 0.5 mol (b) 0.1 mol (c) 0.15 mol (d) 0.2 mol
n is: [Hint: H 2S0 4 + BaCl z ---? BaS04 + 2HCI
i8x 104 amu (b) 1.568 x 107 amu 0,5 mole BaCt z will react with 0.5 mole H 2S0 4 to give 0.5 mole
i8x 103 amu (d) 1.568 X 106 amu BaS04 ] ,

.: 0.5 g Se is present in 100 g enzyme. 10. Ifl021 molecules are removed from 100 mg CO 2 , then number
'II be present In
. -100' x 78.4
. of moles of CO 2 left are:
~ Se WI g enzyme
0.5 (a) 6. lOx. 10-4 (b) 2.8x 10-3 .
= 15680amu (c) 2.28x 10-3 (d) 1.36 x 10-2
= ~.568x 10 amu]
4
[Hint: Number of molecules in 100 mg CO 2
mber of moles of a gas in I m 3 of volume at NTP is: Mass x 6.023 x 1023
(b) 0.446 (c) 1.464 (d) 44.6 Molar mass
1m 3 1000 L
= 0.1 x 6.023 x10 23
1000 44
nber ofnnles =--= 44.6]
22,4 = 1.368 X 1021
:d number of electrons present in 18 mL water (density Molecules remaining = 1.368 x 1021 1021 0.368 X 1021
) is:
21
:3x 1023 (b) 6.023 x 1024 ..
N urnb er 0 f mo Ies remammg
0.368xl0
= ---~
3x 1.025 (d) 6.023 x 1021 6.023 x
 '.
\
\

G.R.B: PHYSICAL CHEMISTRY FOR COMPETITIONS

on one gram ion of Al 3+ ion is: LHint: In the isotope I~C: Number of protons 6
1
: e coulomb (b) - x NA x e coulomb Number of neutrons 8
3
New atomic mass will be 2 x 6 + ~ x 8 16
ecoulomb (d) 3 x NA x e coulomb 2
. 16-14 .
3
: gram ion of A1 + means one mole ion of AI 3+. % Increase In mass = x 100 = 14.28% ]
14· .
mole A1 + 3
3 x e x ~ coulomb.]
17. The mass and charge of I mole electrons will be:
lass ofNzO as well as CO2 is 44 g mol-I. At 25°C (a) I kg; 96500 C (b) 0.55 mg; 96500 C
:essure, 1 L N 2 0 contains n molecules of gas. The (c) 1.55 mg; 96500 C (d) 5.5 mg; 96500 C
~02 molecules in 2 L under same conditions will
18. The simplest formula of the compound containing 50% X
(atomic mass 10 amu) and 50% Y (atomic mass 20 amu) is: .
(b) 2n (a)XYz (b)X 2Y (C)X 2Y3 (d)XY-
[Hint: Element <>4 ""mmle ratio Simplest ratio
. is dissolved in 1 L water. The number of ions of
in 1 mL of this solution will be: 50 5
X 50 =5 -=2
19 22 20 10 2.5
1 (b) l2 x 10 (c) l2 X 1020 (4) o.v2 X 10
nber of mol.,,, of !'laCI 50 = 2.5 2.5
Y 50
Mass = 5.85 = 0.1 20 2.5
Molar mass 58.5
Formula = X 2Y]
lUS (Na + + cr )in 1 L 19. Rest mass of 1 mole neutrons (mn ::: 1.675 X 10-27 kg) is:
(a) 1.8 X 10-3 kg (b) l.008 x 10-4 kg
= 2 x 0.1 x 6.023 x 1023
(c) 1.08 X 10-3 kg (d) 1.008 x 10-3 kg
= 12.046 X 1022
[Hint: .Mass of 1 mole neutrons
12.046 X 1022 1.675 x 10-27 X 6.023 X 1023
)TIS in 1 mL L2x 1020]
1000 = 1.008 X 3
10- kg]
de has the formula X 20 3 '} t can be reduced by 20. Loschmidt number is the number of:
give free metal and water. 0.1596 g of metal oxide (a) molecules present in I mL of a gas at STP
g of hydrogen for complete reduction. The atomic (b) molecules present in 1 gram mole of a gas at STP
al in amu is:
(c) atoms present in 1 mL of a gas at STP
(b) 155.8 (c) 5.58 (d) 55.8
(d) atoms present in I gram mole of a gas at STP
P3 + 3H z ----7 2X + 3HzO 21. Which of the following statements is incorrect?
ml 31001
48) g 6g . 108 -23
(a) One gram mole of sIlver equals - - x 10 g
i2 is required by 0.1596 g oxide 6.023
ill be required by 159.6 g oxide (b) One mole of CH4 and 17 g of NH3 at NTP occupy same
volume
2a + 48 = 159-./5
(c) One mole Ag weighs more than t~at o~~o moles o~Ca
a = 55.8
(d) One gram mole of CO 2 is 6.023 x loZ times heaVier than
tomic mass of metal M. ] one molecule of CO2 .
(PH3 ) decomposes to produce vapours of One atom of an element 'X' weighs 6.664 x 10-23 gm. The
and H2 gas. What will be the change in volume number of gram atoms in 40 kg of it is:
LL of phosphine is decomposed? (a) 10 (b) 100 (c) 10000 (d) 1000
(b) 500 mL The density of a liquid is 1.2 g/mL. There are 35 drops in 2
(d) 500 mL mL. The number of molecules in I drop is (molecular weight
PH 3(g) ----7 Pig) + 6H2(g) ofliquid 70):
4 mL
10 mL
----7

----7
1 mL
100
4
6 mL
~ x 100
4
(a) ~.~ NA (b) C5Y
l
NA

10 mL ----7 25 mL ISO mL (c)~N (d)1.2NA

(35i A
~ses by 75 mL.]
neutron is assumed to half of its original value, 2
[H Volume of one drop = - mL
t of proton is assumed to be twice of its original 35
ile atomic mass of ': C will be: 2x L2 1.2
Number of moles in one drop: "1"" '"7" = ,.",,2
 BASIC PRINCIPLES 59

[Hint: Na2S04·nH20"
nolecules in one drop = L22 x NA ]
(35) Molar mass (l42+lSn)
ne of a liquid will contain 4 mole? Molar mass of Mass of water == 12.6 x (142 + ISn)
oand its density is 1.4 glmL: ' 26.S
(b) 1.6 L (c) 0.8 L (d) 4.8 x l(J23 L 126'
18n'" - ' x (142+ 18n)
t x L liquid contain 4 mole of it. 26.8
n 7]
Mass
.ber of moles 29. Consider the following data:
Molar mass
Element Atomic weight
4 = x x 1000 x 1.4 A 12.01
. 2S0
B 35.5
x = 4 x 2S0 '" O.S L]
1.4 x 1000 A and B combine to form a new substance X. If 4 moles of B
combine with 1 mole of A to give I mole of X, then the weight
ratio of Fe 2+ to Fe 3+ in a mixture of FeS04 and
of I mole of X is:
having equal number of sulphate ions in both
(a) 154 g (b) 74 g (c) 47.S g (d) 160 g
I ferric sulphates is:
30. How many moles ofNa + ions are in 20 mi of 0.4 MNa3P04?
(b) 3: 2
(a) 0.008 . (b) 0.024 (c) 0.05 (d) 0.20
(d) none of these
, MV 0.4 x 20
S04 ~ Fe2+ + SO~- [Hint: No. of moles ofNa 3P0 4 =
1000 1000
04)3 ~ 2Fe3+ + 3S0~- = 0.008
Number of moles ofNa+ '" 3 x Number of moles ofNa 3P04
mole SO~- ions are furnished by both FeS0 4 and
3 x 0.008 = 0.024]
31. The element whose one atom has mass ofl 0.86 x 10-26 kg is:
moles of Fez+ "'x
(a) boron (b) calcium (c) silver (d) zinc
moles ofFe3+ =2 x 32. An electric discharge is passed through a mixture containing
3 50 cc of 02 and 50 cc of Hz. The volume of the gases formed
2 (i) at room temperature, (ii) at 110°C will be:
: Fe3+ ::x:-x
3 (a) (i) 25 cc (ii) 50 cc (b) (i) 50 cc (ii) 75 cc
= 3: 2]
(c) (i) 25 cc (ii) 75 c c ( d ) (i) 75 cc (ii) 75 cc
[Hint: 2H 2 (g) + 02(g) ~ 2Hp
f electrons present in 3.6 rng of N~ are:
(b) 1.2 x Hro (c) 1.2 x 1022 (d)2x 10- 50 cc Hz will combine with 25 cc 02 to form 50 cc Hp
3
Q21
:. 02 left '" 25 cc
umber of electrons in one ion ofNH! 10
At room temperature, HP will be in liquid state but at llO°.C, it
'ions in 3.6 mg NH! will be gaseous. Thus, volume of gases at 25°C and 110°C will be
3 25 cc and 75 cc respectively.]
3.6x 10- x 6.023 X 1023 ", 1.2x 1020 33. The mass of carbon p(esent in 0.5 mole ofK 4[Fe(CN)6] is:
IS
(a) 1.8 g (b) 18 g (c) 3.6 g (d) 36 g
ber lh,lectrons in 3.6 mg NH~ = 1.2 x 1020 x J/J [Hint: 1 mole of~[Fe(CN~ ]contains 6 mole carbon, i.e., 72 g
=1.2xl02 11 carbon,]
:tion 4A + 2B + 3c -----7 A 4 B 2C 3 , what will be the 34. Caffeine has a molecular weight of 194. If it contains 28.9%
. moles of product formed, starting from one mole of by mass of nitrogen, number of atoms of nitrogen in one
Ie of Band 0,72 mole ofC? : molecule of caffeine is:
(b) 0.3 (c) (d) 2.32 0.14 004 ~6 ~2 W3
A + 2B +3C
001 0,6 mol 0,72 !lJl1
:.......-? A4 B2C 3 [Hint: Mass of nitrogen in 194 amu caffeine 2S.9 x 194
.100
~ent case, reactant 'C' wili be the limiting reactant = 56amu
will give least amount of product on being completely :. One molecule of caffeine will contain 4 atoms of nitrogen.]
35. Chlorine can be prepared by reacting HCI with Mn02' The
~ives I mol product, reaction is represented by the equation,
>,

'C' will give 0.24 mol of product.] Mn02(s) + 4HCI(aq.) ~ CI 2 (g)+ MnCI 2 (aq,) + 2H 20(l)
of Na 2 S04'nH2 0 contains 12.6 gm of water. The Assuming that the reaction goes to completion, what mass of
, is: conc. HCI solution (36% HCI by mass) is needed to produce 2.5 g
- - _....... _ -
60 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

36. What is the mass per cent of oxygen in Al2(S04k18H20? x = Atomic mass of metal
The molar mass ofthis substance is 666.43 g/mol : .: 0.006 g Hz reduces 0.1596 g M 20 3
(a) 9.60 (b) 28.8 (c) 43.2 (d) 72
:. 6 g Hz will reduce 0.1596 x 6 gMz03 = 159.6Mz0 3
37. 0.25 g of an element 'M' reacts with excess fluorine to produce 0.006
0.547 g ofthe hexafluoride MF6 • What is the element? 2x + 48 = 159.6
(a) Cr (b) Mo (c) S e d ) Te 2x = 111.6
38. How many electrons are present in 2 x 10-3 moles of 1~02-? x=55.8].
(a) 1.2 x 102 1 (b)9.6x 1021 (c)1.2x 1022 (d) 1.9 x 1022 46. In a compound ofm~lecular formula AmBn:
39. Fluorine reacts with uranium to form UF6 . (a) number of equivalents of A, B 'and AmBn are same
U(s) + 3F2 (g} UF6 (g) (b) number ofmru..es of A, Band AmBn are same
How many fluorine molecul~s are required to produce 2 mg of (c) m x moles 01 A n x moles of B = (m + n) X moles of
UF6 from an excess of uranium? The molar mass ofUF6 is 352 AmBn
(d) n x moles of A = m x moles of B = (m + n) x moles of
g mol-I.
AmBn
(a) 3.4 x 101 8 (b) I X 1019 (c) 2 X 1019 , (d) 3.4 x 102 1 47. 4.4 g of CO 2 and 2.24 litre of H2 at STP are mixed in a
40. What is the formula of a substance with mass percentages of container. The total number of molecules present in the
°
35.79% for S, 62.92% for and 1.13% for H? container will be:
(a) H ZS03 (b) H 2 S04 (c) HiSz07 (d) H 2 S2 0 g (a) 6.02"2 x 1023 (b) 12044 x 1023
41. In 1811, Avogadro calculated the formula of camphor by (c) 6.023 X 1026 . (d) 6.023 x 10M
means of elemental chemical analysis and by measuring the
density of its vapour. Avogadro found the density to be 3.84 48. A partiillly dried clay mineral contains 8% water. The original
gIL when he made the. measurement at 210°C at 1 atrn sample contained 12% water and 45% silica. The % of silica in
pressure. Which of the following is the correct formula of the partially dried sample is nearly:
camphor? (a) ~O% (b) 49%
(a) CIO H140 (b) CIO HI6 0 (c) ClO H I6 0 2 (d) C IO H18 0 (c) 55% (d) 47%
(e) None ofthese [Hint: Initial stage: Clay Silica Water
[Hint: Pm = dRT 43% 45% 12%
Final stage: (92 - x) x 8%
m = dRT = 3.84 x 0.0821 x 483 = 152.27
P 1 Ratio of silica and clay will remain constant, before and after
drying.
:. C IOH IIJ will be the correct formula.]
45 x
42. A quantity of aluminium has a mass of 54 g. What is the mass
of same number of magnesium atoms? 43 92-x
(a) 12.1 g (b)24.3 g (c) 48.6 g (d) 97.2 g x == 47%]
43. When 1 L of CO2 is heated with graphite, the vQlume of the 49. Which ofthe following is isomorphous with MgS04 ·7H20?
gases collected is 1.5 L. Calculate the number of moles of CO (a) Green vitriol (b) Blue vitriol
produced at STP: . (c) Red vitriol (d) Vitriol of mass
1 28 1 (d) 14 50, In the reaction;
(a) 11.2 (b) 22.4 (c) 22.4 22.4 I '-7 2NO
CO + 2 O 2 -------7 COz; N2 + Ory
[Hint: cO2 (g)+ C(s) -------7 2CO(g)
I-x 2x 10 ~ of mixture containing ('~<oon monoxide and nitro~en
Total volume = 1 - x + 2X = 1 + x 1.5 requn-ed 7 mL oxygen to form CO~ and NO, on combustIOn.
x = 0.5 L The volume 9fN2 in the mixture will be:
.. Volume of CO = 2 x 0.5 = 1 L (a) 7/2 mL t'0) 1712 mL (c) 4 mL (d) 7 mL
1
Nwnber of moles of CO = - - ] [Hillt: CO(g) +.~ O,(g) ---t CO 2(g)
22.4 x ·2-
xl2
44. Which of the following has greatest number of atoms?
(a) 1 g of butane (C4 H IO ) (b) 1 gofhitrogen (Nz) y y
(c) 1 g of silver (Ag) (d) Ig of water (H2 0) x + y= 10 ... (i)
°
45. A metal oxide has the formuia M 2 3' It can be reduced by Hz
to give free metal and water. 0.1596 g of M 2 0 3 required 6 mg
X
-+ y=7 ... (ii)
2
OfI:I2 for complete reduction. The atomic mass of the metal is:
Solving eqs. (i) and (ii),
(a) 27.9 (b) 79.8 x=-6 . and y=4]
(c) 55.8. (d) 159.8 51. 1.44 g of titanium (Ti) reacted with excess of0 2 and produced
[Hint: M 20 3 + 3H z -------7 2M + 3HzO x. gm of a nonstoichiometric compound Ti 1.440 ! . The value 0 f
. ,
,; (2x + 48) g 6g x is:
 I
BASIC PRINCIPLES 61

(b) 1.77 Following questions may bave more tban one correct options:
(d) None of these
1. 1l.2 L of a gas at STP weighs 14 g. The gas could be:
Ile reaction:
(a) NzO (b) N02 (c) N2 (d) CO
Ti +02 ~ Til.4401
2. In which of the following pairs do 1 g of each have an equal
101es of titanium = Number of moles ofTil.440] number of molecules? .
1.44 x
(a) N 20 and CO (b) N2 and C30 Z
48 48 x 1.44 + 16
(c) N2 and CO (d) N 20 imd CO2
x=1.77g] 3. 8 g of oxygen has the same number of molecules as in:
le of75% alcohol by mass (d = 0.8 g/cm 3 ) must be (a) 11 g CO2 (b) 22 g CO2 (c)7 g CO (d) 14 g CO
pare 150 cc of 30% alcohol by mass (d 0.9 4. Which of the following has three significant figures?
(a) 6.02 x 1023 (b) 0.25
(b) 56.25 mL
(c) 6.60 x 10-34 (d) 1.50
(d) 3356mL
V mL of alcohol was used .. 5. 1 mole of I~ N 3- ions contains:
~ x V x 0.8 ~ x 150 x 0.9 (a) 7 x 6.023 X 1023 electrons (b) 7 x 6.023 x 1023 protons
100 100 (c) 7 x 6.023 X 1023 neutrons (d) 14 x 6.023 x 1023 protons
V= 67.5 mL]
6. 1 g atom of nitrogen represents:
(a) 14 g nitrogen
(b) 11.2 litre ofN 2 at NTP
(e) 22.4 litre ofN2 at NTP
(d) 6.023 x 1023 molecules ofN 2

.'.
'fIeIZ4
'ect option
2. (b) 3. (a) 4. (d) 5. (b) 6. (e) 7. (a) 8. (a).
10. (a) 11. (d) 12. (b) 13 .. (c) 14.. (d) 15. (e) 16. (b)
18. (b) 19. (d) 20. (a) 21. (a) . 22. (d) 23. (c) 24. (c)
26. (a) 27. (c) 28. (d) ~9. (a) 30. (b) 31. (d) 32. (e)
34. (a) 35. (b) 36. (d) 31. (b) 38. (e)· 39. (b) 40. (e)
42. (c) 43. (c) 44. (a) 45. (c) ';;46. (a) 47. (1;» 48. (d)
50. (c). 51. (b) 52. (c)
'e than one correct options
2. (e, d) 3. (a,c) 4. (a, c, d) 5. (b,'c) 6. (a)
 -.

G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS

Integer Answer TYPE QUESTIONS

o each of the following questions is a 7. 5 g Hz is allowed to react with 14 g Nz for the following
teger, ranging from 0 to 9. If the correct reaction:
.estion numbers X, Y, Z and W (say) are N 2(g)+ 3H2(g)~ 2NH3(g)
respectively, then the correct darkening What mass ofH2 will be left unreacted at the end of reaction?
lliook like the given figure. [Hint :N2 is limiting reactant, thus 14 g N2 will give 17 g NH3'
and xg H2 remains unreacted.
Mass before reaction = Mass after reaction
(5+ 14) (17+x)
x= 2g]
'ous alkane (Cn H 2n + 2 ) is exploded with oxygen. The 8. Calculate the number of moles of water in 976 g BaCI 2 · 2H2o.
! of 02 used and CO2 formed are in the ratio of 7 : 4. 9. If Avogadro's number be 3.01x 1023 then the atomic mass of
e the value of n. carbon will be:
C"H 2n+ 2 + [n+ n; 'J 02 ~ nC02 + (n+ I) H20 10. How many moles of R will be produced when 8 mol of P and 5
mol of Q are allowed to react according to the equation:
(n+ I) 2P+Q~R
n+-- 7 11. The mass ofI x IOZz molecules of blue vitriol (CuS04 ·xH20)
__ 2_=_
n 4 is 4.144 g. The value of 'x' will be:
n = 2] 12. What will be the mass (in kg) of 7.298 x 106 mol electrons?
l1any atoms do a mercury vapour molecule consist of, if 13. Silver (Atomic weight 108 g mor-I) has a density of 10.5 ~
pour density of mercury vapour relative to air is 6.92? cm~3. The number of silver atolllS on a surface area ofI 0- 12 m
ic mass of mercury is 200). The average molar mass of can be expressed in scientific notation as y x I if. The value of
~9 g/mol. xis: (lIT 2010)
Vapour density ofHg vapour Molar mass ofHg [Hint: Mass of I cm 3 Ag = I x 10.5 g
Vapour density of air Molar mass of Air 10.5 23
Number of atoms = - x 6.023 x 10
6.92 m 108 .
29
Number of atoms in I cm == [~~ x 6.023 X 1023JII3
m == 200g/mol 108
mass is same as that of atomic mass hence mercury vapour
18 monoatomic mercury.) Number of atoms in 1 cm2=[to.5 x 6,023 x 1023 J2I3
lole of an element contains 4.2 x 'if"
electrons. What is
108
Number of atoms in IO-2m 2 or 10-8 cm 2
.mic number of the element?
romolecule of iron has molar mass 2800 amu, it contains = to.5 x 6.023 x 1023 J213 x 10-8 == 1.5 X 107 )
III by mass. The number of iron atom in one formula unit 108
macromolecule is: 14. A student performs a titration with different burettes and finds
: Number of iron atoms in one formula unit of compound titre values of25,2 mL, 25.25 mL and 25.0 mL. The number of
= % x Molecular mass .= ~ X 2800 = 4 ] significant figures in average titre value is: (lIT 2010)
100 Atomic mass 100 56 . A . I 25.2+ 25.25+ 25.0
[Hmt : verage titre va ue
~s of 'A' and 10 moles of 'D' are mixed and allowed to . 3
lccording to the equation : 75.45 == 75.4 == 25.1
A+3D ~2C 3 3
l1any mol~s of C are present when there are 4 moles of A (In addition, result is repOlted upto least place of decimal) )
container? ,
l1any water mol~cules will be there in 3 x 10-23 g sample
er? .

r4f#eIZ4
t

2. (1) 3. (7) 4. (4) 5. (4) 6. (1) 7. (2) 8.(8)

~ ___..~~ln (ti) 11 ('\) 1") fLl, 1'1 f7, 1.~ f'n
 BASIC PRINCIPLES 63

"~. LINKED COMPREHENSION TYPE QUEsnONS.~-

1 Answer the following questions:
1. The isotopes of chlorine with mass number 35 and 37 exist in
y, 'mole' is an essential tool for the chemical the ratio of. .... Its average atomic mass is 35.5.
r is a basic Sf unit adopted by the 14th general (a)I:1 (b)2:1 (c)3:1 (d)3:2
Neights and measurements in 1971. A mole contains 2. Which of the following isotopes is/are used to decide the scale
ltary particles as the number of atoms present in 12g of atomic mass?
of a gas at STP occupies 22.4 litre volume. Molar (a) l~C (b) I!C (c) 1~0 (d) I~
'ds and liquids is not definite. Molar mass of a 3. Atomic mass of boron is 10.81. It has two isotopes namely
'0 called gram-atomic mass or gram molar mass. The I~Band ~B with their relative abundance of 801fo and 20%
go of mole is plenty, heap or the collection of large
respectively. The value of x is: .
(a) 10.05 (b) lO (c) 10.01 (d) 10.02
le of a substance contains 6.023 x 1023 elementary
4. The ratio of the mass of 12 C atom to that of an atomQf element
om or molecule. Atomic mass unit (amu) is the unit of X (whose atomicity is four) is I: 9. The moleculal mass of
g., atomic mass ofsingle carbon is 12amu. element X is:
lowing questions: (a) 480 g mol- I (b) 432 g mol-I
; of one amu is approximately: (c) 36 g mol- 1 (d) 84 g mol- 1
(b) 0.5 g 5. 1zCand 14C isotopes are found as 98% and 2% respectively in
(d) 3.2 x 10-24 g any sample. Then, the number of 14C atoms in 12 g of the
)f a gas at STP are found to have a mass of 22 g. The sample will be:
,r mass of the gas is: (a) 1.5 mole atoms (b) 1.032 x 1022 atom~
(b) 44. (c) 88 (d) 33 (c) 2.06x ]02 atoms
1
(d) 2 g atoms
; of one molecule of water is approximately:
(b) 0.5 g • Passage 3
lO-z4 g (d) 3.2 x 10-23 g Empirical fonnula is the simplest fonnula ofthe compound which
ly atoms are present in 49 g of H ZS04 ? gives the atomic ratio of various elements present in one molecule of
023 X 1023 (b) 5 x 6.023 X 1023 the compounl. However, the molecular formula of the compound
gives the number of atoms of various elements present in one
)23 X 1023 (d) 7 x 3.02 X 1023 ' molecule of the compound.
sat STP contains 3 x 1022 molecules. The number of Molecular fonnula = (Ernpiricaljormula) x n
; in x L ozone at STP will be: Molecular mass
22 (b)4 X 1023 (c) 6.02 X 1023 (d) 3 x 1024 n=----~--
Emptrical fonnuZa mass
Iro's number is 1 x 1023 mor- I then the mass of one A compound may have same empirical and molecular formulae.
xygen would be: Both these fonnulae are calculated by using percentage composition
of constituent elements.
nu (b) 16 x 6.02amu
Answer the following questions:
1 (d) 16 x 10-23 amu' 1. Two metallic oxides contain 27.6% and 30% oxygen
respectively. If the formula of first oxide is M 3 0 4 , that of
the Avogadro's number then number of valence
second will be:
.n4.8g of02- is:
(a)MO (b)M02 (c)M20s (d)M2 0 3
(b) 4.2 NA (c) 1.6 NA (d) 3.2 NA
2. Which of the following compounds have same empirical
formula? .
(a) Formaldehyde (b) Glucose
'he atoms of same element; they have same atomic (c) Sucrose (d) Acetic acid
r'ent'mass numbers. Isotopes have different number 3. Which of the following represents the formula ofa substance
feir nucleus. If an element exists in two isotopes which contains 50% oxygen?
asses 'a' and 'b' in the ratio m: n, then average (a) N 2 0 (b) CO 2
mXa+nxb (c) NO z (d) CH3 0H
be .
m+n 4. An oxide of iodine (I = 127) contains 25.4 g of iodine and 8 g
Jpes of same element have same position in the of oxygen. Its formula could be:
'he elements which have single isotope are called (a) IZ03 (b) 120
nents. Greater is the percentage c.0mposition of an (c) 1205 (d) 1207
 G.R.s. PHYSICAL CHEMISTRY FOR COMPETITIONS

lrofluoric acid gas occupies 5.6 litres of volume at Molecular formula of metal chloride = MCt,
e empirical fonnula of the gas is HF, then its Molecular inass = [n x 9.02 + n x 35.5J:: 132
fonnula in the gaseous state will be: .. 11::3
(b) H2F2 (c) H3F3 (d) H4F4 :. Atomic mass of metal:: 3 x 9.02 = 27.06 J
, species having different percentage composition of 2. The vapour density of a mixture containing N02 and N2 0 4 is
38.3 at 27°C. The moles ofN0 2 in 100 moles of mixture are:
)OH and C 6H I2 0 6 (b) CH 3 COOH and CzHsOH (a) 33.48 (b) 53.52 (c) 38.3 (d) 76.6
CH 3 and HCOOH (d) CzHsOH and CH 30CH 3 3. At STP, 5.6 litre of a gas weighs 60 g. The vapour density of
°
.od ofNa, C and contains 0.0887 mo(Na, 0.132
2.65 x 1022 atoms of carbon. The empirical fonnula
gas is:
(a) 60 (b) 120 (c) 30 . (d) 240
lpound is: 4. Which of the following two substances have same vapour
(b) Na 3C 50 2 density? .
°
(d) Na O.0887 C 2.65 x 10 22 0.132 (a) Glucose (b) Fructose (c) Sucrose' (d) Starch
5. Let NH4HS(s) is heated in a closed vessel to decompose.
4
loids are extracted from the extracts of the plants
na. Marijuana owes its activity to tetrahydro The vapour density of the mixture will be:
rich contains 70% as many as carbon atoms as (a) equal to that ofNH4 HS
~ and 15 times as many hydrogen atoms as oxygen (b) lesser than thatofNH4 HS
m of tetrahydro cannabinol is 0.00318. (c) greater than that ofNH4 HS
lowing questions: ' (d) cannot be predicted
If mass of the compound is:
mu (b) 314 amu (c) 143 amu (d) 341 amu • Passage 6
:If fonnula of the compound is:
Precision refers to the closeness of a set of values obtained fol'
3002 (b) C21HI403 identical measurement of a quantity. Precision depends on the
460 (d) none of these limitations of measuring devices and the skills with which it is used.
of oxygen atoms in 1 mol of the' tetrahydro However, accuracy refers to the closeness ofa single measurement to
lol is: its true value.
(b)NA The digits ina properly recorded measurement are known as
3
~ = 6.023 X 102 significant figures. These are meaningful digits in a measured or
ge composition of carbon in the compound is: calculated quantity. The greater the number of significant figures in
;% (b) 70.85% (c) 80.25% (d) 59.64% a reported risult. smaller is the uncertainty and greater is the
precision. The zeros at the beginning are not counted. The zeros to
15 the right of a decimal point are counted. In the numbers that do not
contain a decimal point. "trailing" zeros may 01', may not be
~ity 'of a compound is defined as the ratio of mass of a . significant. The purpose ofzeros at the end of a number is to COfJvey
, of gas to the mass of the same volume ofhydrogen the correct range ofuncertainty. .,
tical conditions oftemperature and pressure. . Answer the following questbms:
Mass ofcertain volu~~o[lfas (22.4 L) at STP 1. If repeated measurements give values close to one another, the
Mass ofsame volume ofH 2 gas (22.4 L) at STP number is:
Mw (a) surely precise . (b) surely accurate
=-
2 (c) surely precise and accurate (d) all of these are correct
~lecular: mass of gas =Vapour density x 2 2. The number of significant figures in a measUred number
, is a unitless quantitj; it is unaffected by variation of contains how man;, uncertain {lUmber of digits?
!d pressure. . (a) Zero (b) 1
llowingquestions: . (c) 2 (d) Cannot be predicted
density· ofa metal chloride ;is 66. Its oxide contains 3. In the number,2.4560, there are .5 signifkruitdigits. Which one
tal. The atomic mass of the metal is: ' is the least significant !iigit?
(b) 54 ,; (c) 27.06 (d) 2.086 (a) 2 (b) 4 (c) 0 (d) 6
, Number of equivalents = ~umber of equivalents. 4. if we add 296.2 and 2.256, we get the answer as 298.456 g.
of metal of oxygen The number of significa~t figures in the result are:
53 47 006 ~5 W4 003
-:::::-
E 8 5. In which of the following numbers, all the zeros are not
significant?
E = 9.02
 BASIC PRINCIPLES 65

[/I~
Passage 1. 1. (c) 2. (c) 3. (d) 4. (d) 5. (a) 6. (c) 7. (a)
Passage 2. 1. (c) 2. (a, c) 3. (b) 4. (b) 5. (b)
Passage 3. 1. (d) 2. (a, b) 3. (d) 4. (c) 5. (b) 6. (b, c) 7. (a)
Passage 4. 1. (b) 2. (a) . 3. (a) 4. (c)
Pl)ssage 5. 1. (c) 2. (c) 3. (b) 4. (a, b) 5. (b)
Passage 6. 1. (a) .2. (b) 3. (c) 4. (c) 5. (d)

¢ SELF ASS·ESSMENT r~
ASSIGNMENT NO.1

8. Which one ofthe following is not a unit oflength?

SECTION;'I
(a) Angstrom (b) Light-year
Straight Objective Type Questions (c) Micron (d) Radian
This section contains 10 multiple choice questions. Each 9. Unit of J pa -] is equivalent to: .
question has 4 cijoices (a), (b), (c) and (d), out of which only .(a)m3 (b)cm 3
one is correct.
(c)dm3 (d) no~e of these
1. Cartisone is a molecular substance containing 21 atoms of
10. The relative abundance of two isotopes of atomic masses 85
carbon per molecule. The mass percentage of carbon in
and 87 are 75% and 25% respectively. The average atomic
cartisone is 69.98%. What is the molecular mass of cartisone? .
mass of element is:
(a) 36004 (b) 176.5 (c) 287.6 (d) 312.8
(a) 86 (b) 40 (c) 85.5 (d) 75.5
2. Total number of atoms present in 25 mg of camphor, CIO H16 0
is: SECTION-II
(a) 2.57 x 1021 (b) 9.89x 1019
Multiple Answers Type Objective Questions
(c) 2.67 X 1021 (d) 6.02x lifO 11. Mass of one atom of oxygen is/are:
. ;;. 3. The oxide of a metal contains 60% of the metal. What will be (a) 16 amu (b) 32 amu
the percentage of bromine in the bromide of the metal, if the (c) 16 gm (d) 2.656 x 1O-23gm
valency of the metal is the same in both, the oxide and the
bromide? 12. Which of the following compounds have same percentage·
(a) 93% (b) 87% (c) 70% (d) 77% composition of carbon?
4. The radius of water molecule having density 19 mL- 1 is: (a) C6 H120 6 (b) CH3 COOH
(a) 1.925 A (b) 73046 A (c) 19.25 A (d) 7.346 A (c) HCOOCH3 (d) C12 H22 0 11
5. 3 g of an oxide of a metal is converted completely to 5 g 13. Which of the following is/are correct about I mole electrons?
chloride. Equivalent mass of metal is: (a)-6.023 x Hr
3
electrons (b) 5048 x 10- 7 kg
(a) 33.25 (b) 3.325 (c) 12 (d) 20 (c) 96500 coulomb charge (d) None of these
6. Quantitative analysis of a compound shows that it contains 14. In which of the following numbers, all zeros are sib'11ificant?
0.110 mole of 'C', 0.0:)5 mole of 'N' and 0.165 mole of '0'. (a) 5.0005 (b) 0.0030 (c) 3.0.000. (d) 0.5200
Its molecular mass is about 270. How many atoms of carbon 15. Which of the following are correct SI units?
are there in empirical and molecular formulae of the (a) Amount ofsubstance in mol L- 1
compound respectively?
(b) Pressure of gas in pascal
Empirical formula Molecular formula
(a) 1 3 (c) Density of a solid in kgm- 3

(b) \2 2 (d) Force in newton

(c) 2 .6
(d) 3 2
SECTION-III
7. Total number of electrons present in 11.2 L of NH} at STP is: Assertion-Reason Type Questions
(a) 6.02 x 1023 (b) 3.01 X 1023 This section ;cohtains 4 questions. Each question contains
Statement~1 (Assertion) and Statement-2 (Reason). Each
(c) 3.01 x 1024 (d) 5.1 x 1024 question has following 4 choices (a), (b), (c) and (d), out of
which only one is correct. .
66 G.R.B. , PHYSICAl CHEMISTRY FOR COMPETITIONS

(a) Statement-! is true; statement-2 is true; statement-2 is a 20. 'Match the Column-I with Colunm-I1: '
corre,t explanation for statement-I. Column-I' Column-II
(b) Statement-I is true; statement-2 is true; statement-2 is not (a) N2 (P) 40% carbon by mass
, a correct explanation for statement-I. (bY CO (q) Empirical formula CH20
(c) Statement-lis true; statement-2 is false. (c) C6H1Z Oq (r) Vapour density = 14
(d) Statement-l is false; staternent-2 is true. (d) CH3 COOH (s) 14NA (NA 6.023 X 1023 )
16. State"ment-I: Avogadro's number is a dimensionless quantity. electrons in a mole
Bet:ause 21. Match the Column-I with Colunm-II:
Statement-2: It is a number of atoms or molet:ules in one Column-I Column-II,
gram mole. (a)IL (P)10- 5 N
17. Statement-I: An element has variable equivalent mass.,
Because (b) I J ' (q)0.2389 cal
Statement-2: The valency of element is varia~le. (c) 9.9 x 106 ,erg (r) 10- 3 m3
18. Statement-I: Vapourdensity ofCH4 is halfo(:0i. ' (d) J Dyne ;. (s) 6.25 X l(j8 eV
" 0" " - \

Because ' 22. Match the Colunm-I with Column-II:

Statement-2: 1.6 g of CH4 contains same number of electrons Column-I 'Column-It
as 3.2 g of02 • " (a) I g mole ofOz(g) (P) mass, 32 g
19. Statement-I: Specific gravity is dimensionless quantity. (b) 0.5 mole ofSOz(g) (q) mass, 24 g
Because' ' (c) 1 gofHz(g) (r)volume, 11.2 LatSTP
Statement-2: Specific gravity is relative, density of a (d) 0.5 mole of 0 3 (g) (s) 1.5 x 6.023 x 1023 atoms
~ubstance, measured with respect to density of water at 4 DC.

SECTION-IV' "
Matrix-Matching Type Questions
This section contains 3 questions. Each question contains
statement given in two columns which have to be matched.
, Statements (a, b, c and d) in Column~I have to bematchedwith
statements (p, q; r and s) in Colunm-II. The answers to these
questions have to be appropriately bubbled as i1iustrated in the
following example&:, . '
If the correct matches are (a-p,s)(b-q,r); (c-p,q) and (d-s);
then the correctly bubbled 4 x 4 matrix should be as follows:

p q r s
a
G @ (0 e
b
®e0 0
c
G e (0 0
d
® @ (0
"
. I. (a) 2. (c) "
:J..(b) 4. (a) 5. (a) 6. (c) 7. (c) 8. (d)
.' 9. (a) 10. (c) n. (a, d) 12. (a"b, c) 13. (a, b, c) 14; (a, c) 15. (b, c, d) 16. (a)
17. (b) 18. (c) 19. (a) 20., (a-r, s) (b-r, s) (c-p, q) (d-p. q) 21. (a-r) (b-q, s) (c-q) (d-~)
22. (a-p) (b~p, r,s) (c-r){d-q, s)