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Chemistry Times August 18

1
Chemistry Times August 18
Introduction
Life without metals in our daily life is simply
inconceivable, be it steel in railway tracks,
aluminium in aircrafts, uranium for electricity or rare
earth metals in magnets and hard discs.
Producing metals and non - metals such as silicon,
from its ores is the domain of extractive metallurgy
has been mistakenly identified, by students, with
inorganic chemistry. In reality, it is hard core
engineering. Extractive metallurgy practitioners
design complex reactors such as blast furnace (for
iron), Hall-Heroult cells (for aluminium), and
Siemens process (for silicon) using principles of
physics, thermodynamics, reaction kinetics, and
transport phenomena. Designing metallurgical
reactors also requires skills in high temperature
experimentation and computer simulation using
techniques such as finite element (volume)
methods. Many extractive metallurgy unit
operations are used for the remediation of air, water
and solid wastes.
Some Important Terms Involved in Metallurgy
 Minerals: The rocks in which metals occur in the
native state or combined state are called minerals.
Every mineral has a definite composition.
 Ores: The minerals from which the metals can be
conveniently and economically extracted are
known as Ores.
All the ores are minerals but all minerals cannot be
ores
Ores occur in nature in two forms:
1. Native Ores: These ores contain metals in a free
state. For example: silver, gold, platinum, mercury,
2
By: P. BRAHMA REDDY
(Alumni of IIT Delhi)
copper etc. Sometime lumps of pure metals are
found known as nuggets.
2. Combined Ores:
These ores contain metals in oxides, sulphides,
carbonates, etc. For example, Al (Bauxite,
Al2 O3 2 H 2 O ), Fe (haematite, Fe2 O3 ) etc.
 Gangue or Matrix: Metallic ores are often found
to contain non-metallic and rocky materials such
as sand, clay, quartz, feldspar, silicates, mica etc.
These unwanted impurities are called gangue or
matrix. Gangue is a waste material present in the
ore.
 Flux and Slag: Ores contain some impurities which
have high melting point. Flux is used to remove
these infusible impurities in the form of a fusible
slag.
Slag has low melting point, it is lighter than the
metal and is insoluble in molten metal. It floats over
the molten metal and is removed from the upper
exit (tap hole) in the furnace. To remove the infusible
impurity ore is mixed with a flux and is then heated
at high temperature. Flux are of two types.
(1) Acidic flux
(2) Basic flux
Acidic Flux: These are used to remove the basic
impurity present in the roasted ore.
For example, in the metallurgy of copper to remove
the basic impurity of FeO present an acidic flux
( SiO2 ) is used.
FeO  SiO2 
 FeSiO3
Impurity flux slag
( ferrous silicate )

Basic flux: These are used to remove the acidic
impurity present in the roasted ore.
For example, in the metallurgy of iron, to remove
the acidic impurity of SiO2 present a basic flux
lime stone (CaCO3 ) is used.
CaCO3  SiO2 
 CaSiO3  CO2
flux impurity slag ( calcium silicate )
 Metallurgical Process
The whole process of obtaining a pure metal from
one of its ores is called metallurgy. In order to extract
the metals from ores, several physical and
chemicals are used. The method used in a particular
case depends upon the nature of the ore, the
properties of the metal and the local conditions.
Thus, it is not possible to have a universal method
for the extraction of all the metals from their ores.
There are three metallurgical process as follows:
1. Hydrometallurgy
Hydrometallurgy is concerned with processes that
use aqueous solutions to extract metals from ores.
The most common hydrometallurgical process is
leaching, which involves dissolution of the
valuable metals into the aqueous solution. After
the solution is separated from the ore solids, the
solution is subjected to various procesess of
purification and concentration before the valuable
metal is recovered either in its metallic state or as a
chemical compound. The final recovery step may
involve precipitation, adsorption and solvent
extraction or an electrochemical process.
Some times, hydrometallurgical processes may be
carried out directly on the ore material without any
pretreatment steps. More often, the ore must be
pretreated by various mineral processing steps and
sometimes by pyrometallurgical processes.
2. Electrometallurgy
Electrometallurgy involves metallurgical processes
that take place in some form of electrolytic cell.
The most common types of electrometallurgical
processes are electrowinning and electro-refining.
Electrowinning is an electrolysis process used to
recover metals in aqueous solution, usually as the
result of an ore having undergone one or more
hydrometallurgical processes. Electrorefining is
used to dissolve an impure metallic anode (typically
from a smelting process) and produce a high purity
cathode. Fused salt electrolysis is another
electrometallurgical process whereby the valuable
Chemistry Times August 18
metal is dissolved into a molten salt, which acts as
the electrolyte, and the valuable metal collects on
the cathode of the cell
3. Pyrometallurgy
Pyrometallutgy involves high temperature
processes where chemical reactions take place
among gases, solids and molten materials. Solids
containing valuable metals are either reacted to form
intermediate compounds for futher processing, or
they are converted into their elemental or metallic
state. Pyrometallurgical processes that involve
gases and solids are typified by roasting
operations. Processes that produce molten
products are collectively referred to as smelting
operations. The energy required to sustain the high
temperature pyrometallurgical processes may come
entirely from the exothermic nature of the chemical
reactions taking place, usually oxidation reactions.
Often, however, energy must be added to the
process by combustion of fuel or in the case of
some smelting processes, by the direct application
of electrical energy.
It is possible to isolate many of the representative
metals by chemical reduction using other elements
as reducing agents. In general, chemical reduction
is much less expensive than electrolysis, and for
this reason, chemical reduction is the method of
choice for the isolation of these elements. For
example, it is possible to produce potassium,
rubidium and cesium by chemical reduction, as it is
possible to reduce the molten chlorides of these
metals with sodium metal. This may be suprising
given that these metals are more reactive than
sodium; however, the metals formed are more
volatile than sodium and can be distilled for
collection. The removal of the metal vapour leads
to a shift in the equilibrium to produce more metal
(via the Le Chatelier’s principle). The production
of Mg, Zn and Sn provide additional examples of
chemical reaction.
Thermodynamics of Pyrometallurgy
The oldest, and still the most common smelting
process for oxide ores involves heating them in
the presence of carbon. Originally, charcoal was
used, but industrial scale smelting uses coke, a
crude form of carbon prepared by pyrolysis
(heating) of coal. The basic reactions are:
MO  C  M  CO ...(i)
1  1
MO  C  O2  M  CO2 ...(ii)
2 2
3
Chemistry Times August 18

 M  CO2 Removal of oxygen from the ore is always

MO  CO  ...(iii)
accompanied by a large increase in the system
Each of these can be regarded as a pair of coupled volume so S for this step is always positive and
reactions in which the metal M and the carbon are
the reaction becomes more spontaneous at higher
effectively competing for oxygen atom. Using
temperatures. The temperature dependence of the
reaction(i) as a example, it can be broken down into
reactions that take up oxygen vary, however (Table
the following two parts:
1).
 M  1 O2
MO  G   0 ...(iv)
Table 1: The temperature dependence of the
2 reactions

1 
C  O2  CO G   0 ...(v)
2
At ordinary environmetal temperatures, reaction
(iv) is always spontaneous in the reverse direction
(that is why ores form in the first place!), so G 
of reaction (iv) will positive. G  for reaction (v)
is always negative, but at low temperatures it will
not be sufficiently negative to drive reaction (iv)
 The smelting process depends on the different A plot of the temperature dependences of the free
ways in which the free energies of reactions vary energies of these reactions, superimposed on similar
with temperature. This temperature dependence is plots for the oxygen removal reactions is called an
almost dominated by the T S  term in the Gibbs ELLINGHAM DIAGRAM. For a given oxide MO
function and thus by the entropy change. to be smeltable, the temperature must be high
enough that reaction falls below that of atleast one
G   H   T S 
of the oxygen consuming reactions. The slopes of
 The latter depends mainly on n( g ) , the change the lines on this diagram are determined by the
in the number of moles of gas in the reaction. sign of the entropy change.

4
 Chemistry Times August 18

 Examination of the Ellingham diagram Pyrometallurgy in the Extraction of the Iron

shown above illustrates why the
metals known to the ancients were
mainly those such as Cu and Pb,
which can be obtained by smelting
at the relatively low temperatures that
were obtainable by the methods
available at the time in which a
charcoal fire supplied both the heat
and the carbon. Thus the bronze age
preceded the iron age; the latter had
to await the development of
technology capable of producing
higher temperatures, such as the
blast furnace. Smelting of aluminium
oxide by carbon requires
temperatures too high to be practical;
commercial production of aluminium
is accomplished by electrolysis of the
moltem ore. In pyrometallurgy, an ore
is heated with a reductant to obtain
the metal. Theoretically, it should be
possible to obtain virtually any metal
from its ore by using coke as the
reductant. For example, the reduction
of calcium metal from CaO (s).


CaO( s )  C ( s )   Ca (l )  CO( g )

Unfortunately, many transition metals

(e.g., Titanium) react with carbon to
form stable binary carbides:
Ti  C  TiC

Consequently, more expensive

reductants (such as hydrogen,
aluminium, magnesium or calcium)
must be used to obtain these metals.
Many metals that occur naturally as
sulfides can be obtained by heating
the sulphide in air, as shown for lead
in the following equation.  The actual reductant is CO, which reduces Fe2 O3 to give Fe and

PbS (s)  O2 (g )   Pb(l )  SO2 (g ) CO2 ( g ) ; the CO2 is then reduced back to CO by reaction with
The reaction is driven to completion excess of carbon.
by the formation of SO2 , a stable
gas.

5
Chemistry Times August 18

 As the ore, lime and coke drop into the furnace, C ( s )  MgO  CO ( g )  Mg ( g )
any silicate minerals in the ore react with the lime
to produce a low melting mixture of calcium silicates CO( g )  Mg ( g )  C ( s )  MgO( s )
called SLAG, which floats on top of the molten iron.  Hence, reducing with carbon would produce no
 Molten iron is then allowed to run out the bottom yield when the vapours moved into the cooler
of the furnace, leaving the slag behind. condensing inside the reactor, even though
Originally, the iron was collected in pools called temporarily there would be intermediate carbon
pigs, which is the origin of the name PIG IRON. monoxide and actual magnesium vapours.
 Iron that is obtained directly from a blast furnace
has an undiserably low melting point (about Pyrometallurgy in the Extraction of Zinc
1100C instead of 1539C ) because it contains a  Zinc smelting is the process of converting zinc ores
into pure zinc.
large amount of dissolved carbon that must be
 Zinc smleting has historically been more difficult
removed because they make iron brittle and
than the smelting of other metals, e.g., iron, because
unsuitable for most structural applications.
in contrast, zinc has a low boiling point.
 In the Bessemer process, oxygen is blown through
 There are two methods of smelting zinc: the
the molten pig iron to remove the impurities by
pyrometallurgical process and the electrolytic
selective oxidation because these impurities are
process; both methods are still used.
more readily oxidized than iron.
 Both of these processes share the same first step:
In the final stage of this process, small amounts of
Roasting.
other metals are added at specific temperatures to
 Zinc ores usually contain zinc sulfide, zinc oxide,
produce steel with the desired combination of
or zinc carbonate. After separation of these
properties.
compounds from the ores, heating in air converts
the ore to zinc oxide by one of the following
Pyrometallurgy in the Extraction of Magnesium
reactions:
 The pidgeon process is one of the methods of

magnesium metal production via a high temperature 2 ZnS ( s )  3O2 ( g )   2 ZnO ( s )  2 SO2 ( g )
(800 - 1400C ) process with silicon as the reducing 
ZnCO3 ( s )   ZnO ( s )  CO2 ( g )
agent (instead of carbon for iron extraction).  Carbon, in the form of coal, reduces the zinc oxide
 The pidgeon process involves the reaction of to form zinc vapour:
magnesium oxide with elemental silicon at high
ZnO( s)  C ( s)  Zn( g )  CO( g )
temperatures to form pure magnesium.

The zinc can be distilled (B.P. 907C ) and
Si ( s )  2 MgO( s )   SiO2 ( s )  2 Mg ( g )
condensed. This zinc contains impurities of ‘Cd’
Although this reaction is unfavorable in terms of
(767C ), ‘Fe’ (2862C ), ‘Pb’ (1750C ) and ‘As’
thermodynamics, the removal of the magnesium
vapour produced takes advantage of Le Chatelier’s (613C ). Careful redistillation produces pure zinc.
principle to continue the forward progress of the “As” and “Cd” are distilled from the zinc because
reaction. Over 75% of the world’s production of they have lower boiling points. At higher
magnesium, primarily in China, comes from this temperatures, the zinc is distilled from the other
process. impurities, mainly lead and iron.
 The usual metallurgical use of carbon as the
reducing agent instead of silicon cannot be used,
because the silicon dioxide is a solid, while the
carbon mono-oxide and dioxide are both gaseous,
and would follow the magnesium into the
condensing zone, reverting the reaction as follows.

6
Chemistry Times August 18

7
Chemistry Times August 18

Pyrometallurgy in the Extraction of Copper

Pyrometallurgy in the Extraction of Tin

 Tin does not occur free in nature. The most important ore is cassiterite, SnO2 , which is also known as tin
stone. The ore is usually associated with siliceous matter, tungstates of iron and maganese ( FeWO4 , MnWO4 ).
It also exists along with the pyrites of copper, iron and zinc. Tin is extracted form cassiterite ore.
 The extraction involves the following steps.
Concentration
The ore is crushed and powered. It is washed with running water which removes lighter siliceous matter. Iron
tungstate is removed by electromagnetic separator. The ore is then roasted in a current of air to remove
sulphur and arsenic as SO2 and As2 O3 , respectively..
Smelting
The roasted ore is mixed with about one fifth of its mass of powered anthracite (carbon) and a little limestone
(flux). The mixture is subjected to heat in a reverberatory furnace when tin oxide is reduced to tin metal. The
liquid metal is drawn off from the furnace.
SnO2  2C  Sn  2CO
The crude tin metal contains a number of impurities. It is further purified by liquation and poling. The crude
metal is heated gently on the sloping hearth of the reverberatory furnace. The tin metal flows down leaving
behind iron, tungsten, etc. In the poling process, the molten is stirred with a green wood pole where by

8
 Chemistry Times August 18

impurities like S, As, are oxidised, and any tin oxide

formed is reduced by the hydrocarbons of wood
Pyrometallurgy in the Extraction of Lead
 Lead is mainly extracted from galena.
 After the concentration of the ore by froth flotation
process, the ore is roasted in a reverberatory
furnace for about six hours at a moderate
temperature in a current of air. Part of galena is
converted into lead oxide and lead sulphate.
 After this, the supply of air is stopped and small (a) Below 400C , formation of X 2 O is a
quantities of carbon, quicklime and cheap iron ore spontaneous process
are added along with increase of temperature. At (b) Above 400C , decomposition of X 2 O is a
this stage, unreacted sulphide reacts with the lead
spontaneous process
oxide and sulphate giving metallic lead :
(c) A reacting mixture of X and O2 would reach
PbS  2 PbO  3Pb  2 SO2
equilibrium at 400C
PbS  PbSO4  2 Pb  2SO2
(d) At all temperatures, X 2 O is thermodynamically
 The obtained lead contains impurities such as Cu,
Ag, Bi, Sb and Sn. Silver is removed by Parke’s stable
process where molten zinc is added to molten impure 3. During extraction of iron from haematite ore by
lead. The former is immiscible with the latter. Silver pyrometallurgy, the charge consists of
is more soluble in molten zinc than in molten lead. (i) powdered ore ( Fe2 O3 )
Zinc-silver alloy solidifies earlier then molten lead
(ii) lime stone (CaCO3 ) and
and thus can be separated.
 After this, crude lead is refined electrolytically (iii) coke (C).
Which of the following reactions does NOT take
(Electrolyte; lead silicofluoride, PbSiF6 and
place inside the blast furnace?
hydrofluosilicic acid, H 2 SiF6 with a little gelatin, (a) 3Fe2 O3  CO  2 Fe3O4  CO2
anode; crude lead and cathode; pure lead).
(b) CaCO3  CaO  CO2
(c) Fe3O4  CO  3FeO  CO2
(d) FeO  Ca  Fe  CaO
4. Following figure shows the Ellingham diagram for
1. In the extraction of iron metal from haematite ore, the reaction:
CaCO3 (lime stone) is one of the constituents of (i) 2CO  O2  2CO2

the charge. The role of CaCO3 in the extraction (ii) 2 Fe  O2  2 FeO

process is to The point of intersection of two lines corresponds
to 750C on the temperature axis.
(a) reduce oxides of iron by providing CO2 gas
Pick a right condition for reduction of one of the
(b) oxidize the metallic impurities to respective
oxides two oxides, viz, CO2 and FeO.
(c) lower the temperature at which haematite gets
reduced to iron
(d) provide CaO to gangue which is separated as
slag
2. For a hypothetical reaction, 4X (s)  O2  2X2O(s),
the Ellingham diagram is shown below.
Referring to the diagram, pick the wrong statement.

9
Chemistry Times August 18
(a) Temperature must be above 750C for
reduction of FeO to Fe by CO2
(b) Temperature must be above 750C for the
reduction of FeO to Fe by CO
(c) Temperature must be below 750C for the
reduction of CO2 to CO by Fe
(d) Temperature must be below 750C for the
reduction of FeO to Fe by CO
5. The common method of extraction of metal from
oxide ores is
(a) reduction with carbon
(b) reduction with hydrogen
(c) reduction with aluminium
(d) electrolytic method
6. Oxidation states of the metal in the minerals
haematite and magnetite, respectively are
(a) II, III in haematite and III in magnetite
(b) II, III in haematite and II in magnetite
(c) II in haematite and II, III in magneitite
(d) III in haematite and II, III in magnetite
7. The chemical process in the production of steel from
haematite ore onvolves
(a) reduction
(b) oxidation
(c) reduction followed by oxidation
(d) oxidation followed by reduction
8. The methods chiefly used for the extraction of lead
and tin from their ores, respectively are
(a) self reduction and carbon reduction
(b) self reduction and electrolytic reduction
(c) carbon reduction and self reduction
(d) cyanide process and carbon reduction
9. In order to refine “Blister copper” it is melted in a
furnace and is stirred with green logs of wood. The
purpose is
(a) to expel the dissolved gases in blister copper
13.
10
(b) to bring the impurities to surface and oxidize
them
(c) to increase the carbon content of copper
(d) to reduce the metallic oxide impurities with
hydrocarbon gases liberated from the wood
10. Removal of Fe, Cu and W from Sn metal after
smelting is by ............ because .............
(a) Poling; of more affinity towards oxygen for
impurities
(b) Selective oxidation; of more affinity towards
oxygen for impurities
(c) electrolytic refining; impurities undissolved in
electrolyte
(d) liquation; Sn having low melting point compared
to impurities
11. In the manufacture of Mg by Carbon reduction of
MgO, why is the product cooled in the stream of
an inert gas?
(a) to enhance Mg formation
(b) Mg reacts with CO to form Mg (CO3 )2
(c) to prevent reversible reaction
(d) None of these
12. Statement-I: Carbon monoxide is capable of
reducing FeO to Fe at certain temperature.
Statement-II: At the given temperature, standard
free energy of reaction, 2 Fe  O2  2 FeO is more
negative compared to the standard free energy of
the reaction, 2CO  O2  2CO2
(a) Statement-I and Statement-II are true and
Statement-II is the correct explanation of
Statement-I.
(b) Statement-I and Statement-II are true, but
Statement-II is not the correct explanation of
Statement -I
(c) Statement-I is true, but Statement -II is false
(d) Statement-I is false, but Statement -II is true
 Chemistry Times August 18

(a) (i) - (Q), (ii) - (P), (iii) - (R), (iv) - (S) 7.Sol: First, by calcination and roasting, the ferrous
(b) (i) - (S), (ii) - (R), (iii) - (P), (iv) - (Q) oxide is oxidised to ferric oxide. Then, in blast
(c) (i) - (Q), (ii) - (R), (iii) - (P), (iv) - (S) furnace smelting is done, where it is reduced to get
(d) (i) - (S), (ii) - (P), (iii) - (R), (iv) - (Q) iron.
8.Sol: The methods cheifly used for the extraction of
lead and tin from their ores are self reduction and
carbon reduction, respectively.
Tin is extracted from oxide ore cassiterite by
1. d 2. d 3. d 4. d 5. a reduction with carbon in a reverberatory furnace.
6. d 7. d 8. a 9. d 10. d Lead is mainly extracted from sulphide ore called
11. c 12. c 13. a galena. Self reduction finally takes place.
9.Sol:
2Cu2 S  3O2  2Cu2O  2SO2
3Cu2 O  CH 4 (from green logs of wood)

1.Sol: Acidic impurities can be removed by using CaO,  6Cu  2 H 2 O  CO

flux which forms Slag
2.Sol: Note that X 2 O is thermodynamically stable
only below 400C . A substance is
thermodynamically stable if G of formation of
that compound is negative.
3.Sol: Refer Flow chart of pyrometallurgy in the
extraction of iron.
4.Sol: Based on Ellingham diagram principles and
spontaneity based on Gibbs Helmholtz equation.
6.Sol: Haematite, Fe2 O3 ; oxidation state of Fe = +3
Magnetite, Fe3O4 ( FeO  Fe2O3 ); oxidation state
of Fe = +2, +3
10.Sol: Liquation is the principle based on difference
in melting points
11.Sol: The reduction of MgO is a reversible process.
In order to prevent the reaction between Mg and
CO, the temperature of the products is reduced in a
steam of an inert gas. Inert gas does not permit the
reaction of Mg with air.
MgO + C  Mg + CO
12.Sol: At the given temperature, free energy of
reaction, 2 Fe  O2  2 FeO, is less negative.

11
Chemistry Times August 18

PHOTOELECTRIC EFFECT

5. The binding energy of electrons in a metal is 250 kJ/

mol. The threshold energy of metal is
Section A: Only one option correct (a) 6 1014 Hz (b) 1014 Hz
1. Einstein’s photoelectric equation states that (c) 4 1014 Hz (d) 25  1014 Hz
Ek  h  W . In this equation, Ek refers to 6. A photon of wave length 4 107 m strikes on
(a) kinetic energy of all ejected electrons metal surface, the work function of the metal being
(b) Mean kinetic energy of emitted electrons 2.13 eV. The velocity of the photoelectron is
(c) Minimum kinetic energy of emitted electrons
(a) 1.56 109 m / s (b) 5.85 105 m / s
(d) Maximum kinetic energy of emitted electrons
2. The ratio of slopes of K max vs  and V vs  (c) 4.97  105 m / s (d) 5.85 105 cm / s
curves in the photoelectric effect gives 7. The wave length of the photoelectric threshold of a
metal is 230 nm. The K.E. of photoelectron ejected
(  = frequency, K max = maximum kinetic energy,, from the surface by UV radiation emitted from the
V = stopping potential): second longest wavelength transition (downward)
(a) Charge of electron of electron in Lyman series of the atomic spectrum
(b) Planck’s constant of hydrogen is
(c) Work function (a) 0.074 1016 J (b) 1.074 1018 J
(d) The ratio of Planck’s constant of electronic (c) 6.213 1018 J (d) 7.123 1010 J
charge
8. Work function of an alkali metal is 1.55 eV. When the
3. In photoelectric effect, electrons should be removed
surface of this metal is irradiated with light,
from the
photoelectric emission took place and the
(a) inner shells (b) surface
photoelectrons were found to be moving at a speed
(c) from core (d) the nucleus
4. Light of wavelength 5000A falls on a metal surface of 5.93  105 m / s. If the source of light was an
of work function 1.9 eV. The K.E. of photoelectrons electronic transition in H - atom, determine the type
is of transition i.e., orbit number of between which
the transition was occuring.
(a) 9.3 eV (b) 9.3 1019 J
(a) 4  2 (b) 3  2 (c) 4  3 (d) 5  4
(c) 9.3 1020 J (d) 1020 J 9. When a metal was irradiated with a light of frequency
1.6 1016 Hz, the photoelectrons emitted had twice

12

the K.E. as did photoelectrons emitted when the
same metal was irradiated with light of frequency
1016 Hz. The threshold frequency ( ) of metal is
(a) 1015 Hz (b) 2 1015 Hz
(c) 3 1015 Hz (d) 4 1015 Hz
10. The critical frequency for emitting photoelectrons
from a metal surface is 5  1014 sec 1 . The kinetic
energy of photoelectron emitted by exposing the
surface with radiations of frequency 1015 sec1 is
(a) 5 1014 kJ (b) 6.626 1034 J
(c) 3.311019 J (d) 0 J
11. Photoelectric effect can take place only when
photons strike bound electrons or electrons
embedded in the metal surface, since it is impossible
for a photon to give up all its energy and
momentum to a free electron. This is in accordance
with
(a) Law of conservation of energy
(b) Law of conservation of mass
(c) Law of conservation of momentum
(d) Law of conservation of both energy and
momentum
12. Photons of energy 6 eV are incident on a potassium
surface of work function 2.11 eV. What is the
stopping potential?
(a) - 6 V (b) - 2.1 V (c) -3.9 V (d) -8.1 V
13. The work function of Platinum is twice that of the
work function of Calcium. If the minimum photon
energy required to emit photoelectrons from the
surface of Platinum is E, then that for the surface of
Calcium would be
(a) 2E (b) 3E/2 (c) E/2
(d) Cannot be determined
14. 2.4 mole of H 2 sample was taken. In one experiment
60% of the sample was exposed to continuous
radiations of frequency 4.47  1015 Hz of which all
the electrons are removed from the atom. In another
experiment, remaining sample was irradiated with
light of wavelength 600 A , when all the electrons
are removed from the surface. The ratio of maximum
velocity of the ejected electrons in the two cases is
(a) 1.72 (b) 1.22 (c) 2 (d) 2.22
Chemistry Times August 18
Section B: One or more than one correct option
questions
15. Choose the correct statement(s) regarding the
photo-electric effect.
(a) No electrons are ejected, regardless of the
intensity of the radiation, unless the frequency
exceeds a threshold value characteristic of the
metal
(b) The kinetic energy of the ejected electrons
varies linearly with the frequency of the incident
radiation and its intensity
(c) Even at low intensities, electrons are ejected
immediately if the frequency is above the
threshold value
(d) An intense and a weak beam of monochromatic
radiations differ in having number of photons
and not in the energy of photons
16. The light source emits light of wavelength of 450
nm. The table lists the only available metals and
their work functions:
Metal: Ba Li Ta W
Work function (eV): 2.5 2.3 4.2 4.5
Which metal(s) can be used to produce electrons
by the photoelectric effect from given source of
light?
(a) Ba (b) Li (c) Ta (d) W
17. Which of the following statements is true for
photoelectric effect?
(a) Photoelectric current is proportional to the
frequency of the radiation used, for all retarding
voltages.
(b) Photoelectric current is proportional to the
intensity of light used for all retarding voltages.
(c) Photoelectric current is proportional to the
wavelength of radiation used, for all retarding
voltages.
(d) Photoelectric current is proportional to energy
of the radiation used for all retarding voltages.
18. Which of the following statements is true about
photoelectric effect?
(a) There is no time lag t between the arrival of
light (photons) on the surface of a metal, and
the emission of photoelectrons (within limits
of experimental accuracy  109 sec).
(b) There is always a specific time lag t , between
the arrival of photons on the surface and
emission of photoelectrons.
(c) There is a specific time lag t only in some
exceptional cases, particularly in some specific
metals.
13
Chemistry Times August 18

(d) There is a specific time lag t only when the

6.625  1034  3  108
photon energy is very less.  10
 1.9 1.6  1019
5000 10
19. A metallic surface is first irradiated with Ultraviolet
light and then with Infrared light. What will be the  9.3 1020 J
change in the K.E. of the emitted photoelectrons
and what will be the change in the photoelectric 250  103
5.Sol: h  23
J  4.15  1019 J
current I P ? 6.023  10

(a) K.E. will remain same. I P will remain same. 4.15 1019 4.15 1019
    6 1014 Hz
h 6.625 1034
(b) K.E. will increase. I P will increase.
(c) K.E. will decrease. I P will decrease. hc
6.Sol: K .E.  h  h   h 

(d) K.E. will decrease. I P will remain same.
Section C: Assertion & Reason Type Questions  6.625  1034  3  108  19
   2.13  1.6  10
(a) Statement-I and Statement-II are true and  4  107 
Statement-II is the correct explanation of
Statement-I.  1.56  1019 J
(b) Statement-I and Statement-II are true, but
(1 / 2)mu 2  1.56  1019 J
Statement-II is not the correct explanation of
Statement -I 1
(c) Statement-I is true, but Statement -II is false  9.108  1031  u 2  1.56  1019
2
(d) Statement-I is false, but Statement -II is true
20. Statement- 1 : The kinetic energy of photo- u  5.85 105 m / s
electrons increases with increase in frequency of 7.Sol: According to Planck’s quantum theory,
incident light. K.E. of photoelectron  h  h
Statement - 2: Whenever intensity of light is
increased the number of photo-electron ejected hc 6.625  1034  3 108
h     8.63  1019
always increases.  230 10 9
For spectral line in Lyman series of H atom,
1  1 
 R 1  2 
  n 
1. d 2. a 3. b 4. c 5. a For the 2nd longest wavelength transition, n = 3,
6. b 7. b 8. a 9. d 10. c so
11. d 12. c 13. c 14. b 15. a, c, d
16. a, b 17. b 18. a 19. d 20. b 1 8 8
 R   1.09677  107 m 1
 9 9
   1.025 107 m  102.4nm
Energy of photon corresponding to this
wavelength is as given below
1.Sol: The energy of photon absorbed is used in doing
work against forces of attraction and imparting hc 6.625 1034  3  108
E   1.937 1018 J
kinetic energy to electrons  1.025  107
2.Sol: K .E.  h  h  eV  h  h K.E. of photoelectron  19.37 1019  8.63 1019
h  1.074 1018 J
Ratio of slopes  (h / e)  e
8.Sol: Energy, E  (1/ 2)mu 2
hc  0.5  9.1 1031 (5.93  105 ) 2 J = 1ev
4.Sol: K.E. = h - Work function =  Workfunction


14
 Chemistry Times August 18

Energy of incident radiation must have been 2.55eV Moles of atoms obtained by 60% sample
Since energy of a stationary orbit of H - atom is  1.44  2  2.88
13.6 Number of atoms obtained
expressed as En  eV and at n=2, E =3.4eV
n2 2  2.88  6.023 1023 1.73 1024
This suggests that the electronic transition leading Number of electrons ejected  1.73 1024 (one H -
to emission of radiation of energy 2.55 eV must be atom one electron)
occurring in the vicinity of second orbit. Let us Applying photo-electric effect,
consider an electronic transition from nth orbit to
K .E.  h  IE  h  IE
2nd orbit gives the desired radiation, then
 6.625  1034 (4.47  1015 )  13.6  1.6  1019
1 1 
2.55  13.6   2 
4 n   7.86 1019 J

13.6 1 2  7.86  1019

 3.4  2.55  0.85  n  4 KE  mu12  u1 
n2 2 9.11031
Hence, the desired electronic transition is n = 4 to  1.3  106 m / s
n = 2.
Applying photo-electric effect,
9.Sol: 1  1.6  1016 Hz 2  106 Hz
K .E.  h  IE  h  IE
According to given data,
6.625  1034  3  108
KE2  2 KE1  h1  h  2( h2  h )   13.6  1.6 1019
600  1010
  22  21  2  1016  1.6  1016
 1.137 1018 J
16 15
 0.4 10 Hz  4 10 Hz
1 2  1.137  1018
10.Sol: K.E.  h  h  h(   ) KE  mu22  u2 
2 9.1  1031
 6.625  1034 (1015  5  1014 )  3.31 1019 J
 1.58 106 m / s
11.Sol: This law states that if there is no net forces on
a system, it will have the same momentum at all u1 1.3  106 u 1
times. If there is no extenal energy imposed on   0.83  2   1.22
u2 1.56  106 u1 0.83
system it will remain consant. This is also related
to Newton’s first law which says that bodies remain 15.Sol: According to photoelectric effect concept
constant when no force is applied onto them. hc 12400
Thus, a photoelectric effect can only take place 16.Sol: Energy of light (E)    2.755 eV
 450
when a photons strike the electrons otherwise its
2.755 eV > work function of Ba and Li
not possible for a photon to give up all the energy
18.Sol: There is no time lag in the incidence of photon
and momentum to free its electron.
and emission of electron. It is assumed that in
12.Sol: K.E.  h  h  (6  2.1)eV  3.9eV photoelectric effect photon collides with electron
eV  3.9eV of metal and the time taken in collision is negligible.
This collision is inelastic
Thus, stopping potential = -3.9 V
19.Sol: The kinetic energy of the ejected electrons
13.Sol: WPt  2  WCa increases linearly with the frequency of the incident
E  2  (h)Ca radiation but is independent of the intensity of the
radiation. Photo electric current is only dependent
(h)Ca  E / 2 on intensity of the radiations.
14.Sol: Moles of H 2 exposed to radiation of The frequency of UV radiations is more than the IR
radiations, so K.E. decreases.
60 20.Sol: h  h  K .E.
4.47 1015 Hz  100  2.4  1.44

15
Chemistry Times August 18

STRUCTURE OF ATOM

1. Which one is the wrong statement? [2017] 4. Magnetic moment 2.84 B.M. is given by:
(At.numbers Ni  28, Ti  22, Cr  24, Co  27)
h
(a) The uncertainty principle is E  t  . [2015]
4
(b) Half filled and fully filled orbitals have greater (a) Cr 2  (b) Co2  (c) Ni 2  (d) Ti 3
stability due to greater exchange energy, greater 5. The angular momentum of electrons in ‘d’ orbital
symmetry and more balanced arrangement. is equal to [2015]
(c) The energy of 2s-orbital is less than the energy (a) 2 3h (b) h (c) 6 h (d) 2 h
of 2p-orbital in case of hydrogen like atoms. 6. Calculate the energy in joule corresponding to light
h of wavelength 45 nm:
(d) de-Broglie’s wavelength is given by   ,
mv (Planck’s constant h  6.63 1034 Js;
where m = mass of the particle, v = group speed of light c  3  108 ms 1 ) [2014]
velocity of the particle.
(a) 6.67 10 15 (b) 6.67 10 11
2. Two electrons occupying the same orbital are
distinguished by: [2016] (c) 4.42 1015 (d) 4.42 1018
(a) Spin quantum number
7. What is the maximum number of orbitals that can
(b) Principal quantum number
be identified with the following quantum numbers?
(c) Magnetic quantum number
(d) Azimuthal quantum number n  3,   1, m  0 [2014]
(a) 1 (b) 2 (c) 3 (d) 4
3. The number of d-electrons in Fe 2  ( Z  26) is not
equal to the number of electrons in which one of  Z2 
8. Based on equation E  2.178 1018 J  2 ,
the following [2015] n 
(a) d-electrons in Fe ( Z  26) certain conclusions are written. Which of them is
(b) p-electrons in Ne ( Z  10) not correct? [2013]
(a) The larger the values of n, the larger is the orbit
(c) s-electrons in Mg ( Z  12) radius
(d) p-electrons in Cl ( Z  17) (b) Equation can be used to calculate the change
in energy when the electron changes orbit

16
 Chemistry Times August 18

(c) For n  1 , the electron has a more negative 15. If n  6 , the correct sequence for filling of
energy than it does for n  6 which means that electrons will be [2011]
the electron is more loosely bound in the (a) ns  np  (n  1)d  (n  2) f
smallest allowed orbit
(d) The negative sign in equation simply means (b) ns  (n  2) f  (n  1)d  np
that the energy of electron bound to the nucleus (c) ns  (n  1)d  (n  2) f  np
is lower than it would be if the electrons were
at the infinite distance from the nucleus. (d) ns  (n  2) f  np  (n  1)d
9. What is the maximum number of electrons that 16. The total number of atomic orbitals in fourth
can be associated with a following set of quantum energy level of an atom is [2011]
(a) 4 (b) 8 (c)16 (d) 32
numbers? (n  3, l  1 and m  1 ) [2013]
17. A 0.66 kg ball is moving with a speed of 100 m/
(a) 2 (b) 4 (c) 6 (d) 10 s.The associated wavelength will be [2010]
10. The value of Planck’s constant is 6.63 1034 Js. (a) 6.6 1032 m (b) 6.6 1034 m
17 1
The speed of light is 3 10 nm s . Which value (c) 1.0 1035 m (d) 1.0 1032 m
is closest to the wavelength in nanometer of a
18. The energy absorbed by each molecule  A2  of a
quantum of light with frequency of 6 1015 s 1 ?
[2013] substance is 4.4 1019 J and bond energy per
(a) 25 (b) 50 (c) 75 (d) 10 molecule is 4.0 1019 J. The kinetic energy of the
11. The orbital angular momentum of a p-electron is
molecule per atom will be [2009]
given as [2012]
20
(a) 2.0 10 J (b) 2.2 1019 J
h h
(a) 6. (b) 3 (c) 2.0 1019 J (d) 4.0 1020 J
2 2
19. Which of the following is not permissible
3 h h arrangement of electrons in an atom ? [2009]
(c) (d)
2 2 (a) n  3, l  2, m  2, s   1/ 2
12. The correct set of four quantum numbers for the (b) n  4, l  0, m  0, s  1/ 2
valence electron of rubidium atom ( Z  37) is
(c) n  5, l  3, m  0, s   1/ 2
[2012]
(d) n  3, l  3, m  3, s  1/ 2
1 1
(a) 5, 0, 0,  (b) 5,1, 0,  20. Maximum number of electrons in a sub-shell of
2 2 an atom is determined by the following [2009]
1 1 (a) 2n 2 (b) 4l+2 (c) 2l+1 (d) 4l-2
(c) 5,1,1,  (d) 6, 0, 0, 
2 2 21. The measurement of the electron position is
13. Maximum number of electrons in a sub-shell with associated with an uncertainty in momentum,
l  3 and n  4 is [2012] 18
which is equal to 110 g cm s 1 . The
uncertainty in electron velocity is (mass of an
(a) 10 (b) 12 (c) 14 (d) 16
electron is 9 1028 g) [2008]
14. The energies E1 and E2 of two radiations are 25
6 1
eV and 50 eV respectively. The relation between (a) 1  10 cm s (b) 1  105 cm s 1
their wavelengths, i.e., 1 and 2 will be (c) 1  1011 cm s 1 (d) 1.1 109 cm s 1
[2011] 22. If uncertainty in position and momentum are equal,
(a)   2 (b) 1  22 then uncertainty in velocity is [2008]

1
(c) 1  2 (d) 1  42
2

17
Chemistry Times August 18

h 5.Sol: Angular momentum  (  1) h

1 h
(a) 2 (b) For d-orbital, l  2
m 
h 1 h Angular momentum  2(2  1) h  6 h
(c) (d)
 2m  34 8
6.Sol: hc  6.63  10  3 10
23. Consider the following sets of quantum numbers
 45  109
[2007]
n l m s  4.42 1018 J
(i) 3 0 0 +1/2 7.Sol: Given: n  3, l  1, m  0
(ii) 2 2 1 +1/2 Hence orbitals is 3p
(iii) 4 3 -2 +1/2
(iv) 1 0 -1 -1/2
(v) 3 2 3 +1/2
Hence the number of orbitals identified by m=0
Which of the following sets of quantum number
can be one only
is not possible?
(a) (ii), (iii) and (iv) (b) (i), (ii), (iii) and (iv) 8.Sol: For n  1 , the electron has a more negative
(c) (ii), (iv),and (v) (d) (i) and (iii) energy than it does for n  6 which means that
the electron is more loosely bound in the smallest
allowed orbit. This is not correct. Electron is more
tightly held in the first orbit.
9.Sol: (n  3, l  1 is 3p sub-shell and thus 2 electrons
1. c 2. a 3. d 4. c 5. c
6. d 7. a 8. c 9. a 10. b can exist in one of the 3p-orbital  m  1
11. d 12. a 13. c 14. b 15. b 10.Sol: Given,
16. c 17. c 18. a 19. d 20. b h  6.63  1034 Js,
21. d 22. d 23. c  ms 1 , v  6  105 s 1
17 9
c  3 10 10 c
 v

 5  108  109 nm  50nm

1.Sol: In case of hydrogen like atoms, energy depends h

11.Sol: Orbital angular momentum  l (  1) 
on the principal quantum number only. Hence, 2s- 2
orbital will have energy equal to 2p-orbital.
2.Sol: Same orbital can have two different values of
For p-electron  l  1
1 1
spin of e , i.e.,  and  h h h
2 2  l (  1)   2 
2 2 2
3.Sol: Number of d-electrons is Fe2   6
Number of p-electrons in Cl  11 12.Sol: The electronic configuration of 37 R b is:
2 2 6 2 6 10 2 6 1
1s , 2 s 2 p 3s 3 p 3d , 4 s 4 p , 5 s
4.Sol: Magnetic moment (m)  n(n  2)
2.84 B.M. corresponding to 2 unpaired electrons. 1 1
n  5, l  0, m  0, s   or 
Cr 2 4
 3d , 4 unpaired electrons 2 2
2 13.Sol: If n  4 and l  3 , it means it is 4f-orbital.
Co  3d 7 ,3 unpaired electrons
Therefore, the total number of electrons in 4 f-
Ni 2   3d 8 , 2 unpaired electrons orbitals is 14.
Ti 3  3d 1 ,1 unpaired electron

18
 Chemistry Times August 18

hc hc p  1 10 18 g cm sec1
14.Sol: E1   and E2  
1 2 m  u  11018
E1 2 25  2 1 1018
 E    u   1.1 109 cm sec1
2 1 50 1 9 10 28

22.Sol:
 1  22
h
15.Sol: np is filled after ns in each shell. x  p  x.p 
4
16.Sol: Number of atomic orbitals  n 2
h
Number of atomic orbitals in 4th energy shell or P  mv 
4
 42  16
h
h 6.6  1034 Now, x.v 
17.Sol:     1 1035 m 4 m
mv 0.66  100
18.Sol: KE of molecule = energy absorbed by h 4 1 h
molecule -BE per molecule  v    
4 m h 2m 
  4.4  1019    4.0  10 19  J  0.4  10 19 J 23.Sol: The value of 1 varies from 0 to (n  1) and the
value of m varies from -1 to +1 through zero.
0.4  10 19
KE per atom  J  2.0  1020 J The value of ‘s’ 1 / 2 which signifies the spin of
2
electron.
19.Sol: ‘m’ value cannot be more than ‘l’
The correct sets of quantum number are:
20.Sol: Total number of sub-shells  (2l  1) n l m s
Maximum number of electrons in the sub-shells (ii) 2 1 1 +1/2
 2(2l  1)  4l  2 (iv) 1 0 0 -1/2
(v) 3 2 2 +1/2
h
21.Sol: x  u 
4 m

19
Chemistry Times August 18
CLASSIFICATION OF ELEMENTS & PERIODICITY IN PROPERTIES
Introduction
Need of Classification of Elements
Elements are the basic constituents of all types of
matter.  The  discovery  of  chemical  elements  has
been  an  ongoing  process  since  ancient  times.
Certain elements, such as gold, appear in nature in
elemental  form  and  were  thus  discovered
thousands years  ago.  In  contrast, some  elements
although stable are dispersed widely in nature and
incorporated  into  numerous  compounds.  For
centuries,  therefore,  they  are  unaware  of  their
existence.
At  the  beginning  of  the  18th  century,  only  a  few
elements were known. During 18th and early 19th
century,  advances  in  chemistry  made  easier  to
isolate elements from their compounds. As a result,
the  number  of  known  elements  had  more  than
doubled from 31 in 1800 to 63 by 1865.
At present, 118 elements are known. Out of these,
recently  discovered  elements are  not  natural  but
synthetic, i.e., man - made and efforts are still going
to  synthesise  new  elements  by  artifical
transmutation.
As the number of of known elements increased, it
became rather impossible to study individually the
chemistry of these elements and their innumerable
compounds  and  scientists  began  investigate  the
possibilities of classifying them in useful ways.
Brief Historical Development of
the Periodic Table
Some of the earlier classifications based on atomic
masses of the elements are described below:
(1) Proust’s Hypothesis:
 The atomic weights of all elements are simple
multiple of atomic weight of hydrogen.
 Proust gave this hypothesis on the basis of
Dalton’s atomic theory and the atomic weights
of some elements known at that time. But this
20
hypothesis could not last longer, because there
are some atomic weights which are fractional
and not in whole number.
(2) Dobereiner’s Triads
According to Dobereiner, when elements of
same properties are kept in the increasing order
of their atomic weights, the atomic weight of
middle element is equal to the mean atomic
weight of remaining two elements. Such
a group of elements is called Dobereiner’s
triad.
Eg: Atomic weight
Cl 35.5
Br 80
I 127
 Dobereiner could arrange only a few elements
as triads and there are some such elements
present in a triad, whose atomic weights are
approximately equal,
e.g. Fe Co Ni
Ru Rh Pd
Therefore, this hypothesis was not acceptable
for all elements.
(3) Newland’s Rule of Octave :
As in music, the eighth node is same as the first
node. If the elements are arranged in the
increasing order of atomic weights, on starting
with an element, the first element will exhibit
similarities with the eighth element e.g.
Symbol of element    Li      Be     B     C     N     O       F
                7          9     11    12   14    16    19
Symbol of element    Na     Mg    Al    Si     P      S     Cl
               23      24     27    28   31    32   35.5
 It is clear from the above table that sodium is
the eighth element from lithium, whose
properties resemble that of lithium.
 This type of classification was limited up to only
20 elements.
 As more and more elements were discovered,

they could not be fitted into Newland’s Octaves.
 After the discovery of the noble gases, the idea
of octaves failed.
(4) Lothar Meyer’s Volume Curves
 The graphs of atomic volumes against atomic
weights are known as Lothar Meyer volume
curves.
 The alkali metals have highest atomic volumes.
(5) Mendeleev’s periodic classification:
Periodic Law: “Physical and chemical
properties of different elements are periodic
function of their atomic weights”.
If the elements are arranged in the order of their
increasing atomic weights, after a regular interval
elements with similar properties are repeated
(inert gases were not discovered then).
(6)Classification with respect to Atomic
Number(Z)
Moseley’s Law describes the relationship
Chemistry Times August 18
between atomic number and wavelength of a
spectral line:
K
  ,
(Z  )2
where K and  (Screening constant) are
constants for a given spectral line. Moseley
discovered the atomic numbers from X-ray
spectra of elements by bombarding the elements
with cathode rays where the elements
emitted respective X-rays of characteristic
frequency.
Atomic number ‘Z’ can be related to frequency
of  the X-rays emitted by using
v  a( Z  b)  where ‘a’( C K ),
‘b’ (Screening constant) are constants for an
element. As atomic number increases the
frequency of characteristics X-rays increases.
21
Chemistry Times August 18
A plot of  v against Z gives a straight line.
Atomic number has provided a better basis for the
periodic arrangement of the elements.
The chemistry of an atom depends only on the
number of electrons, which equals the number of
protons and is called the atomic number.
Modern Periodic Law :

“Physical and Chemical properties of the
elements are Periodic function of their Atomic
number”.
 Periodic Law is essentially the consequence of
periodic variation in electronic configurations,
which actually determine the physical and
chemical properties of the elements and their
compounds.
Modern periodic table or Long form
of periodic table
 It is also called as Bohr, Burry and Fang Werner
periodic table.
 The horizontal rows (In Mendeleev table-series)
are called periods and the vertical columns, groups.
 32 elements are present  in
3rd group(4 from d-block + 28 from f-block - Lanthanides and Actinides)
22
 According to IUPAC, groups are numbered from 1-
18 instead of Mendeleev numbering system of
Roman numerals IA to VIIA, Zero, IB to VIIB & VIII
group.
Elements  in  period  are  arranged  in  the  order  of
increasing atomic number while in group as per
same outer electronic configuration.
 In periods, elements are arranged according to the
(n+l) values order (Aufbau-Rule). Long form  of
the periodic  table is a Graphical Representation
of the Aufbau-Rule.
 Every period starts with an Alkali Metal and ends
with Noble gas.
 Two Series of elements, Lanthanides with atomic
numbers 58-71(Ce to Lu) and Actinides 90-103 (Th-
Lr) are placed below the periodic table because it
extends the table.
 1st Period is very short period with 2 elements, 2nd
and 3rd are short periods with 8 elements each, 4th
and 5th periods are long periods with 18 elements
each, 6th  and 7th period is very long period with 32
elements  each.
 Periodic table shows a transition of elements from
metals  to  non  metals  which  are  separated  by
metalloids (Semi metals).
Chemistry Times August 18

23
Chemistry Times August 18
6th period (2 from s-block, 14 from f-block, 10 from d-block and 6 from p block)
7th period (2 from s-block, 14 from f-block, 10 from d-block and 6 from p block)
 Only group with all non metals is 17th group (Halogens).
 Group with only gaseous elements is 18th (Noble gases).
(7) Classification based on electronic configuration:
(I) s- Block elements:
 The elements of the periodic table in which the
last electron enters in s–orbital, are called s–
block elements.
 GEC (General Electronic Configuration) is ns1
and ns2 indicating that s-block has only two
groups (1&2 or IA & IIA).
 Hydrogen in IA is non metal gaseous element
while all other elements in s-Block are active
metals.
 Cesium and Francium (radio-active element) are
liquids at about 30oC.
(II) p - Block elements:
 The elements in periodic table in which the last
 electron enters in p-orbital, are called p-block
elements.
 GEC is ns2 np1-6 indicating that p-block has 6
groups.(13 to 18  or IIIA to VIIA & Zero)
 Group is also referred as family and named by
considering 1st element of the group.
Boron family, Carbon family, Nitrogen family
(Pnictogens), Oxygen - Sulphur family
(Chalcogens), Halogens and Inert  gases.
 p-Block constitutes all non-Metals (Except
Hydrogen) and also contains few metals and
metalloids.
 Compounds of p-Block elements are mostly
covalent in nature.
 Helium though have 1s2 configuration is a p-
24
block element due to completely filled ultimate
shell.
(III) d - Block elements:
 The elements in periodic table in which the last
 electron enters in penultimate shell or (n-1)d -
orbitals are called d-block elements.
 GEC of these elements is (n-1) d1-10ns2 indicating
that d-block has 10 groups.
 There are four series viz., 3d-series (Z=21 to 30),
4d-series (Z=39 to 48), 5d-series (Z=57, 72 to 80)
and 6d-series (Z=89, 104 to 112).
 All the elements are less active metals and form
ionic and complex compounds.
 These elements form cations of high charge and
also exhibit variable oxidation states.
 They form alloys and interstitial (non-
stoichiometric) compounds.
 Metals with unpaired electrons in their
compounds exhibit colour and magnetic
properties.
(IV) f - Block elements:
 The elements in periodic table in which the last
electron enters into antipenultimate shell or (n-
2)f - orbitals are called f-block elements.
 GEC of these elements is
( n  2) f 114 ( n  1) d  ( or )1ns 2
 Two series of elements : Lanthanides and
Actinides. As these elements fall in between 3rd
and 4th group transition
 Chemistry Times August 18

elements, hence they are named as inner transition elements.
 Properties of these elements are similar to d-block elements.
 First few elements of lanthanides show properties similar to Calcium and then with increase in atomic
number shows properties similar to Aluminium.
 Lanthanides form Hydrides, Carbides and hydroxides. Hydroxides are basic like alkaline earth metal
oxides andhydroxides.

Actinides are very reactive metals in finely divided state.  All the metals in this series are Radioactive and
beyond Uranium (Z=92) all elements are synthetic elements or transuranic elements.

(8) Classification based on properties:

   

(I) Noble gases (TYPE - I)  These elements constitute Metals, Metalloids

 Elements with completely filled outer most shell
(nth).
 GEC is  ns 2 np 6  except for He which has 1s2.
 All elements show chemical inertness due to
completed octet configuration.
 All are monoatomic gases.
 They are also known as Rare gases as they are
present in 1% by volume in atmosphere.
Aerogens since present only in air.
 Heavier elements (Kr, Xe) form compounds
under special controlled conditions with Oxygen
and Fluorine. Hence they are referred as Noble
gases.
(II) Representative elements (TYPE - II)
 Elements with outermost shell or ultimate shell
(nth) is incomplete.
 GEC is ns1-2 ,np1-5 .
and Non-metals.
 These elements are abundant and active.
 Undergo Chemical reactions by losing, sharing
or by gaining electrons and attain nearest noble
gas configuration.
 1, 2, 13 to 17 groups are referred as representative
elements [R.E].
(III) Transition elements (TYPE - III)
 Elements with ultimate (nth) and penultimate (n-
1) shell are incomplete.
1-10
 GEC is  n - 1 d ns 0-2 .
 Elements in their native state or in any of their
possible oxidation state having incomplete d-
sub shell are referred as Transition elements.
 The characteristic properties of transition
elements are
i. They are hard and heavy metals.

25
Chemistry Times August 18

ii.The Common O.S is +2 but also show variable
oxidation states.
iii. Form  coloured ions in solution due to d-d-
transition .
iv. Form metal complexes.
v. Paramagnetic in nature due to presence of
 Volatile nature is due to inability of d-electrons to
unpaired electrons.
participate  in  metallic  bonding  thus  reducing
vi. Most of the metals are used as Catalysts.
attractive forces between metal atoms resulting low
vii. Show High M.P, B.P and densities.
MP and BP.
viii.Good conductors of heat and electricity.
 Exhibit  Pseudo  Inert  gas  configuration  in  +2
ix. They form Alloys.
oxidation state.
These characteristic properties are due to
 GEC is (n-1)s2 (n-1)p6 (n-1)d10ns2
Small size.

 They  belong  to  d-block  but  are  not  Transition
 High nuclear charge.

elements.
 Unpaired electrons in d-orbitals.

 Properties similar to representative elements.
(IV) Inner transition elements (TYPE - IV)
 Elements with three outermost shells
incomplete.{nth, (n-1) and (n-2)} IUPAC Nomenclature for Elements
 GEC is  n  2  f 113  n  1)d
  or 1
ns 2 .  . with Z > 100
Nomenclature of elements CNIC (Commission on
 f-Block elements are referred as Inner Transition
Nomenclature of Inorganic Chemistry) appointed
elements.
by  IUPAC  in  1994,  approved  a  nomenclature
 There are two series of inner transition elements
scheme  as  well  as  also  gave  official  names  for
viz.,
elements after Z > 100. This nomenclature is to be
(A) 4f-series - Lanthanide series present
followed for naming the elements until their names
between
are officially recognised. The names are derived
La57 & Hf 72 by  using  roots  for  the  three  digits  in  the  atomic
(B) 5f - series - Actinide series present between number  of  the  element  and  adding  “ium”  at  the
Ac89 & Rf104 . end.  The roots for the numbers are.
 Lanthanides are rare earths due to poor
availability in earth crust.
 Actinides are mostly synthetic. Elements from
Z = 93 onwards are referred as transuranic
elements.   
 These elements show common oxidation state
of +3.

  

26

Periodic Properties
The recurrence of similar properties of elements at
regular intervals when they are arranged in the order
of increasing atomic number is called periodicity.
Reason :  Due  to  recurrence  of  similar  outer
electronic configuration at regular intervals.
Slater’s Rule :
The recurrence of properties is observed after 2, 8,
8, 18, 18 and 32 elements which are referred as magic
numbers.
The following are periodic properties.
 Atomic radius
 Valency and oxidation state
 Ionic radius
 Oxidation and Reduction ability
 Ionisation Enthalpy
 Acidic or Basic nature of the Oxides
 Electron Gain Enthalpy
 Metallic nature
 Electro negativity
Specific heat,  Refractive index and Colour are not
periodic  properties  and  are  not  related  to  the
electronic configuration of elements.
Screening Effect:
1. In  a  multielectron  atom  the  electrons  of  the
valency shell are attracted towards the nucleus and
also  these  electron  are  repelled  by  the  electrons
present in the inner shells.  On account of this the
actual force of attraction between the nucleus and
the valency electrons is some what decreased by
the repulsive forces acting in opposite direction.
This decrease in force of attraction exerted by the
nucleus  on  the  valency  electrons  due  to  the
presence of electrons in the inner shells is called
Chemistry Times August 18
Screening effect or Shielding effect.
2. The  magnitude  of  screening  effect  depends
upon the  number  of  inner  electrons  .  The
screening  effect  constant  is  represented  by  the
symbol ‘s’. The magnitude of ‘s’ is determined by
the “Slater Rules”.
3. The  contribution  of  inner  electrons  to  the
magnitude of ‘s’ is calculated in the following way.
i) Write out the electronic configuration of the
element in the following order and groupings :
(1s) (2s, 2p) (3s, 3p) (3d) (4s, 4p) (4d) (4f) (5s,
4p), etc.
ii) Electrons in any group to the right of the (ns,
np)group contribute nothing to the shielding
constant
iii) a) For calculating s on a s or p electron (other
than on 1s)
Rule-1 : Each (ns, nP) electron contributes to a
screening factor of 0.35.
Rule-2 : Each (n – 1)th shell electron contributes
to a screening factor of 0.85.
Rule-3 : Each (n – 2)nd and deeper shell electron
contributes to a screening factor of 1.
[*On 1s, the screening factor due to other
electron is taken as 0.3.  For He   = 0.30]
b) For calculating s on d or f electron.
Rule-1 : Each screening causing electron (d
or f ) of same shell has factor of 0.35.
Rule-2 : All electrons in groups lying in the left
of the nd or nf group contribute 1.00 each to
the   .
Effective Nuclear charge
1. Due to screening effect the valency electron
experiences less attraction towards nucleus.
This brings decrease in the nuclear charge (Z)
actually present on the nucleus.  The reduced
nuclear charge is termed effective nuclear charge
and is represented by   Zeff  .
2. It is observed that magnitude of effective
nuclear charge increases in a period when we
move from left to right.
3. In a group the magnitude of effective nuclear
charge remains almost the same.
4. The effective nuclear charge   Zeff   can be
calculated by two methods :
27
Chemistry Times August 18
E n2 
a)  Z eff  or Z eff 
1312KJ / mol
Where E = The energy neccessary to remove
an electron from an atom
 n = The principal quantum number of the
electron
b)  Zeff  Z  S  or  Zeff  Z  
Where Z = Nuclear charge
S = Shielding or Screening constant
(1) Atomic radius:
 The distance between the centre of the nucleus
and the electron cloud of outermost energy
level is called atomic radius.
Atomic radius cannot be determined directly
because in atoms, the electron cloud around
the nucleus extends to infinity, but can be
measured from the inter nuclear distance of
combined atoms, using X-ray diffraction
techniques.
 Atomic radius depends on
a) Nature of bonding
b) Number of bonds (multiplicity of  bonding)
c) Oxidation states
d) Co-ordination number of atom
e) Bond character etc.
 Three types of atomic radii are considered based
on the nature of bonding they are:
a) Crystal radius or Metallic Radius.
b) Covalent radius
c) Van der waals radius
Units:Atomic radii expressed in angstrom,
Units:
       nanometers, picometer.
1Ao  10 10 m, 1nm  10 9 m, 1 pm  10 12 m
(I) Crystal radius
Half  of the internuclear distance between the
adjacent atoms of a solid metallic crystal is
called crystal radius or metallic radius.
28
Mr > actual size [Slight difference]
E n2 
Eg : Distance between two sodium atoms is
13.6eV / atom
3.72A0,crystal radius of Na = 3.72 / 2 = 1.86A0.
(II) Covalent radius
Half of the internuclear distance of the two atoms
held together by a covalent bond is called
covalent radius and is generally used to refer
radius of non-metals.
Cr < actual atom size [Slight difference]
(A)For Homoatomic molecules
dA–A = rA + rA or 2rA
dAA
rA = 
2
(B) For a heteroatomic molecules (Stevenson
&Schomaker equation)
Bond length  l  rA  rB  0.09( X A  X B ) A0
or
d A  B  rA  rB  9.0(X A  X B ) pm
Where, XA = Electronegativity of more
electronegative atom
XB= Electronegativity of less electronegative
atom
Later on modified and more accurate formula was
proposed by Porterfield as given below;
d A  B  rA  rB  7.0(X A  X B ) 2
Probability of finding the electron is never zero
even at large distance from the nucleus. Based
on probability concept, an atom does not have
well defined boundary. Hence exact value of the
atomic radius can’t be evaluated. Atomic radius
is taken as the effective size which is the distance
of the closest approach of one atom to another
atom in a given bonding state.
(III) Vander Waal’s radius:
It is the Half of the internuclear distance between
two atoms of different molecules which are very
close to each other in solid state due to vander
waals forces is called Van der waals radius.
 Chemistry Times August 18

 On moving from left to right across a particular
period, the atomic radius decreases upto
Halogens and then increases to Inert gases.
 In a given period, alkali metal is the largest and
halogen is the smallest in size.
Variation of atomic radius in Groups
 In groups from top to bottom, the atomic radius
increases.
Reason: Z increases, n (principal quantum
number) increases, Zeff remains constant.
  
n2
Since  rn α , hence  r α n 2 (Z  remaining
Zeff n eff

constant)
 Atomic radius is least for hydrogen and highest
(A)The values of atomic radii in noble gases are for  Caesium among the available elements.
always determined as van der Waals radii.  Variation of atomic radius in IA group is
Therefore, the value of  van der waals radius Li < Na < K< Rb < Cs
of a noble gas is always greater than that of
the halogen coming before it in the same
period.
(B)It is used for molecular substances and inert
gases in the solid state only.
(C)Vander waals radius is 40% greater than
covalent radius.      

               Alkali Metals
Order of different atomic radii : Van der Waals
Variation of atomic radius in transition elements
radius > Metallic radius > Covalent radius
 The decrease in size in a period across a
As  the  number  of  covalent  bonds  between  two
particular transition series is less than in case of
atoms  increases  the  covalent  radius  further
representative elements, this is due to screening
decreases.
effect of  (n-1)d-electrons.
E.g: The covalent radius of carbon decreases with
 From Cr to Cu the covalent radii is almost same.
increase in the number of bonds between carbon
This is due to
atoms.
i) shielding effect of core electrons
C C
0
C C
0
 C  0C ii) additional shielding effect of 3d electrons.
1.54 A 1.34 A 1.2 A
 Covalent radii of Zn is more than Cu due to
Variation of atomic radius in Periods repulsions among 3d electrons.
 In a period from left to right, atomic radius
decreases.
Reason: Z increases, Zeff increases, n (principal
quantum number) remain constant. Electrons are
pulled close to the nucleus due increased Zeff..
1                    
rn 
Z eff
Example : Variation of atomic radius in second
period   Li  Be  B  C  N  O  F     Transition elements
29
Chemistry Times August 18
Variation of atomic radius in lanthanides:
 In Lanthanides (Ce-Lu) the atomic radii decreases steadily. This steady decrease in atomic radii is known
as “Lanthanide Contraction”
 The contraction is due to the fact that f-orbitals are not capable of providing effective shielding for the

valence electrons from nuclear attraction due to diffused shape.
 Consequences of Lanthanide contraction
(i) Atomic sizes of 4d and 5d transition elements
become almost equal, due to which their
properties are very close.
(ii) Zr and Hf, Nb and Ta, Mo and W resemble
very closely.
(iii) The crystal structure and other properties of
lanthanides are very similar.
(iv) Separation of lanthanides is not easy from
their mixture. Chromotographic techniques
can not separate lanthanides from their
mixture.
(v) Super heavy metals of p- block exhibit inert
pair effect.  Eg : Tl, Pb, Bi
Variation of atomic radius in actinides
The size of the atom of these elements decreases
regularly as we move from left to  right is called
as Actinide contraction.
(2) Ionic radius
The distance between the nucleus and the point
where the nucleus exerts its influence on the
electron cloud in ion is Ionic radius. Ion with
positive charge is Cation and negative charge is
Anion.
 Cation is formed by loss of electrons which is
always smaller than neutral atom due to higher
Zeff. Greater the Magnitude of charge smaller is
the size.
Eg : Na  Na   , Fe  Fe2   Fe3 ,
 Anion is formed by gain of electrons which is
always larger in size than neutral atom due to
30
reduced  Zeff
Greater the Magnitude of charge larger is the
size.
Eg : Cl   Cl  ,   O 2  O   O
Variation of ionic radius in Groups
 In a particular group, the ions (cations or anions)
increase in size on moving from top to bottom
due to increase in number of shells.
Eg: Li   Na   K   Rb   Cs  ,
F   Cl   Br   I 
 In Lanthanides and Actinides the ionic radii of
trivalent ions decreases steadily.
 Isoelectronic Species: The species (atoms or
ions) having the same number of electrons are
known as isoelectronic species.
In isoelectronic species the size decreases as
the atomic number increase.
1
Size 
effective nuclear charge
Eg: C4-  >  N3- >  O2- > F- > Ne >  Na+ >  Mg2+ >
Al3+ > Si4+
(3) Ionization energy
The minimum amount of energy required to
remove the most loosely bounded electron from
an isolated gaseous atom is known as Ionization
energy (I.E.) or Ionization potential (I.P.).
Units : kJ mol–1, k calmol–1, eV per atom.
 Ionisation energy is endothermic (endoergic)
i.e., requires energy hence  H  is +ve
 Chemistry Times August 18

 Electron gain Enthalpy

 M   e
M  Energy ( IE1 )  When expressed in terms of enthalpy change
 M   e
M  H  IE1 ( H ) then it is termed as E.G.E. Remember that
 2 
M 
M e H  IE2 H  = – ve for exothermic change.
M 2
M
 3
e 
H  IE3 For EA1, energy is released  H /EA1 = – ve
For EA2, onwards is required H /EA2 = + ve
EA1 + EA2 , energy is always required.
 Factors affecting Electron Affinity
(I) Atomic size : varies inversely
(II) Nuclear change : varies directly
(III) Half filled and completely filled electronic
Always IE3> IE2> IE1
configuration containing elements.
 General Trend: Along a period, electron affinity
 Factors affecting Ionisation Energy
increases [with exception] as Zeff Increases.
(I) Atomic size : Varies inversely
Along a group, electron affinity decreases after
(II) Screening effect : varies inversely
3rd period. Between 2nd and 3rd period in p
(III) Nuclear charge : varies directly
block, electron affinity of 2nd period is lesser
(IV) Half filled and completely filled orbital
due to high electron density.
containingelements possesses high ionization
energy
 General Trend:Along period I.E. increases
[with some exception] [Zeff  ]
 Along a group I.E. decrease [Zeff constant, n
 A fully filled and half filled which have low values
] or even sometimes energy is required rather than
Exception getting released.
 Along a period, half filled and fully filled have  2nd  period  has  lower  value  than  3rd  owing  to
higher I.E. e.g. Be > B and N > O. repulsion between electrons.
 along a group, Ga > Al
(5) Electronegativity (E.N.)
The tendency of an atom in a compound to
attract a pair of bonded electrons towards itself
is known as electronegativity of the atom.
Properties affected by Ionisation Energy:
(1)Metallic character
(2)Tending to stay in which state A+1. A+2 or  A+3
(3)Other properties based on (1)
It  is  important  to  note  that  electron  affinity  and
electronegativity both measure the  electrons
(4) Electron affinity (E.A.) attra-cting power but the former refers to an isolated
The amount of energy released when an electron gaseous  atom  while  the  latter  to  an  atom  in  a
is added to an isolated gaseous atom is known compound. Thus electron affinity is attraction for
as electron affinity. a single electron while  electronegativity is for a
Units : k J mol-1 ,  kcal mol-1 and  eV per atom. pair of bonded electrons. Further electron affinity
 Addition of electron results in release of energy is energy while electronegativity is a tendency.
i.e., exothermic process in most of the cases but
2nd  E.A. is always energy required process i.e.,  Factors affecting the value of electronegativity
endothermic process. The sum of  EA1&  EA2 (I) The size of the atom.
is energy required.

31
Chemistry Times August 18

(II) Electronic configuration. from the conversion of kcal to electron volt
Small atoms attract electrons more than the (1 eV = 23.0  kcal/mole), while
larger one and are therefore more
electronegative. Secondly, atoms with nearly E  Actual bond energy   (E A  A  E B  B )
filled shell of electrons, will tend to have
higher electronegativity than those sparsely
occupied  ones.
 Variation of electronegativity in the periodic
table
Pauling and Mulliken values of electronegativities
(I) In a period, electronegativity increases from
are related as below
left to right. This is due to decrease in size
and increase in nuclear charge. Thus the  (Pauling) = 0.34    (Mulliken) – 0.2
alkali metals possess the lowest value, while
the halogens have the highest. Inert gases  Importance of electronegativity :
have zero electronegativity. (A) Nature of  the bond between two atoms can
(II) In a group, electronegativity decreases from be predicted from the electronegativity
top to bottom. This is due to increase in difference of the two atoms.
atomic size. (a) The difference  X A  X B  0, i.e.,
If an element exhibits various oxidation state,
the atom in the higher oxidation state will be X A  X B the bond is purely covalent.
more negative due to greater attraction for (b) The difference  X A  X B  is small,  i.e.,
the electron, e.g., Sn II (1.30) and Sn IV (1.90).
 Electronegativity may be expressed on the X A  X B , the bond is polar covalent.
following three scales (c) The difference  is 1.7, the bond is 50%
(I) Mulliken’s scale : Mulliken regarded covalent and 50% ionic.
electronegativity as the average value of (d) The difference is very high, the bond is
ionisation potential and electron affinity of more ionic and less covalent.
an atom. Percentage ionic character may be calculated
Ionisation potential  Electron affinity by Henny Smith equation,
           Electronegativity  Percentage of ionic character
2
(II) Allred-Rochow scale : Allred and Rochow  16 | X A  X B |  3 . 5( X A  X B )2
defined electronegativity as the electrostatic
force exerted by the nucleus on the valence where X A  and  X B  represents
0 .359 Z electronegativity of bonded atoms A and B
electrons. Thus     0 .744
(B) Greater the value of difference  ( X A  X B )
r2
where Z is the effective nuclear charge and r more stable will be the bond.
is the covalent radius of the atom in Å.
(III) Pauling scale : Pauling scale of
electronegativity is the most widely used. It
isbased on excess bond  energies. He
determined electronegativity difference
between the two atoms and then by
assigning  arbitrary values to few elements Stability  of compounds in which  X A  X B  is
(e.g. 4.00 to fluorine, 2.5 to carbon and 2.1 to   very  small  are  unstable  in  nature,
hydrogen), he calculated the SiH1 (0.3), NCl3 (0, 0),
electronegativity of the other elements.
PH 3 (0), AsH 3 (0 .1)  are unstable.
 A   B  0 . 208 E where  A  and
(C)  ( X  X A ) difference predicts the nature of
O
 B are electronegativities of the atoms A
A
and B respectively, the factor 0.208 arises the oxides formed by the element A.  X O is the

32
 Chemistry Times August 18

electronegativity of oxygen.
X O  X A  is large, the oxide shows basic nature, (e.g., Na 2 O ) is small, the oxide shows acidic nature,
(e.g.,SO2).
(D) Ionic compounds having percentage ionic character less than 20% were found coloured, Ex:

(Lesser the percentage ionic character, darker will be the colour.)
(7) Nature of oxides:
 The normal oxide formed by the element on extreme left is the most basic (e.g.Na2O), whereas that formed
by the element on extreme right is the most acidic(e.g.Cl2O7). Oxides of elements in the centre are amphoteric
(e.g.Al2O3,  As2O3) or neutral (e.g. CO,NO,N2O).
 If difference of the two electronegativities (XO– XA) is 2.3 or more than 2.3 then the oxide will be basic in
nature. Similarly if value of XO–XA is lower than 2.3 then the compound will be first amphoteric then acidic
in nature.

 Periodic Trend in groups

(I) Acidic nature of oxides decreases down the group.
(II) Basic nature of oxides increases down the group.
 Periodic trend in periods
(I) Basic nature of oxides decreases from Left to Right in a period
(II) Acidic nature of oxides increases from Left to Right in a period
(8) Valency or Oxidation state
The valence is the most characteristic property of the elements and can be understood in terms of their
electronic configurations.  The valence of representative elements is usually (though not necessarily)
equal to the number of electrons in the outermost orbitals and / or equal to eight minus the number of
outermost electrons as shown below.
Group IA IIA IIIA IVA VA VIA VIIA Zero
Number of valence electron 1 2 3 4 5   6   7   8
Valence 1 2 3 4 3,5   2,6   1,7 0,8
Valency of normal elements with respect oxygen increases from 1 to 7.

33
Chemistry Times August 18

Valency of normal elements with respect to hydrogen and chlorine increases from 1 to 4 and then decreases
to 1 again.

(9) Metallic and non-metallic character

 The tendency of an element to lose electrons and form cations is referred as Electropositive  character or
Metallic  character.  Metal has low electronegativity, low IE and high Electropositivity.
Eg: The groups IA and IIA elements have strong metallic nature.
Metals are solids at room temperature except mercury(Hg). Ga,Cs have very low melting points 303K and
302K respectively hence they exists as liquids at room temperature.
 The tendency of an element to accept electrons to form an anion is called its non-metallic or electronegative
character. Non metal has high electron affinity (or high electronegativity) have higher tendency to gain
electrons.
Eg: Group VIA and VIIA elements have strong non-metallic nature.
 Non-metals are usually solids or gases at room temperature {Except Bromine (liquid)}with  low melting
and boiling points. (Boron and Carbon are exceptions which have high MP and BP)
 Some elements in periodic table shows both metallic and non-metallic nature. They are called metalloids or
semi metals.  Eg: Boron, Silicon. Germanium, Arsenic, Antimony, Tellurium.
Variation of metallic character in a group
 Non Metallic nature decreases and Metallic nature increases down the group.
Eg:

 Order of metallic nature : Alkali metals > Alkaline earth metals > d-block > p-block

 Reactivity of metals : The tendency to lose electrons increases as we go down a group. So, the reactivity
of metals increases down the group.
 Reactivity of non-metals: The reactivity of non-metals in a group decreases as we go down the group.
Variation of metallic character in a period
 Metallic nature decreases and Non Metallic nature increases
Eg:

 Reactivity of metals : The tendency of an  element to lose of electrons decreases in going from left to right

34

in a period. So, the reactivity of metals
decreases in a period from left to right.
 Reactivity of non-metals :  The reactivity of
non-metals increases from left to right in a
period.
Hydration and Hydration energy
 The  enthalpy  change  accompanied  during
dissolution of 1 mole of gaseous ions in water is
referred as Hydration energy and the phenomenon
as Hydration.
   MP’s of elements usually decrease down the
Li(g )  H 2 O   Li  H 2 O   ; H  806 kJ mol 1
 Factors influencing Hydration
(i) Size of the ion: Hydration capacity is inversely
proportional to size of the ion.
(ii) Charge on the ion: Hydration capacity is directly
proportional to the charge on the ion.
 Greater  charge  results  smaller  ionic  size  which
increases extent of hydration resulting large value
of Hydration energy.
 Effects of Hydration
i. Size of hydrated ion increases : Greater the extent
of hydration larger is the size of hydrated ion
Eg. Li(aq )  Na(aq )  K(aq )  Rb(aq )  Cs(aq )  ;
Na(aq )  Mg(2aq )  Al(3aq )
Chemistry Times August 18
ii. Ionic mobility : Greater than extent of hydration
lower is the mobility.
Eg :  Li(aq )  Na(aq )  K(aq )  Rb(aq )  Cs(aq ) ;
Na(aq )  Mg(2aq )  Al(3aq )
(10) Melting and boiling points
Both melting and boiling points of an element
indicate the nature and extent of binding
between the atoms of the element. The
periodicity of these elements are shown in the
following graph.
 The noble gases have very low MP’s.
  MP’s of elements in any period increases
gradually to group 14 and then decreases to
Noble gas.
group. Exception is Halogens where MP
increases down the group.

The high melting points of transition metals
are attributed to the involvement of greater
number of electrons from (n-1)d in addition to
the ns electrons in the interatomic metallic
bonding. In any row the melting points of these
metals rise to a maximum at d5 except for
anomalous values of Mn and Tc and  fall
regularly as the atomic number increases. The
sudden fall from IB to IIB is explained on the
fact that completed d-orbitals which do not
participate in metallic bonding.
35
Chemistry Times August 18
Diagonal Relationship
In the periodic table the first element of a group
has similar properties with the second element of
the next group. This is called diagonal relationship.
The  diagonal  relationship  disappears  after  IVA
group.
Diagonal relationship is due to following factors,
 Similar sizes of atoms or ions.
 (17) Element most found on earth – Al
 Same electronegativities of the participating
 (18) Gaseous elements – 11 (He, Ne, Ar, Kr, Xe, Rn,
elements
 Same polarising power.
 (19) Liquid elements – 5(Br, Hg, Ga, Cs, Fr)
ionic ch arg e
Polarising power =  2
 ionic radius 
Similarities between properties of Li and Mg are
as follows.
 Li and Mg both reacts directly with nitrogen to
form lithium nitride (Li3N) and magnesium nitride
(Mg3N2).
 Fluoride, carbonate and phosphate of Li and
Mg are insoluble in water.
 LiOH and Mg(OH)2 both are weak bases.
 By thermal decomposition of LiNO3 and Mg
(NO3)2 give Li2O and MgO.
 Thermal stability of Li2CO3 and Mg CO3 is very
less and they liberate CO2 gas easily.
Similarities between properties of Be and Al
 BeO amphoteric, Al
 O  amphoteric
2 3
 2C or Al4C3 produce methane on hydrolysis.
  Be
 Be and Al both forms halogen bridge halides.
 (34) Volatile d-block elements : Zn, Cd, Hg
      
Some Important Points
The periodic table proposed by – Rang.
Modified by – Werner
Extended by – Burry and his co-workers
(1) Triad rule – Dobereiner
(2) Octet rule – Newland
(3) Study of atomic volume – Lothar Mayer
(4) Inventor of atomic number – Moseley
(5) Godfather of periodic table – Mendeleef
36
(6) Maker of modern periodic table – Bohr
(7) Mg is bridge element, which joins metals of IIA
and II B groups.
(8) Elements after atomic number 92 are transuranic
elements.
(9) Artificial element is Tc43.
(10) Liquid non-metal – Br
(11) Liquid metal – Hg, Ga, Cs, Fr
(12) Solid volatile non-metal – Iodine
(13) Lightest metal – Li
(14) Heaviest metal – Ir
(15) Hardest metal – W
(16) Noble metals – Pc, Pt, Au, Ag
H2, N2, O2, Cl2, F2)
(20) Submetals – 5(B, Si, As, Te, At)
(21) Inert gases – 6
(22) Lowest electronegativity : Cs
(23) Highest electronegativity : F
(24) Highest ionization potential : He
(25) Lowest ionization potential : Cs
(26) Highest electron affinity : Chlorine (Cl)
(27) Least electropositive element : Fluorine (F)
(28) Most reactive solid element : Li
(29) Most reactive liquid element : Cs
(30) Most stable element : Te
(31) Largest atomic size : Cs
(32) Most electropositive element :
Cs; Fr
(in stable element)      (In all element)
(33) Group containing maximum no. of gaseous
elements in periodic table :
Zero gp ; next to zero gp is VII gp or halogen gp
(F2 and Cl2)
(35) Most abundant element on earth : Oxygen
followed with Si
(36) Most stable carbonate : Cs2CO3
(37) Strongest alkali : Cs(OH)
(38) Element kept in water : P
(39) Elements kept in kerosene oil : Na, K, I, Cs
(40) Liquid non metal : Br2
(41) Bridge metals : Na, Mg
(42) Lightest element : H
(43) Poorest conductor of current : Pb(metal), S
(non metal)
(44) Most abundant gas : N2
(45) Lightest solid metal : Li
(46) Heaviest solid metal : Os(highest density 22.6
g/cm3)
 Chemistry Times August 18

(47) Natural explosive : NCl3 (b) Atomic number = 8, 16, 34, 2
(48) Dry ice : CO2 (c) Atomic number = 11, 18, 27, 5
(d) Atomic number = 24, 47, 42, 55
9. There are 10 neutrons in the nucleus of the element
9. 
z M 19 .  It belongs to -
(a) f-block (b) s-block
LEVEL-1 (c) d-block (d) None of these
1. The first list of 23 elements was compiled in the 10. The IUPAC symbol of the element with atomic
late 1790s by number Z = 109 is
(a) Dimitri Medeleev (b) Lother Meyer (a) Unp (b) Uns (c) Uno (d) Une
(c) Antione Lavoisier (d) John New land 11. The  IUPAC  name  of  the  element  with  atomic
2. Elements which occupied position in the Lother number Z = 112 is
Meyer curve, on the peaks, were (a) Seaborgium (b) Copernicium
(a) Alkali metals (c) Dubnium (d) Hassium
(b) Highly electro positive elements
12. If the atomic radius of non-metal bromine is 1.14 Å ,
(c) Elements having large atomic volume
its covalent radius is
(d) All
3. The period number in the long form of the periodic (a) 1.14  Å (b) 1.12 Å
table is equal to (c) 1.16 Å (d) 0.57 Å
(a) Magnetic quantum number of any element of
13. In the isoelectronic species the ionic radii ( Å ) of
the period.
N3–, O2–, F– are respectively given by
(b) Atomic number of any element of the period.
(a) 1.36, 1.71, 1.40 (b) 1.36, 1.40, 1.71
(c) Maximum Principal quantum number of any
(c) 1.71, 1.36, 1.40 (d) 1.71, 1.40, 1.36
element of the period.
14. Which of the following is the wrong statement ?
(d) Maximum Azimuthal quantum number of any
(a) All the actinide elements are radioactive.
element of the period.
(b) Alkali and alkaline earth metals are s-block
4. The discovery of which of the following group of
elements.
elements gave a death blow to the Newland Law
(c) Chalcogens and halogens are p-block
of Octaves.
elements.
(a) Inert gases (b) Alkaline earths
(d) The first member of the lanthanide series is
(c) Rare earths (d) Actinides
lanthanum.
5. Which  of  the  following  set  of  elements  obeys
15. The ionic size decreases in the order
Newland’s octave rule?
(a) Na, K, Rb (b) Mg, Ca, Sr (a)  K   S 2   Sc3  V 5  Mn7 
(c) Cl,Br, I (d) Be, Mg, Ca (b)  S 2   K   Sc3  V 5  Mn7 
6. As applied to periodic table, which of the following
6. 
(c)  Mn7   V 5  Sc3  K   S 2 
sets include only magic numbers
(a) 2, 8, 20, 28, 50, 82, 126  (b) 2, 8, 8, 18, 18, 32 (d)  Mn7   V 5  Sc3  S 2   K 
(c) 2, 2, 8, 8, 18, 32 (d) 2, 8, 18, 18, 32, 32 16. The ionic radius of Cr is minimum in which or the
16. 
7.  Pd  has  exceptional  valence  shell  electronic following compounds?
configuration of  4d 10 5s 0 .  It is a member of (a)  CrF3 (b)  CrCl3   (c)  Cr2 O3  (d)  K 2 CrO4
(a)  5th  Period, Group 10 17. 
17. Arrange  Ce , La 3 , Pm3  and  Yb3  in increasing
3

(b)  4th  Period, Group 12 order of their size

(c)  6th  Period, Group 10 (a)  Yb3  Pm3  Ce3  La 3
(d)  5th  Period, Group 14 (b)  Ce3  Yb3  Pm3  La3
8. From the list given below, elements which belongs
8. (c)  Yb3  Pm3  La3  Ce3
to the same group or sub-group are
(a) Atomic number = 12, 20, 4, 88 (d)  Pm3  La3  Ce3  Yb3

37
Chemistry Times August 18

18. 
18. The incorrect statement among the following is LEVEL-2
(a) The first ionisation potential of Al is less than 1. Modern  periodic  table  is  based  on  atomic  no.
the first ionisation potential of Mg. experiments which proved importance of at no. was
(b) The second ionisation potential of Mg is -
greater than the second ionisation potential of (a) Bragg’s work on X-ray diffraction
Na. (b) Moseley’s work on X-ray spectrum
(c) The first ionisation potential of Na is less than (c) Mulliken’s oil drop experiment
the first ionisation potential of Mg. (d) Lother meyer curve plotted between at vol. &
(d) The third ionisation potential of Mg is greater at. wt.
than third ionisation potential of Al. 2. The atomic weights of “Be” and “In” were corrected
19. Correct orders of 1st I.P. are
19. by Mendeleev using the formula
(i) Li < B < Be < C
(ii) O < N < F (a)  v  a( Z  b)
(iii) Be < N < Ne nh
(a) (i), (ii) (b) (ii), (iii) (b)  mvr 
2
(c) (i), (iii) (d) (i), (ii), (iii)
20. The I1 values of Li, Be and C are 5.4 eV/atom, 9.32 (c) Atomic weight = Equivalent weight x valency
eV/atom and 11.26 eV/atom. The I1 value of Boron (d) Equivalent weight = Atomic weight x valency
is 3. Atomic  radius  decreases  in  a  period,  but  after
(a)  13.6 eV/atom (b) 8.29 eV/atom halogens,  the  atomic  radius  suddenly  increases.
(c) 14.5 eV/atom (d) 21.5 eV/atom Thus,  inert  gases  has  almost  highest  radius  in  a
21. Which of the following metals require radiation of period. The explanation for such an increase is
highest frequency to cause emission of electrons ? (a) Inert gases has most stable configuration
(a)  Na (b)  Mg (c)  K (d) Ca (b) Inert gases do not take part in bonding
22. From the ground state electronic configurations of (c) Van der Waal’s radius is reported in case of inert
the  elements  given  below,  pick  up  the  one  with gases
highest value of second ionisation enthalpy (d) None of these
4. 3 students Ram, Shyam and Raj measured the radius
(a) 1s 2 2s 2 2p 6 3s 2 (b) 1s 2 2s 2 2p 6 3s1 of an element A. The values of their practical were
(c) 1s 2 2s 2 2p 6 (d) 1s 2 2s 2 2p5 not same (Ram = 110 nm, Shyam = 190 nm and Raj =
108  nm).  Their  teacher  explained  that  their
23. Which of the following has the lowest ionisation
measurements  were  correct  by  saying  that  the
enthalpy?
recorded values are
(a) 4s1 (b) 3d2 (c) 3p6 (d) 2p6
(a) Metallic, van der Waal and covalent radii
24. Among the following arrangements, the order is
24. 
respectively
not according to the property indicated against it
(b) Covalent, Metallic and Van der Waal radii
is
respectively
(a)  Li  Na  K  Rb :  Increasing metallic radius (c) Van der Waal, Metallic and covalent radii
(b)  I  Br  F  Cl :  Increasing electron gain respectively
enthalpy with negative sign (d) None of these
(c)  B  C  N  O :  Increasing first ionisation 5. The correct order of size would be
enthalpy (a)  Ni  Pd  Pt (b)  Pd  Pt  Ni
(d)  Al 3  Mg 2   Na   F  :   Increasing  ionic (c)  Pt  Ni  Pd (d)  Pd  Pt  Ni
size 6.  Calculate the energy needed to convert three moles
25. Among halogens, the correct order of amount of of  sodium  atoms  in  the  gaseous  state  to  sodium
energy  released  in  electron  gain  (electron  gain ions.  The  ionization  energy  of  sodium  is
enthalpy) is 495 kJ mol 1 .
(a) F > Cl > Br > I (b) F < Cl < Br < I (a) 1485 kJ (b) 495 kJ    (c) 148.5 kJ     (d) None
(c) F < Cl > Br > I (d) F > Cl < Br < I 7. Which one of the following arrangements represents
the correct order of electron gain enthalpy (with
negative sign) of given atomic species?

38
 Chemistry Times August 18

(a) F< Cl < O < S (b) S < O < Cl < F 6. a

6. 7. c
7. 8. c
8. 9. c
9.  10. c
10.
(c) O < S < F < Cl (d) Cl < F < S < O
8. A, B and C are hydroxy-compounds of the elements
X, Y and Z respectively. X, Y and Z are in the same
period  of the periodic  table. A gives an aqueous LEVEL-1
solution of pH less than seven. B reacts with both 4.Sol: With the discovery of inert gases (Group zero in
4.Sol:
strong  acids  and  strong  alkalies.  C  gives  an Mendeleev’s  periodic  table),  the  law  of  octaves
aqueous solution which is strongly alkaline lost its original significance since it was now the
Which of the following statements is/are true: nineth element which had properties similar to the
I : The three elements are metals first one.
II : The electronegativities decrease from X to Y to 7.Sol:  4d 10 5s 0  is the exceptional configuration of Pd.
Z.
Its  electronic  configuration  should  be
III : The atomic radius decreases in the order X, Y
and Z. [36 Kr ]4d 8 , 5s 2 .  Thus its Period = 5th
IV : X, Y and Z could be phosphorus, aluminium Group = ns + (n - 1)d electrons = 2 + 8 =10
and sodium respectively : 9.Sol: Z = 19-10 = 9 i.e., Flourine element which belongs
9.Sol: 
(a) I, II, III only correct to p-block elements.
(b) I, III only correct 10.Sol: Une stands for unnilennium
10.Sol:
(c) II, IV only correct 12.Sol: The term covalent radius is applicable for non
12.Sol:
(d) II, III, IV only correct metal atomic radius.
Paragraph(9-10) 14.Sol: First member of lanthanide series is Cerium, Ce
14.Sol: 
Look at the location of elements A,B,C and D in the 15.Sol: All of them are isoelectronic species.
15.Sol:
following Periodic Table : 16.Sol:  Cr  has  maximum  oxidation  number  (+6)  in
16.Sol:
K 2 CrO4  and thus, has minimum ionic radius.
17.Sol:  Lanthanide  contraction  is  observed  in  these
17.Sol:
ions, i.e., ionic radius decreases as atomic number
increases.
18.Sol:  Na ( z  11) :1s 2 2 s 2 2 p 6 3s1
 
Mg (12)  1s 2 2 s 2 2 p 6 3s 2
Na  :1s 2 2 s 2 2 p 6

9. The oxide in these elements with highest oxidation Al (13)  1s 2 2 s 2 2 p 6 3s 2 3 p1
state 19.Sol: Due to stability of half-filled and completely
19.Sol: 
(a) A (b) B (c) C (d) D filled orbitals.
10. Basic, acidic and amphoteric oxides among them 20.Sol: I.E., of B < Be
20.Sol:
(a) A, B ,C (b) B, A, C 22.Sol: Here,  IE 2  involves the removal of an electron
22.Sol: 
(c) A, C, B (d) B, C, A
from the inert gas configuration  1s 2s 2p 
2 2 6

23.Sol: 1 is a s-block element.
23.Sol: 4s
25.Sol: 
25.Sol: F experience greater inter electronic repulsion
on addition of electron due to smaller size compared
LEVEL-1 to Cl. Hence F electron affinity is less than Cl.
1. c
1.  2. d
2.  3. c
3. 4. a
4.  5. c
5.  LEVEL-2
6. b
6.  7. a 8. a
8. 9. d
9.  10. d
10.  6.Sol:
6.Sol: Energy needed to convert 1 mole of sodium (g)
11. b 12. a
12. 13. d
13.  14. d
14. 15. b
15. to sodium ions = 495 kJ
16. d
16. 17. a
17.  18. b
18. 19. d
19.  20. b
20.
  energy needed to convert 3 mole of Na (g) to  Na 
21. b
21. 22. b
22. 23. a
23.  24. b
24.  25. c
25.
LEVEL-2 ions   495  3  1485kJ
1. b
1.  2. c
2. 3. c
3. 4. a
4.  5. a
5.  9.Sol: SO3
9.Sol:
10.Sol: CaO, SO3, Al2O3
10.Sol:
39
Chemistry Times August 18

SOLUTIONS

[ONLINE QUESTIONS]
5. Determination of the molar mass of acetic acid in
1. 5 g of Na2 SO4 was dissolved in x g of H 2 O . The benzene using freezing point depression is affected
by: [2015]
change in freezing point was found to be 3.820 C . (a) Partial ionisation (b) Complex formation
If Na2 SO4 is 81.5% ionised, the value of x ( K f for (c) Dissociation (d) Association
6. For an ideal solution of two components A and B,
water  1.860 C kg mol 1 ) is approximately : which of the following is true? [2014]
(molar mass of S = 32 g mol 1 and that of Na = (a) H mixing  0(zero)
(b) A - A, B - B and A - B interactions are identical
23 g mol 1 ) [2017]
(c) A - B interactions is stronger than A - A and B
- B interactions
(a) 25 g (b) 65 g (c) 15 g (d) 45 g
(d) H mixing  0(zero)
2. The freezing point of benzene decrease by 0.45 C
7. The observed osmotic pressure for a 0.10 M
when 0.2 g of acetic acid is added to 20 g of
benzene. If acetic acid associates to form a dimer solution of Fe(NH 4 )2 (SO 4 ) 2 at 25 C is 10.8 atm.
in benzene then the % of association will be :- The expected and experimental (observed) values
(Kf for benzene  5.12 K kg mol1 ) [2017] of Van’s Hoff factor (i) will be respectively:
(a) 80.4% (b) 74.6% (c) 64.6% (d) 94.6% (R = 0.082 L atm K1mol1 ) [2014]
3. The solubility of N 2 in water at 300 K and 500 torr (a) 3 and 5.42 (b) 5 and 3.42
(c) 4 and 4.00 (d) 5 and 4.42
partial pressure is 0.01gL1 . The solubility (in 8. Choose the correct statement with respect to the
vapour pressure of a liquid among the following
gL1 ) at 750 torr partial pressure is : [2016]
:- [2014]
(a) 0.02 (b) 0.015 (c) 0.0075 (d) 0.005 (a) Increase linearly with increasing temperature
4. An aqueous solution of a salt MX 2 at certain (b) Decrease non-linearly with increasing
temperature has a Van’t Hoff factor of 2. The temperature
degree of dissociation for this solution of the salt (c) Decrease linearly with increasing temperature
is : [2016] (d) Increase non-linearly with increasing
(a) 0.67 (b) 0.33 (c) 0.80 (d) 0.50 temperature

40
 Chemistry Times August 18

9. How many grams of methyl alcohol should be


added to 10 litre tank of water to prevent its 1  0.527
2
freezing at 268 K ( K f for water is 1.86 K kg
  0.945
mol1 ) [2013] % degree of association = 94.5%
(a) 880.07g (b) 899.04g 3.Sol: According to Henry’s law
(c) 886.02g (d) 868.06g
P1 S1

P2 S2
 S1 & S2 are solubility of gas (g/L)

500 0.01
1. d 2. d 3. b 4. d 5. d 
6. b 7. d 8. d 9. d 750 S2

750 0.01
 S2   0.015g / L
500
4.Sol: For MX 2 type salt
1.Sol : Van’t factor (i)  1  2  2
Na2 SO4  2 Na   SO4 2     0.5
i  1  (3  1) 0.815  2.63 5.Sol: Acetic acid contain carboxylic group - COOH
which can form H-bonding so acetic acid
5  1000 dimerises.
3.82  1.86  2.63 
142  x
1.86  2.63  5000
x   45 gm
142  3.82
2.Sol: In benzene 7.Sol:   iCST
2CH 3 COOH  (CH 3 COOH) 2  10.8
i 
CST 0.1 0.0821 298
1 
i  1    1  i = 4.42 (observed)
2 
9.Sol: T f  K f m

i  1 Here  is degree of association w
2 273  268  1.86 
m v
Tf  ik f m
w
 0.2  5  1.86
  32  10
  60 
0.45   1    5.12   5  32  10
 2 20 w
1000 1.86
 860.2  868.06g

41
Chemistry Times August 18
THERMODYNAMICS
Introduction
 Thermodynamics is the branch of physical
chemistry which deals with the transfer of heat
between a chemical system and its surrounding
when a change of phase or a chemical reaction
takes place within the system. It is also termed as
chemical energetics.
 Thermodynamics deals about heat changes
occurring between system and surroundings.
 Thermodynamics predicts the extent to which
the chemical reaction can occur before the
equilibrium is attained but fails to explain about
the systems away from equilibrium.
 Thermodynamics predicts the feasibility of the
chemical reaction under the given set of conditions
but fails to suggest rate of reaction.
Thermodynamic terms
 To understand chemical reactions and the energy
changes accompanying them we need to know
certain thermodynamic terms.
(1) System
A system is defined as any part of universe that is
under thermodynamic study at that instant. A
system may consist of one or more substances.
Eg:
 A crystal (for a crystallographer)
 A physical process (for a physicist)
 Chemical reaction (for a chemist)
Surroundings : The remaining part of the universe
other than system is surroundings.
Thus Universe = system + surroundings
However, the entire universe other than the system
is not affected by the changes taking place in the
system. Therefore, for all practical purpos-
es, the surroundings are that portion of the remai-
ning universe which can interact with the system
constitutes its surroundings.
42
Eg : If we are studying the reaction between two
substances, the beaker containing the reaction
mixture is the system and the room where the beaker
is kept is the surroundings.
(2) Types of system
(I)Systems are classified on the basis of their
interaction with the surroundings.
(A) open system
Matter and energy exchanged with surroundings
are known as open system.
System is not sealed and not insulated
Eg: Plants and living beings
(B) Closed system
Energy but not the matter exchanged with
surroundings is known as closed system.
System is sealed but not insulated
Eg: A closed steel container with hot water
(C) Isolated system
Neither matter nor energy exchanged with
surroundings are known as isolated system.
System is sealed and insulated
Eg: A substance in ideal thermally insulated flask
(II) On the basis of composition, there are two
types of systems.
(A) Homogeneous system : A system is said to be
homogeneous when it is completely uniform
throughout. It consists of one phase only.
Eg: Pure solid, a liquid or a mixture of gases.
(B) Heterogeneous system : It is not uniform
throughout. It consists of two or more phases.
Eg: Ice in contact with water, two or more immisc-
ible liquids, insoluble solid in contact with a
liquid.
(3) Thermodynamic Process
The operation which brings about the changes
in the state of the system is termed as thermody-
namic process.The various types of the processes
are:

(V) Cyclic process : When a system undergoes a
number of different processes and finally returns
to its initial state, it is termed as Cyclic process.
For a cyclic process,
E  0, H  0, S  0, G  0 .
(VI) Reversible process : A reversible process is
considered to proceed from initial state to final
state through an infinite series of infinitesimally
small stages and at every state it is virtually in the
state of equilibrium.
A reversible process has the following
characteristics:
 It involves a slow change during operations
and surroundings are always in equilibrium
with system
 The process may take place in either direction
 Driving force and the opposing forces differ
with each other by an infinitesimal value
 It gives to maximum work during studies
 The net work involved in two process (if cyclic)
=0
Chemistry Times August 18
 A reversible process is a process than can be
reversed by an infinitesimal change in a variable
 Reversible process are quasistatic.
(VII) Irreversible process : The process goes from
initial to final state in a single step or finite number
of steps in finite time and cannot be reve-
rsed exactly by small changes in state variables
like P, V, and T etc. All processes which naturally
occur are irreversible.
An irreversible process has the following
characteristics:
 It involves fast changes during operations and
equilibrium exists at the initial and final stages
only
 These are unidirectional processes
 Driving force and the opposing forces differ
by a large amount.
43
Chemistry Times August 18
 It gives rise to net workdone, i.e., somewhat
lesser work than the reversible work or Wrev >
Wirrev.
(4) Thermodynamics Properties
(I) Macroscopic properties : Thermodynamics
deals with matter in terms of bulk (large number of
chemical species) behaviour. The properties of the
system which arise from the bulk behaviour of
matter are called macroscopic properties. The
macroscopic properties can be subdivided into
two types.
(A) Extensive properties : The properties whose
magnitude depends upon the quantity of matter
present in the system are called extensive
properties.
Eg : Mass, volume of a gas, internal energy,
enthalpy, entropy, heat capacity, Gibb’s energy.
Extensive property is additive for independent,
noninteracting subsystems.
(B) Intensive properties : The properties whose
magnitude is independent of the quantity of
matter present in the system are called intensive
properties.
Eg: Pressure, Temperature, Density, Molar
properties (such as molar volume, molar entropy,
molar heat capacity), Surface tension, Viscocity,
Specific heat, Refractive index, Boiling point,
Freezing point, Vapour pressure.
 Intensive property is non additive.
 The ratio of the two extensive properties become
intensive in nature.
Eg: Mass and volume are extensive properties,
but the ratio of mass and volume, i.e., density is
intensive.
(5) State of a system
 The system is said to be in a certain state,
when it’s macroscopic properties have definite
values. It is defined in terms of its state
44
functions such as P,V,T etc.
 If any one of the state functions is changed,
the state of that system is said to be changed.
Eg: Water is in liquid from 0  100C at 1 atm
pressure. Below 0C , it is solid and at above
100C , it is in vapour state.
(6) State functions or state variables
The thermodynamic properties whose value
depend only upon the initial and final states of
the system and are independent of the path are
called state functions.
Eg: Internal energy (E), Enthalpy (H), Entropy
(S), Gibb’s energy (G), Pressure (P), Temperature
(T), Volume (V), Number of moles(n).
(7) Path Function
Thermodynamic properties whose value depends
on the path of transformation n is known as path
function.
Eg: Heat, Work.
A person standing on the roof of a five storeyed
building has a fixed potential energy, irrespective
of the fact whether he reached there by stairs or
by lift. Thus the potential energy of the person is
a State function. On the other hand, the work done
by the legs of the person to reach the same height,
is not same in the two cases i.e., whether he went
by lift or by stairs. Hence Work is a Path function.
(8) Thermodynamic equilibrium
A system in which state function (P, V, or T)
have constant values throughout the system is
said to be in thermodynamic equilibrium. The
criteria for equilibrium are
(I) Thermal equilibrium
The temperature of the system must be uniform
and must be the same as the temperature of
surroundings
(II) Mechanical equilibrium
No mechanical work is done by one part of the
system on any other part of the system. Thus, the
mechanical properties must be uniform throughout
the system.
(III) Chemical equilibrium
The chemical composition of the system must be
uniform with no net chemical change.
Internal Energy (E (or) U)
 A quantity which represents the total energy
of the system.

 It is the sum of all types of potential and kinetic
energies of constituent particles of a given
substance at given temperature.
 Internal energy of a system depends upon :
a) The quantity of substance,
b) Its chemical nature,
c) Temperature, pressure and volume.
 Internal energy of the system may change,
when
a) Heat passes into or out of the system.
b) Work is done on or by the system.
c) Matter enters or leaves the system.
 The absolute value of internal energy of a
substance cannot be calculated because it is not
possible to determine the exact value for the
constituent energies such as translational, vibra-
tional, rotational energy, etc.
 However, change in internal energy can be
determined experimentally using a bomb
calorimeter.
The derived S.I. unit of internal energy E, is Joule
(J).
 Change in internal energy of a system is :
U  U final - U initial
 For a chemical reaction : U  U products - U reactants
 For a cyclic process : U  0
 For Isothermal process : U  0 , since
temperature is constant
Heat and Work
When a change in the state of a system occurs,
energy is transferred to or from the surroundings.
This energy may be transferred as heat or
mechanical work.
(1) Heat
 Internal energy of a system changes by transfer
of energy from the surroundings to the system or
vice-versa without expenditure of work.
This exchange of energy, which is a result of
temperature difference is called heat, q.
Chemistry Times August 18
 When a system and surroundings are at different
temperatures, then the heat (energy) transfer
continues until the system and the surroundings
reach the same temperature. At this stage, these
are said to be in a state of thermal equilibrium.
 According to the IUPAC convention:
Heat absorbed by the system is positive
Heat given out by the system is negative.
To be more clear:
Heat absorbed in that change = +q
Heat evolved in that change = -q.
 Unit of Heat : SI unit : Joule (J), Calorie (Cal),
Erg (CGS).
1 J = 107 ergs = 0.2390 cal
1 cal = 4.184 J.
(2) Work
 Work is a mode of energy transfer to or from a
system with reference to the surroundings.
 If an object is displaced through a distance dx
against a force of F, then the amount of work done
is defined as W = F  dx
a) Gravitational work = (mg)  h, where m = mass,
g = acceleration due to gravity, h =
height.
b) Electrical work = charge  potential = q  V
c) Mechanical work = Pext (V2 - V1) = Pext V ,
where
Pext = external pressure
V = increase or decrease in volume.
 Work is expressed as the product of two factors,
i.e.,
W = Intensity factor x Capacity factor
Where, intensity factor is a measure of force
responsible for work. Capacity factor is a measure
of extent for which work is done.
 In elementary thermodynamics, the only type of
work generally considered is the work done in
expansion (or compression) of a gas. This is known
as Pressure - Volume work or PV work.
45
Chemistry Times August 18

 The work done by the system is now against

the pressure P2 throughout the whole expansion.
w irr = - P2 (V2 - V1 )
It is important to remember that it is the external
pressure, Pext and not the internal pressure of the
gas itself which is used in evaluating work. It is
true whether it be expansion or contraction.

 Work convention:
Expansion (V2 > V1) : Work done by the system,
W = -ve
Compression (V2 < V1): Work done on the system
, W = +ve

 The positive values of W signify that work has

Thus work done in reversible expansion is greater
been done on the system by the surroundings
than that of irreversible expansion.
and it has contributed to an increase in the internal
(III) Work done in Free Expansion of a gas :
energy of the system.
 Expansion of a gas into vacuum is called free
 The negative values of W indicate that work has
expansion.
been done by the system and it has contributed to
 Work done during free expansion of a gas is zero
a decrease in the internal energy of the system.
since Pext = 0

 Unit of Work : SI unit : Joule (J), Calorie (Cal),

Erg (CGS). Zeroth Law of Thermodynamics or
1L.atm = 101.3 J Law of thermal Equilibrium
(I) Isothermal Reversible Expansion work of a gas  The zeroth law of thermodynamics forms the basis
 The reversible expansion of the gas takes place of concept of temperature.
in a finite number of infinitesimally small  If two systems are in thermal equilibrium with a
intermediate steps where work is observed in third system, they must be in thermal equilibrium
each step. with each other.
 The total amount of work done by the isother-  The zeroth law allows us to introduce the concept
mal reversible expansion of a gas from V1 to of temperature to measure hotness or coldness of
V2 is : a body.
V2
wrev = -2.303nRTlog10 or
V1
P1
w rev = -2.303nRTlog10
P2 Temperature is a measure of intensity of heat
energy i.e., how much energetic each individual
(II) Isothermal Irreversible Expansion work of a gas particle is. The temperature of a sample remains
 The irreversible expansion of the gas takes constant at its melting point, boiling point and
place when the Pext is at once dropped to the phase transition even though heat is being
final pressure P2. supplied.

46

First Law of Thermodyamics
The first law of thermodynamics is, in fact, an
application of the broad principle known as the
Law of conservation of energy to the
thermodynamic systems. It states that,
“ The total energy of an isolated system remains
constant though it may change from one form
to another.”
 First law rules out the existence of a perpetual
motion machine of 1st kind that can work without
consuming any form of energy.
(1) Mathematical statement of the 1st law
 When a system goes from initial state to the final
state, it undergoes a change in the internal energy
from U1 to U2. Thus, U can be written as
U  U 2  U1
 The change in internal energy can be brought
about in two ways:
 Work done under adiabatic conditions is state
function.
 Heat given to a system under constant volume is
state function.
(3) Limitations of first law of thermodyna-
mics
 It does not indicate whether a process occur in a
specific direction without involving any external
agency.
Chemistry Times August 18
(a) Either by allowing the heat to flow into the
system (absorption) or out of the system
(evolution).
(b) By doing work on the system or the work done
by the system.
 Consider a system whose internal energy is U1. If
the system is supplied ‘q’ amount of heat,
the internal energy of the system will become U1+
q.
Now if work ‘w’ is also done by the system, the
final internal energy becomes U2. Thus,
U2 = U1 + q - w or U2 - U1 = q - w
ΔU = q  w
q  Heat absorbed, w  Work done by the
system.
 According to IUPAC : q  dU  w
q = ΔU + PΔV
Some Useful Conclusions from the First Law
 It does not indicate what fraction of one form of
energy is converted into another form inany
transformation.
m It is practically found that whole of heat can
never be converted into work. The first law has
no answer to this observation.
Thus, first law fails to tell extent to which the
interchange of heat into work and vice versa is
possible.
Enthalpy of a system
 In a process carried at constant volume, the heat
content of a system is the same as U, as no PV
47
Chemistry Times August 18
work is done. But in a constant pressure process,
the total heat content of a system is equivalent to
the U plus the PV energy.
H = U + PV
Enthalpy of a system is called total heat content
of the system. It is the net energy available in a
system which can be converted into heat.
 It is impossible to determine the absolute value of
enthalpy.
 The total heat content of a system at constant
pressure and temperature is called its enthalpy
change ΔH = QP , ΔH = ΔU + pΔV
 The most stable state of a substance at 1 atm
and 250C is called its standard state. If an element
exists in different allotropic forms, thermodynami-
cally most stable allotrope has zero enthalpy.
The enthalpies of all elements in their standard
state are taken as zero.
Element stable form (standard state)
Carbon Graphite
Sulphur Rhombic
Phosphorus Black
Relation between H & E :
The difference between H and E is not
usually significant for systems consisting of only
solids and or liquids. Solids and liquids do not
suffer any significant volume changes upon
heating.
The difference, however becomes significant
when gases are involved.
For any chemical reaction, at any constant
temperature, H  U  ng RT
Δn g = n 2 - n1
n2 = total number of moles of gaseous products
n1 = total number of moles of gaseous reactants
(1) Heat capacity (c)
 It is the amount of heat required to raise the
temperature of a system through 1ºC.
 If ‘q’ is the amount of heat supplied to a
system and as a result let the temperature rise
from T1 to T20 C .
48
q q
Then , heat capacity, c = =
m  T2 -T1  mΔT
If m = 1g  c = specific heat
If m = Molar mass  C = Molar heat capacity
(2) Molar heat capacity (C)
 It is the amount of heat required to raise the
temperature of one mole of a system through 1ºC.
Molar heat capacity = Specific heat  molecular
weight of the substance.
 Heat capacity is not a state function. It is, theref-
ore, necessary to specify the process by which
the temperature is raised by one degree.
 For gases, heat capacity is of two types -Heat
capacity at constant volume (CV) and heat
capacity at constant pressure (CP).
(I) Molar Heat Capacity at constant volume (CV) :
From 1st law : dq = dU + PdV
dq dU  PdV
Molar heat Capacity : C  
dT dT
At constant volume dV = 0
 dU  ; dU
C Cv 
 dT
 dT V
 Thus CV is the measure of the change of internal
energy ( ΔU ) of a system with temperature.
ΔU = nC V ΔT
In adiabatic expansion of an ideal gas
ΔU =  W  nCV ΔT  q=0 
(II) Molar Heat Capacity at constant Pressure (CP):
qp
 dH 
CP    
 dT  p dT
 Thus CP gives the measure of the change of
enthalpy ( ΔH ) of a system with temperature.
ΔH = nCP ΔT
CP is always greater than CV : When gas is heated
at constant volume, as the gas is not allowed
to expand, heat is required for raising the
temperature of one mole of a gas through 1o.
When gas is heated at constant pressure, it
expands, the gas has done some work against
external pressure. More heat is, therefore, supplied
to raise its temperature through 1o.
Thus CP > CV for gases, while for liquids and solids
CP = CV

Relation between CP and CV for an ideal gas
 C p  Cv  R
CP
 C   (POISON’S RATIO)
V reaction as
  values depends upon the atomicity of gaseous
molecules
5 3
1. For monoatomic, CP = R and CV = R 
2 2
C 5
  P   1.66
CV 3
Eg : He, Ne, Ar, Kr.
7 5
2. For diatomic, C P = R and C V = R
2 2
  =1.40
Eg : O2, N2, H2 etc.,
3. For triatomic, CP = 4R and CV = 3R   =1.33
Eg : CO2, SO2, K2O2, O3 etc.,
Calorimetry
We can measure energy changes associated with
chemical or physical processes by an experimental
technique called calorimetry. In calorimetry, the
process is carried out in an vessel called
calorimeter, which is immersed in a known volume
of a liquid. Knowing the heat capcity of the liquid
in which calorimeter is immersed and the heat
capacity of calorimeter, it is possible to determine
the heat evovled in the process by measuring
temperature changes. Measurements are made
under two different conditions :
1. At constant volume ( qV )
2. At constant pressure ( qp )
 Experimental measurement of heat output of a
chemical reaction
The heat change that occurs during a chemical
reaction is measured in a simple calorimetric
experiment. Heat produced or consumed are
measured in terms of heat transfer to the
surroundings, usually a closed calorimeter (Bomb
calorimeter). A bomb calorimeter consists of a
heavy walled steel container. The sample is placed
Chemistry Times August 18
inside the container, which is then sealed and
placed in a water bath. An electric current is passed
through the sample to ignite it and the heat given
off by the reaction rises up the temperature of the
entire apparatus. We measure the increase in
temperature and then use the heat capacity of the
calorimeter (the entire assembly) to convert the
change in temperature into heat released by the
Q  mST
Here, ‘m’ is mass of calorimeter content, ‘S’ is
specific heat and T is temperature rise.
Enthalpy of reaction
 The enthalpy change accompanying a reaction is
called the reaction enthalpy (  rH).
 Standard enthalpy of reaction is the enthalpy
change for a reaction when all the participating
substances are in their standard states.
 The standard state of a substance at a specified
temperature is its pure form at 1 bar.
Eg : The standard state of liquid ethanol at 298 K
is pure liquid ethanol at 1 bar.
Standard state of solid iron at 500 K is pure iron at
1 bar.
 A balanced chemical equation together with the
value of its  rH is called a thermochemical
equation.
 Exothermic reactions : A chemical reaction, which
occurs with the evolution of heat.
In Exothermic reaction : HP < HR   rH = -ve
Eg : N2(g) + 3H2(g)  2NH3(g);  rH = - 92 K J
 Endothermic reactions : A chemical reaction,
which occurs with the absorption of heat.
In Endothermic reaction : HP > HR   rH = +ve
Eg : N2(g) + O2(g)  2NO(g) ;  rH = +180.8 K J
 Enthalpy diagram for Exothermic and Endothermic
Reactions
49
Chemistry Times August 18

 If the standard enthalpy of formation is positive,

the compound is called endothermic compound.
Eg:

Enthalpy of reaction refers to entire chemical 1 1

equation and not to any particular reactant or
product.
Factors influencing enthalpy of reaction
 Physical nature of reactants and products
 Reaction carried out at constant pressure or
temperature:
Heat changes at constant pressure are expressed
in terms of  H. Heat changes at constant volume
are expressed in terms of  U.
The two values are however related by,
 H =  U +  ngRT T
 Temperature (Kirchhoff’s equation):
The variation in “H values with temperature are
due to variation in heat capacities of system with
temperature.
d(  H) =  CP..dT
 If temperature range of interest is small or CP is
assumed to be independent of temperature, then
 H2 -  H1 =  CP (T2 - T1)
Similarly,
 U2 -  U1 =  CV (T2 - T1)
Here,
 CP = Sum of CP values of products - sum of CP
values of reactants.
 CV = Sum of CV values of products - sum of CV
values of reactants.
N + O   NO g  ;ΔH=90.4kJ/mol
2 2 g  2 2 g 
 Exothermic compounds are thermodynamically
more stable than endothermic compounds.
 Enthalpy change (  rH) of a reaction can be
calculated from Δ f H of compounds.
Δr H =  Δf HProducts -  Δf HReactants
In some cases enthalpy of reaction and enthalpy
of formation may be same.
(2) Enthalpy of combustion( Δc H )
 The quantity of heat evolved when one mole of a
substance burns completely in excess of oxygen
at a given temperature is called enthalpy of
combustion.
 The enthalpy change per mole of a substance,
when it undergoes combustion and all the reactants
and products being in their standard states at
the specified temperature is known as standard
enthalpy of combustion( Δ c H ).
 It can be used to calculate the calorific value of a
fuel, i.e., amount of heat produced when 1 g of the
substance is completely burnt.

(1) Enthalpy of Formation( Δ f H ) Δ c H of fuel

Calorific Value = MolWt of fuel
 The amount of heat evolved or absorbed when
one mole of a compound formed from its consti-  Enthalpy change (  rH) of a reaction can be
tuent elements at constant temperature is called calculated from Δ c H of compounds.
enthalpy of formation.
 The amount of heat evolved or absorbed, when
one mole of a compound is formed from its Δr H or Δf H =  Δc HReactants -  Δc HProducts
constituent elements in their standard states is
known as the standard enthalpy of formation
( Δ f H ).
 If the standard enthalpy of formation is negative,
the compound is called exothermic compound.
 Enthalpy of combustion is always exothermic in
Eg :
nature, i.e.,  H = -ve.
C graphite +O2 g 
 CO2 g ;ΔH=-393.5kJ/mol

50

 Some reactions which involve reaction with oxygen
with absorption of heat, although these are not
enthalpy of combustion data because partial
combustion has takes place.
N2 + O2  2NO;  H = +ve
Reaction with F2 with O2 is also not heat combu-
stion because F2 is reduced and not oxidised.
(3) Enthalpy of Neutralisation
 The quantity of heat evolved, when one gram
equivalent of a base is completely neutralised
byone gram equivalent of an acid in aqueous
solutions, is known as the heat of neutralisation.
 The heat evolved, when 1 g equivalent of H+ ions
react with 1 g equivalent of OH - ions in aqueous
solutions to form one mole of water, is known as
heat of neutralisation.
H+ (aq) + OH- (aq)  H2O (l) ;  H = -57.3 kJ
 The heat of neutralisation is maximum, when a
strong base is neutralised by a strong acid.
Heat evolved is 57.3 kJ (or) 13.7 kcals.
Eg : HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(l) ;
 H = -57.3 kJ
 If the acid or base or both are weak, the heat
evolved is less than 57.3 kJ or 13.7 kcal
Eg: CH3COOH(aq) + NaOH(aq) 
CH3COONa(aq) +
H2O(l) ; H = -55.22 kJ
Heat of ionisation of weak acid/base = Enthalpy of
neutralisation + 57.3
Thus, heat of ionization of CH3COOH = -55.22 +
57.3 kJ = + 2.08 kJ.
(4) Enthalpy of Solution (  sol H )
 The Enthalpy change when one mole of substance
is dissolved in a specified amount of solvent is
called enthalpy of solution.
 The enthalpy of solution at infinite dilution is the
enthalpy change observed on dissolving the
substance in an infinite amount of solvent when
the interactions between the ions are negligible.
Chemistry Times August 18
 The enthalpy of solution of AB(s), sol H , in water
is, therefore, determined by the selective values
of the lattice enthalpy,  sol H and enthalpy of
hydration of ions,  sol H as  sol H =
 lattice H + hyd H .
 For most of the ionic compounds,  sol H  is
positive and the dissociation process is endothe-
rmic. Therefore, the solubility of most salts in water
increases with rise of temperature. If the lattice
enthalpy is very high, the dissolution of the
compound may not take place at all.
(5) Enthalpy of ionisation in aqueous
solutions
 The enthalpy change in the formation of an ion at
unit activity (or concentration) from its elements
in aqueous solution is enthalpy of
ionisation.
 The absolute value is not possible. Therefore,

the enthalpy of H  aq  at 298 K is taken as zero
arbitarily
1/ 2 H 2 g   aq  H aq   e ; H 0  0.0 KJ
 The enthalpy of formation of other ions are

determined relative to this value of zero for H  aq 
Eg: For OH  it is -228.51 KJ
(6) Enthalpy of Dilution
 The change of enthalpy when a solution
containing one mole of a solute is diluted from
one concentration to another is called enthalpy
of dilution.
 When a solution is so dilute that further dilution
causes no noticeable heat change, the solution
is said to be at infinite dilution.
(7) Enthalpy of Hydration ( Hyd H )
 The enthalpy change accompanying the hydrati-
tion of one mole of an anhydrous salt by combi-
ning with specific number of moles of water.
CuSO4( s )  5 H 2 O( l )  CuSO4 .5 H 2 O( s ) ;
H  78.2 K .J
CaCl 2 l   6H 2 O l  
 CaCl 2  6H 2 O ;
H=-18.8 kcal
51
Chemistry Times August 18
It is always exothermic.
(8) Enthalpy of atomisation(  a H  )
 The heat required to dissociate one mole of a
simple molecule in the gaseous state into its
constituent atoms is called enthalpy of
atomisation.
 This is an endothermic process.
Eg: H 2 g   2 H  g  ; H  43.51kJ
O2 g   2O g  ; H  489.5 kJ
N 2 g   2 N g  ; H  937.4kJ
(9) Enthalpy of phase transition
 The heat change involved in the change of phase
or physical state of one mole of compound at
atmospheric pressure is called enthalpy of phase
transition.
 Different phase transitions taking place are
Solid - Liquid (fusion or melting)
Liquid - Gas (Vapourisation)
Liquid - Solid (Freezing)
Solid - Gas (Sublimation)
One crystalline form  Another crystalline form
Eg :   sulphur    sulphur
C s   C g  ; H  1439.2 KJ
S monoclinic   S r hom bic  ; H  2.5 KJ
S r hom bic   S monoclinic  ; H  2.5 KJ
 All these phase changes occur on change of
temperature at atmospheric pressure.
(I) Molar enthalpy of fusion
The enthalpy change that accompanies melting of
one mole of a solid substance in standard state is
called standard enthalpy of fusion or molar
enthalpy of fusion  fus H
H 2 O( s )  H 2O(l ) ;  fus H  6.00KJmol 1
(II) Molar enthalpy of vapourisation 
Amount of heat required to vapourise one mole of
a liquid at constant temperature and under
standard pressure (1bar) is called its standard
52
enthalpy of vapourisation.
H 2O(l )  H 2O( g ) ; vap H   40.79 KJmol 1
(III) Molar enthalpy of sublimation
 Conversion of a substance in the solid state into
the gaseous state directly on heating is known as

sublimation. Solid   Gas
 The amount of heat required to convert one mole
of a simple substance in the solid state
into the gaseous state without decompositi-
tion of the substance is called molar enthalpy
of sublimation.
 This process is an endothermic process
 H  ve 
Eg:

 Solid I 2   I 2 vapour

 Naphthalene s    Naphthalene g 
 Solid CO2 or “dry ice” sublimes at 195K with
 sub H    25.2 kJmol 1
 Sublimation is possible only if the pressure at
which heating is carried out is much below the
triple point pressure of the compound subliming.
  sub H   fus H   vap H
(10) Bond Enthalpy
 When a bond is formed between atoms, e n e r g y
is released. Obviously same amount of energy
will be required to break the bond called Bond
enthalpy.
 The amount of energy required to break 1 mole
of a particular bond in a given compound and to
separate the resulting gaseous atoms or ions or
radicals from one another is bond dissociation
enthalpy.
 2Cl g  ;Δ Bond H=242 kJmol-1
Cl 2 g  
 The bond dissociation energy in polyatomic
vap H  molecules will be only average value, because in
each step of dissociation different fragments are
involved.
Eg: In water molecule

H 2 O g  
 H  g  +OH  g  ;ΔH=501.87kJmol
 O g  +H g  ;ΔH = 423.38kJmol-1
OH g  
501.82+423.38
Δ Bond H = kJmol-1 = 462.6 kJ
2
mol-1
 Enthalpy change (  rH) of a reaction can be
calculated from Δ Bond H of bonds in compouds.
Δr H =  ΔBond HReactants -  ΔBond HProducts
Laws of Thermochemistry
(1) Lavoisier and Laplace law
The enthalpy of decomposition of a compound
is numerically equal to the enthalpy of ``formation
of that compound with opposite sign.
CO2( g )  C( s )  O2( g ) ; H  94.3K .cal
C  O2  CO2 ; H  94.3 kcal
(2) Hess’s law of constant heat summation
 The heat energy released or absorbed in a process
is same whether the process occurs in one step or
in several steps. This is known as H e s s ’s
law of constant heat summation.
 According to Hess’s law, the heat energy released
or absorbed in a process depends only on the
initial state and final state but not on the path, in
which the process occurs.
 Hess’s law is applicable to both physical and
chemical changes.
 Hess law is an application of first law of
thermodynamics or law of conservation of energy.
1  q1  q2  q3
 Applications of Hess’s law: Used to determine
(I) Heat formation of intermediate compounds
which are unstable and it cannot be isolated.
(II) Heat of combustion of a substance
(III) Heat of transition
(IV) Lattice energy of ionic compounds
Spontaneous Process
 A process is said to be spontaneous if it occurs
on its own without the intervention of any external
agency of any kind.
Chemistry Times August 18
Eg: Flow of heat from high temperature to low
-1 temperature.
Flow of water from high level to low level.
Flow of gas from high pressure to low pressure.
Spontaneous (or) natural processes are
thermodynamically irreversible.
 The phenomenon like flow of water down hill or
fall of a stone on to the ground. We find that there
is a net decrease in potential energy in the direction
of change.
(1) Criteria for spontaneity
 By analogy, we may be tempted to state that a
chemical reaction is spontaneous in a given
direction, because decrease in energy has taken
place, as in the case of exothermic reaction.
Eg:
1 3
N2  g   H 2  g   NH 3  g  ; r H   46.1kJmol 1
2 2
 Thus, the postulate “Driving force for a chemical
reaction may be due to decrease in energy”
 The following reactions are spontaneous even
though they are endothermic.
1
N 2  g   O2  g   NO2  g  ;  r H   33.2kJmol 1
2
C  graphite, s   2S  l   CS2  l  ;  r H   128.5kJmol 1
 Therefore, decrease in enthalpy may be contri-
butory factor for spontaneity, but it is not true for
all cases.
 Nature tends to move spontaneity from a state of
lower probability to one of higher probability, i.e.,
things tend to change from organised to disorg-
anised.
 Thus, the second factor which is responsible for
the spontaneity of a process is the tendency to
acquire maximum randomness.
Driving Forces for Spontaneous Processes
Tendency of a system to achieve a state of
minimum energy.
53
Chemistry Times August 18

 Tendency of a system to achieve a state of

T1 Q
maximum randomness (entropy).   1  1 1
 The overall tendency of a process to be T2 Q2
spontaneous depends on the resultant of the Where Q2 is the heat absorbed from the source at
above two factors. The resultant of the two
tendencies or overall tendency for a process to T2 and Q1 is the heat lost to the sink at T1 .
occur is termed the driving force. Thus “it is impossible to convert heat into
q Here, it should be noted that these tendencies are equivalent amount of work without compensatio-
independent of each other. Both may act in the n”.
same or in opposite directions in a process.
a)   1100%efficiency  only when
Case I: When enthalpy factor is absent then
randomness factor decides spontaneity of a T1  0 K  i.e., 2730 C  which is not practically
process.
Case II: When randomness factor is absent then possible
enthalpy or energy factor decides spontaneity of b) Greater the difference between T2 and T1
a process greater is the value of  . Hence superheated
Case III: When both factors takes place steam (under high pressure) is used in an
simultaneously then magnitude of the tendencies engine with a boiler.
becomes important to decide spontaneity.

Second law of Thermodynamics Entropy (S)

 Entropy is a measure of randomness (or ) disorder
 All spontaneous processes are thermodynamica-
of the particles of a system.
lly irreversible and entropy of the system
 It depends on the temperature, pressure of the
increases.
state.
 Heat cannot flow from a colder body to a hotter
 Entropy is a state function and is an extensive
body on its own.
property
 It is impossible to construct a machine working in
cycles and transfers heat from a lower temperature  S =  Sfinal–  Sinitial
region to a higher temperature region without =  Sproducts –  S reactants ( for a chemical reaction)
intervention of an external agency (such an
V2
imaginary machine is called perpetual motion nRT log e
machine of second kind). q W V1 V2
 S  rev  rev   nR log e
 Heat cannot be converted into work completely T T T V1
without causing some permanent changes in the
system or in the surroundings. V2 P
 2.303 nR log10  2.303 nR log10 1
 It is impossible to take heat from a hot reservoir V1 P2
and convert it completely into work by a cyclic
process without transferring a part of it to a cold Where, qrev is the heat supplied to a system at
reservoir (Carnot) temperature T(K) under reversible conditions.
 At constant P, qrev  H rev
 The entropy of a system increases when it absorbs
heat. Entropy of a system also increases during
isothermal expansion.
  S is more +ve when the system absorbs heat at
lower temp rather that at higher temp.
 Carnot cycle having efficiency   Units of S and  S are J.K-1. mol-1
 At a given temp Sgas > Sliquid > Ssolid
W T2  T1 Q2  Q1
  
Q2 T2 Q2

54
 Chemistry Times August 18

(1) Standard entropy liquid changes to vapour at its boiling point.

 Entropy of one mole of a substance in pure state H vapourisation
at one atmosphere and 250 C (298K) is t e r m e d Svapourisation =
Boiling po int( K )
as standard entropy, represented as S 0 (III) Entropy of sublimation
 For a reaction in standard state, A  B It is the change of entropy when one mole of solid
changes into vapour at a particular temperature.
S 0  S B0  S A0 or
H sub
S 0   S 0(products)   S 0(reactants)  Ssub = Svapour – Ssolid 
T
(2) Entropy and spontaneity (5) Calculation of entropy in chemical
 Entropy, S, is related to thermodynamic probability, reactions
W by the relation: For the general reaction
S  k log e W  2.303k log10 W pA  qB  mC  nD
Where k is Boltzmann’s constant
S 0 is given by,,
 For a spontaneous process in an isolated system
S 0   mS c0  nSc0    pS A0  qS B0 
 S>0 i.e., positive.
 When a system is non isolated the entropy S 0 are molar entropies
changes of the surroundings also must be
Eg: For a reaction H2(g) + 1/2O2(g)  H2O(l)
considered.
Then  STotal =  Ssystem +  S surroundings(for a  1 
S 0  SH0 2O ( l )   SH0 2 ( g )  SO02 ( g ) 
spontaneous process  Stotal > 0).  2 
 When  S is +ve, the process is spontaneous. (6) Entropy Change in irreversible
 When  S is -ve, the process is non -spontaneous. processes
 When  S = 0, the process is in equilibrium. Consider a system at higher temperature T1 and
(3) Entropy change in exothermic and its surroundings at lower temperature T 2. ‘q’
amount of heat goes irreversibly from system to
endothermic reactions
surroundings.
 In exothermic reactions heat released by the
reaction increases the disorder of the surroundings q
Ssystem 
and overall entropy change is positive. T1
 S  ve  q
 In endothermic reactions heat flows from the Ssurroundings 
T2
surroundings into the system. The entropy of the
surroundings decreases and the system increases. Sprocess  Ssystem  Ssurroundings
Total entropy change is positive hence the change
is spontaneous. q q
 
(4) Entropy Change during Phase T1 T2
Transformation
 T  T2 
(I) Entropy of fusion  q 1 
It is the change in entropy when one mole of a  T1T2 
solid changes to a liquid at its melting point.
But T1  T2 ,  T1  T2   ve
qrev H fusion
S fusion  S  melting po int( K ) or Sprocess  0
T
Hence, entropy increases in an irreversible process
(II) Entropy of vapourisation
It is the change in entropy when one mole of a

55
Chemistry Times August 18

Gibb’s energy (or) Gibb’s function (G)

 H  ve may be a condition but not a necessa-
ry and sufficient condition for the spontaneous
nature of a reaction.
 S  ve may also be a condition but not a
 Change in entropy for an ideal gas under different necessary and sufficient condition for the
conditions may be calculated as: spontaneous nature of the reaction.
Entropy change for ideal gas  To explain spontaneity, Gibbs introduced another
(i) when changes from initial state (1) to state (2) thermodynamic function involving both enthalpy
(H) and entropy (S) functions. This is known as
T  V  free energy function (G)
S  2.303 nCV log  2   2.303 nR log  2   G is referred as Gibbs energy (or) Gibbs function.
T
 1  V1   G is represented as G  H  TS
(when T and V are variables)  Gibb’s function, G is an extensive property and is
a state function.
T  P   The change in Gibb’s energy for the system, Gsys
S  2.303 nCP log  2   2.303 nR log  2 
T
 1  P1  can be written as
(when T and V are variables) Gsys  H sys  T S sys  S sys T
(ii) Entropy change for isothermal process :  At constant temperature T  0
V   Gsys  H sys  T S sys
S  2.303 nR log  2 
 V1   The subscript ‘system’ is dropped and write this
equation as
P  G  H  T S
S  2.303 nR log  1 
 P2  The above equation is referred to as the Gibb’s
equation.
Entropy change for isobaric process (at constant
G has units of energy because, both H and
P) :
the T S are energy terms, since T S =(K) (J/K)=J.
T 
S  2.303 nC P log  2   We know, Stotal  S sys  S surr
 T1  If the system is in thermal equilibrium with the
surroundings, then the temperature of the
V 
S  2.303 nCP log  2  surroundings is same as that of the system.
 V1  Thus, increase in enthalpy of the surroundings is
(iv) Entropy change for isochoric process (at equal to decrease in the enthalpy of the system.
constant V) : Therefore, entropy change of surroundings,

T  H surr H sys

S  2.303 nCV log  2  S surr  
T T
 T1 
 H sys 
P  Stotal  S sys    
S  2.303 nCV log  2   T 
 P1 
Rearranging the above equation:
(v) Entropy change in mixing of ideal gases :
T Stotal  T S sys  H sys
S  2.303 R  n1 log x1  n2 log x2 
For spontaneous process, Stotal  0,
 Entropy change in adiabatic expansion will be zero,
S  0 T S sys  H sys  0

56
 Chemistry Times August 18

taken into account, the value of K extent of

   H sys  T S sys   0
chemical reaction will also be affected, depend-
Using G  H  T S equation the above ing upon whether  r S is positive or negative.
equation can be written as G  0
(2) Free energy change and electrical work
G  H  T S  0 done in a cell
 H sys is the enthalpy change of a reaction. G  nFE
T S sys is the energy which is not available to do F = Faraday = 96,500 coulombs,
E = E.M.F of the cell ,
useful work. So, G is the net energy available to n = no.of electrons involved in balanced
do useful work and is thus a measure of the ‘free electrochemical reaction.
energy’. For this reason, it is also known as the
free energy of the reaction. G 0  nFE 0
 G gives a criteria for spontaneity at constant E 0 =standard E.M.F of the cell
pressure and temperature. (3) Effect of enthalpy, entropy and temper-
(a) If G is negative (< 0), the process is ature on the spontaneity of a proces
spontaneous.
(b) If G is positive (< 0), the process is non
spontaneous.
(c) Standard Gibb’s free energy G  of a reaction
can be calculated from the following equation.
 r G    f G (products)    f G (reactants)
(1) Gibb’s energy change and equilibrium
  r G is related to the equilibrium constant of
the reaction as follows:
Δ r G   -RT ln K
G  2.303RT log Keq
K eq  equilibrium constant
ΔG  Third law of Thermodynamics
Keq = e-ΔG/RT (or) K = 10- 2.303RT  This is also known as NERNST HEAT
eq
THEOREM.
 For strongly endothermic reactions, the value of It was proposed by Max Plank W.Richard & Walter
 r H may be large and positive. In such a case, in different forms.
value of K will be much smaller than 1 and the  “The entropy of a pure and perfectly ordered
reaction is unlikely to form much product. substance is zero at the absolute zero
temperature.(-2730C)
 In case of exothermic reactions,  r H is large and
SlimT 0  0
negative, and  r G is likely to be large and
 Third law imposes a limitaion on entropy value
negative too. In such cases, K will be much larger but not leads to any new thermodyamic concept.
than 1.  Absolute entropy of a substance at a temperature
 We may expect strongly exothermic reactions to T,
have a large K, and hence can go to near
T
completion.  r G also depends upon rS, if CP
ST   dT
T
the changes in the entropy of reaction is also 0

57
Chemistry Times August 18

2. A thermodynamic state function is a quantity

 Accurate determination of energy  ST  requires
(a) Used to determine heat changes
that the heat capacity at constant pressure  CP  (b) Whose value is independent of path
(c) Used to determine pressure-volume work
must be determined accurately. But  CP  cannot (d) Whose value depends on temperature only
3. The initial state A has the temperature TA,UA as
be measured at absolute zero  273 C 
0
(or) the internal energy of the system. By applying the
around absolute zero. mechanical work, new state B is achieved with the
temperature TB and having the internal energy UB.
 CV value at absolute zero is obtained by using Given that TB > TA What is the correct expression
the extra polating technique and the “Debye
for the change in internal energy  ΔU  ?
equation”.
Debye equation : (a) U B  U A (b) U B  U A
Cv = aT3
a = Constant for a substance (c) U A  U B (d) None of these
 At the vicinity of absolute zero Cp = Cv 4. Identify the state function among the following:
Hence absolute value of ‘S’ can be calculated using (a) q (b) q - w (c) q/w (d) q+w
Cv value. 5. If a refrigerator’s door is kept open, then
(a) Room will be cooled
(b) Room will be heated
(c) May get cooled or heated depending upon the
weather
(d) No effect on room
6. What will be the work done on an ideal gas
enclosed in a cylinder, when it is compressed by a
Clapeyron-Clausius equation represents the constant external pressure, Pext in a single step as
variation of vapour pressure with temperature. shown in fig?
(or boiling point with pressure)
d ln P ΔH v
=
dT RT2
Van’t Hoff isochore represents the variation of
equilibrium constant with temperature.
d ln K p ΔHo
=
dT RT2 (a) (b)

LEVEL-1 (c) (d)

1. Thermodynamics is not concerned about
(a) Energy changes involved in a chemical reaction.
(b) The extent to which a chemical reaction 7. The work done in ergs for the reversible expansion
proceeds. of one mole of an ideal gas from a volume of 10
(c) The rate at which a reaction proceeds.
litres to 20 litres at 250 C is
(d) The feasibility of a chemical reaction.

58
 Chemistry Times August 18

(a)- 2.303  298  0.082 log 2 3. For a gaseous reaction

2 A2 ( g )  5 B2 ( g )  2 A2 B5 ( g )
(b)- 298  107  8.31 2.303 log 2
at 27C the heat change at constant pressure is
(c) 2.303  298  0.082 log 0.5 found to be -50160 J. Calculate the value of internal
(d) 2.303  298  2 log 2. energy change (E ). Given that
8. A system is provided 50 J of heat and work done R  8.314 J / K mol.
on the system is 10 J. The change in internal energy
during the process is (a) -34689 J (b) - 37689 J
(a) 40 J (b) 60 J (c) 80 J (d) 50 J (c) -27689 J (d) -38689 J
9. A gas absorbs 250 J of heat and expands from 1 4. In the reaction :
litre to 10 litre at constant temperature against CS2 l  +3O 2 g   CO 2 g  +2SO2 g  ; ΔH=  265 kcal
external pressure of 0.5 atm. The values of w and The enthalpies of formation for both CO2 and SO2
ΔU will be respectively.. are negative and are in the ratio 4 : 3. The enthalpy
(a) 455 J, 710 J (b) -455 J, -205 J of formation for CS2 is + 26 kcal/mol. The enthalpy
(c) -455 J, -710 J (d) 455 J, 205 J of formation for SO2 is
10. The molar heat capacity of water in equilibrium (a) 90 kcal/mol (b) 52 kcal/mol
with ice at constant pressure is :
(c) 78 kcal/mol (d) 71.7 kcal/mol
(a) Zero (b) Infinity
(c) 40.45 J/(K mol) (d) 75.48 J/(K mol) 5. The standard heats of formation for CCl( g ) , H 2 O( g ) ,
CO2( g ) and HCl( g ) are 25.5, 57.8, 94.1 and
LEVEL-2
1. The state functions out of the following : 22.1 kcal respectively. Calculate H (298 K ) (in
Enthalpy, entropy, heat, temperature, work, free
kcal) for the reaction :
energy.
(a) Enthalpy, Entropy, Temperature CCl4( g )  2 H 2 O( g )  CO2( g )  4 HCl( g )
(b) Heat, Work (a) -41.4 (b) 41.4 (c) 4.14 (d) 414
(c) Enthalpy, Entropy, Temperature, Free energy
(d) Free energy, Heat, Work
2. In Harber’s process of ammonia manufacture :
N 2 g  +3H 2 g   2NH3 g  ; H250 C =  92.2 kJ

Molecule N 2 g  H 2 g  NH3 g  LEVEL-1

CPJ/(K mol) 29.1 28.8 35.1 1. c 2. b 3. b 4. d 5. b
If CP is independent of temperature, then reaction 6. a 7. b 8. b 9. b 10. b
at 100C as compared to that of 25C will be :
(a) More endothermic (c) Less endothermic LEVEL-2
(c) More exothermic (d) Less exothermic 1. c 2. c 3. b 4. d 5. a

59
Chemistry Times August 18

By: A.N.S. SANKARA RAO (Hyderabad)

OXY ACIDS

Learning structural aspects, reactions of 29 oxyacids N(4), P(10), S(11) and Cl(4) is very easy and are
very important for competitive as well as, state, central board exams.

Trick to write structures: Follow the order It is due to decrease of E.N. down the group.
Central atom  Oxygen  Hydrogen  No. of  Conc.HNO3 oxidises C to H2CO3, S8 to H2SO4, P4
bonds. to H3PO4, I2 to HIO3.
No. of bonds formed by H=1, O=2, N=3 or 4  dil.HNO3 is reduced to NO (with H2S, SO2, Cu,
(If L.P. also form a dative bond), S=2 or 4 or 6, Hg, Ag, Pb, FeSO4), N2O (when reaction
P=3 or 5, Cl = 1 or 3 or 5 or 7. between Zn and hot, dil HNO3).
I. Oxyacids of N  Conc.HNO3 is always reduced to NO2
1. HNO or H2N2O2 Hypo Nitrous ous acid 3Cu  8HNO3 (dil )  3Cu ( NO3 ) 2  4 H 2 O  2NO
(Oxi. state of N = +1)
4 Zn  10 HNO3 (dil , hot )  4Zn( NO3 ) 2  5H 2 O  N 2 O
HO-N=N-OH
2. HNO2 Nitrous
ous acid (+3) Zn  4 HNO3 (Conc.)  Zn( NO3 ) 2  2 H 2 O  2NO2
HO-N=O  Fe Cr, Ni, Al become passive in conc.HNO3 (due
3. HNO3 Nitric
ic acid (+5) to formation of thin protective layer of metal
oxide)
II. Oxyacids of P
 P of oxyacids undergo sp3 hybridization.
4. HNO4 Per nitric
ic acid (+5)  P-H bonds are responsible for reduction.
 P-OH bonds are responsibile for acidic nature.
 P forms phosphorous (or phosphonic) or
phosphoric acids.
- O - O - peroxy bond is present
 P=O, P-OH (or P-H) bonds are common in all
Oxidation state of peroxy oxygen = -1,
oxyacids, whereas some oxyacids contain P-P bond
Normal oxygen = -2
(eg: H4P2O6), P-O-P bonds [eg: H4P2O5, H4P2O7,
 O.S of N = +1-1-1+x-2-2=0 (HPO3)n] and peroxy bond (H3PO5 & H4P2O8)
 O.S. of N = +5 1. HPO2 Meta phosphorous ous acid (+3)
 N of oxyacids undergo sp2 hybridization
HO-P=O
 In nitration mixture, HNO3 acts as base as it
2. HPO3 Meta phosphoric ic acid (+5)
donates OH-,
 
H O  N O2  H  HSO4   H 2 O  NO2   HSO4 
 Order of Acid strength & solubility:
HNO3  H 3 PO4  H 3 AsO4  H 3 SbO4

60
 Chemistry Times August 18

 Trimer of HPO3  It has P-O-P linkage

 It has 3 P-O-P bonds.  Dibasic
 This structure is similar to benzene  Strongly reducing
 Write 3 times P-O in ring form, then write =O and 8. H4P2O6 Hypo phosphoric
ic acid (+4)
- OH.
3. H3PO2 Hypo phosphorous ous acid (+1)

 Tetrabasic
 Hygroscopic (attracts water)
 It is powerful reducing agent  Does not show reducing property
 Monobasic  On heating disproportionates into HPO3 &
 Disproportionates at high temp. into H3PO4 & H3PO3
PH3 9. H4P2O7 Pyro phosphoricic acid (+5)

2H 3 PO2   H 3 PO4  PH 3
4. H3PO3 Phosphorousous or phosphonic
nic acid (+3)

 Tetrabasic
 P-O-P linkage
 On strong heating gives HPO3
 It is dibasic 10. H4P2O8 Peroxo diphosphoric acid (+5)
 It is obtained by hydrolysis of P4O6
 It disproportionates on heating
4 H 3 PO3  3H 3 PO4  PH 3
5. H3PO4 (ortho) Phosphoric ic acid (+5)
 Tetrabasic
 P-O-O-P linkage (peroxy bond)
III. Oxyacids of “S”
 S of oxyacids undergo sp3 hybridization.
 Double bonds present in oxyacids of P, S, Cl are
 It is tribasic acid d  p
 It is obtained by hydrolysis of P4O10.
 On heating gives HPO3 & H4P2O7 1. H2SO3 Sulphurous
ous acisd (+4)
525 K 875 K
2 H 3 PO4 
 H 2O
 H 4 P2 O7 
 H 2O
 2 HPO3
6. H3PO5 Peroxo phosphoric
ic acid (+5) 2. H2SO4 Sulphuric ic acid (+6)
(or) oil of vitriol

 It has peroxy linkage (-O-O-)

7. H4P2O5 Pyro phosphorous ous acid (+3) 3. H2SO5 Peroxo mono sulphuric
ic acid (+6)
(or) caro’s acid

61
Chemistry Times August 18

contains -O-O- bond. 10. H2S2O7 Pyro sulphuric ic acid (or) oleum or
4. H2S2O2 Thionous or Thio sulphurous
ous acid (-2, Disulphuric acid (+6, +6)
+4)

 S=S linkage
 Trick: Structure is similar to H2SO3 just replace
O with S(becomes thio)
5. H2S2O3 Thionic or Thio sulphuric ic acid (-2, +6)

 S-O-S linkage
11. H2S2O8 Peroxo di sulphuric
ic acid (or)
Marshall’s acid (+6, +6)
 S=S linkage
6. H2S2O4 Di Thionous
ous acid (+3, +3)

 S-S linkage
 Dehydrating agent
 Show charring action with carbohydrates
 Hot, conc.H2SO4 gives SO2 with Cu, S, C.
7. H2S2O5 Pyro sulphurous
ous acid (+3, +5)  Contains S-O-O-S i.e., peroxy -O-O- linkage is
present.
 Oxyacids contain
S-S linkage = H2S2O4, H2SO5, H2S2O6
S-O-S linkage = H2S2O7
S=S linkage = H2S2O2, H2S2O3
-O-O- linkage = H2SO5, H2S2O8
IV. Oxyacids of “Cl”
 Cl in oxyacids undergo sp3 hybridisation
 All are monobasic
 Acid strength  E.N  No. of “O” atoms
 S-S linkage  Acid strength & thermal stability:
8. H2S2O6 Di thionic
ic acid (+5, +5) HClO > HBrO > HIO,
HClO4 > HBrO4 > HIO4,
HClO4 > HClO3 > HClO2 > HClO
 Hypohalites disproportionate in aqueous solution
on heating
300 K
3OX    3 X   XO3
9. H2Sn+2O6 Poly thio ic acid (0, +5)
thionic
 Rate of disproportionation: IO   BrO   ClO 
 Oxidising power:
HOCl  HClO2  HClO3  HClO4

No. of L.P.S: HOCl

3
 HClO2  HClO3  HClO4
2 1 0

Bond angles:
HClO2  HClO4  HClO3  HClO
(1110 ) 109 28 '
0
0
106 
0 103 

62
 Chemistry Times August 18

1. HOCl Hypo chlorous acid (+1) 3. PCl5 reacts with water to form a compound X.
Bent Basicity of X is
(a) 1 (b) 2 (c) 3 (d) 4
(but bond angle in ClO- is 1800 and shape is
linear) 4. Number of S  S bonds in SO3 trimer is
2. HClO2 Chlorous acid (+3) (a) 0 (b) 1 (c) 2 (d) 3
5. S  S linkage is present in
(a) H 2 S2O4 (b) H 2 SO5

 Disproportionates (auto-oxidation) into (c) H 2 S2O6 (d) H 2 S2O3

HClO & HClO3 6. S  O  S linkage is present in
2 HClO2  2 HClO  HClO3 (a) H 2 S2O6 (b) H 2 S2O7
 Angular (c) H 2 S2O8 (d) H 2 S n  2 O6
 Bond angle 1110
3. HClO3 Chloric acid (+5) 7. In OF2 molecule, total number of bond pairs and
lone pairs of electrons present respectively are
(a) 2, 8 (b) 2, 0 (c) 2, 10 (d) 2, 9
8. p  d  bonding is found in
 Pyramidal
(a) CO32 (b) SO32 (c) NO3 (d) BO33
 Bond angle 1060
4. HClO4 Per chloric acid (+7) 9. The oxidation numbers of S in H 2 S2O8 is
(a) 7, 7 (b) 6, 6 (c) 7, 6 (d) 5, 6
10. Incorrect acid strength among the following is
(a) HF  H 2 O  NH 3
(b) HClO3  HClO2  HClO
 Tetrahedral (c) HIO4  HBrO4  HClO4
 Bond angle 1090 28'
(d) HI  HBr  HCl
11. Strongest reducing agent among the following is
1. Aprotic acid among the following is
(a) H 3 PO2 (b) H 3 PO3 (c) H 3 PO4 (d) H 4 P2 O7
(a) SO (OH )2 (b) SO2 (OH )2
(c) PO (OH )3 (d) B (OH )3
2. The acid that can give 3 series of salts among the
following is
1. d 2. c 3. c 4. a 5. d
(a) H 3 PO2 (b) H 3 PO3
6. b 7. a 8. b 9. b 10. c
(c) H 3 PO4 (d) H 2 SO4 11. a

RANK EDGE AKADEMI OF CHEMISTRY

Deepthisri nagar, Hyderabad.
Mobile
M obile No: 9848685179
Email: rasayanam.Jeeneet@gmail.Com

63
Chemistry Times August 18

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