INTRODUCTION

The word thermodynamics implies flow of heat. It deals with energy changes accompanying all
types of physical and chemical processes.
It helps to lay down the criteria for predicting feasibility or spontaneity of a process, including a
chemical reaction, under a given set of conditions. It also helps to determine the extent to which a
process, including a chemical reaction, can proceed before attainment of equilibrium.
Thermodynamics is based on two generalizations called the first and second law of
thermodynamics. These are based on human experience.
SOME BASIC TERMS
System
system is defined as any specified portion of matter under study which is separated from the
rest of the universe with a bounding surface. system may consist of one or more substances.
Surroundings
The rest of the universe which might be in a position to exchange energy and matter with the
system is called the surroundings.
Types of system
(i) Isolted system
system which can exchange neither energy nor matter with its surrounding is called an isolated
system.
(ii) Open system
system which can exchange matter as well as energy with its surroundings is said to be an
open system.
(iii) Closed system
system which can exchange energy but not matter with its surroundings is called a closed
system.
M!ros!opi! properties
The properties associated with a macroscopic system !i.e. consisting of large number of particles"
are called macroscopic properties. These properties are pressure, volume, temperature,
composition, density etc.
E"tensi#e nd Intensi#e properties
n extensive property of a system is that which depends upon the amount of the substance
present in the system li#e mass, volume and energy.
n intensive property of a system is that which is independent of the amount of the substance
present in the system li#e temperature, pressure, density, concentration, viscosity, surface
tension, refractive index etc.
Stte of system
$hen macroscopic properties of a system have definite values, the system is said to be in
definite state. $henever there is a change in any one of the macroscopic properties, the system
is said to change into a different state. Thus, the state of a system is fixed by its macroscopic
properties.
Stte #ri$les
%ince the state of a system changed with change in any of the macroscopic properties, these
properties are called state variables or the thermodynamics parameters which depends only upon
the initial and final states of the system and independent of the manner as to how the change is
brought are called state functions. %ome common state functions are internal energy, enthalpy,
entropy, free energy, pressure, temperature, volume etc.
T%ermodynmi! e&uili$rium
system in which the macroscopic properties do not undergo any change with time is said to be
in thermodynamic equilibrium.
T%ermodynmi! pro!ess nd t%eir types
The operation by which a system changes form one state to another is called a process.
$henever a system changes from one state to another it is accompanied by change in energy. In
case of open systems, there may be change of matter as well.
T%e follo'ing types of pro!ess re (no'n
Isot%erml pro!ess
process is said to be isothermal if the temperature of the system remains constant during each
stage of the process.
Adi$ti! pro!ess
process is said to be adiabatic if the heat enters or leaves the system during any step of the
process.
Iso$ri! pro!ess
process is said to be isobaric if the pressure of the system remains constant during each step
of the process.
Illustration 1. Thermodynamics is concerned with
(A) total energy in a system (B) energy changes in a system
(C) rate of a chemical change (D) mass changes in nuclear reactions
Solution: (B)
Iso!%ori! )ro!ess
process is said to be isochoric if the volume of the system
remains constant during each step of the process.
Re#ersi$le nd Irre#ersi$le pro!ess
process which is carried out infinitesimally slowly in such a
manner that the system remains almost in a state of
equilibrium at every stage or a process carried out
infinitesimally slowly so that the driving force is only
infinitesimally greater than the opposing force is called a
reversible process.

Iso$ri!
Isot%erml
Adi$ti!
*olume
)
r
e
s
s
u
r
e

I
s
o
!
%
o
r
i
!


ny process which does not ta#e place in the above manner i.e. a process which does not ta#e
place infinitesimally slowly, is said to be an irreversible process.
In fact, all the natural processes are irreversible processes.
INTERNA+ ENER,-
&very substance is associated with a definite amount of energy which depends upon its chemical
nature as well as upon its temperature, pressure and volume. This energy is #nown as internal
energy. Internal energy of the system is the energy possessed by all its constituent molecules.
Internal energy is a state property i.e. its value depends only upon the state of the substance but
does not depend upon how that state is achieved. The absolute value of internal energy of a
substance can not be determined. 'owever determining the absolute values of internal energies
is neither necessary nor required. It is the change in internal energy accompanying a chemical or
a physical process that is of interest and this is a measurable quantity.
T%e first l' of t%ermodynmi!s
The first law of thermodynamics states that energy can neither be created nor destroyed,
although it can be transformed from one form to another. This is also #nown as the law of
conservation of energy.
MAT.EMATICA+ E/)RESSION O0 0IRST +A1
(et ) be the energy of a system in its state and )* be the energy in its state *. %uppose the
system while undergoing change from state to state * absorbs heat q from the surroundings
and also performs some wor# !mechanical or electrical", equal to w. The absorption of heat by
the system tends to raise the energy of the system. The performance of wor# by the system, on
the other hand, tends to lower the energy of the system because performance of wor# requires
expenditure of energy. 'ence the change of internal energy, ), accompanying the above
process will be given by
*
) ) ) q w
In general, if in a given process the quantity of heat transferred from the surrounding to the
system is q and wor# done in the process is w, then the change in internal energy,
) + q , w
This is the mathematical statement of the first law of thermodynamics.
If wor# is done by the surroundings on the system !as during the compression of a gas", w is
ta#en as positive so that ) + q , w. if however wor# is done by the system on the surroundings
!as during the expansion of a gas", w is ta#en as negative so that ) + q - w.
Illustration 2. 1 mole of ideal monoatomic gas at 27C exands adia!atically against a constant
external ressure of 1." atm from a #olume of $dm
%
to 1& dm
%
.
Calculate (i) ' (ii) w and (iii) (
Solution: !i" %ince process is adiabatic q + .
!ii" s the gas expands against the constant external pressure.
$ + ( )
/ 0
1 2 0.3 2 2
+ ( )
4
0.3 05 6 07 atm dm
!iii" ) + q , w + ( )
4
. 07 07 atm dm +
Exercise 1.
Calculate the internal energy change, when a system absorbs 5 KJ o heat an! !oes
1 KJ o wor".
ENT.A+)- O0 A S-STEM
The quantity ) , 12 is #nown as the enthalpy of the system and is denoted by '. It represents
the total energy stored in the system. Thus
' + ) , 12
It may be noted that li#e internal energy, enthalpy is also an extensive property as well as a state
function. The absolute value of enthalpy can not be determined, however the change in enthalpy
can be experimentally determined.
' + ) , !12"
*rious (inds of pro!esses2
!i" Isot%erml re#ersi$le e"pnsion of n Idel gs2 %ince internal energy of an Ideal gas
is a function of temperature and it remains constant throughout the process hence
& + . and ' + & , 12
Q
& + .
and 1020 + 1/2/ at constant temperature for a given amount of the gas
'+ .
8alculation of q and w9
Q
& + q , w
:or an Isothermal process, w + ;q
This shows that in an Isothermal expansion, the wor# done by the gas is equal to amount
of heat absorbed.
and w + ; n <T ln!2/=20" + ; n <T ln!10=1/".
Illustration #. 1) gm of *elium at 127C is exanded isothermally from 1)) atm to 1 atm
Calculate the wor+ done when the exansion is carried out (i) in single ste (ii) in
three stes the intermediate ressure !eing &) and %) atm resecti#ely and (iii)
re#ersi!ly.
Solution: !i" $or# done + 2.1
2 +
3
3
0. 7.406 6..
74.06 0.
6 0.. 0.

_

,
m
4

%o $ +
3
74.06
0.
!0..;0" 0.
3
+ 3456738 97
!ii" In three steps
2I + 74.06 0.
;3
m
4

$I

+ !74.06 0.
;3
" !0..;5." 0.
3
+ 44/3.5 >ules
2 II +
3 4
3
/.3 7.406 6..
047.35 0. m
5. 0.

$II + 2. 1
$II + 047.35 0.
;3
!5.;4." 0.
3
+ 6035.?? 603@ >.
2III +
3 4
3
/.3 7.406 6..
/@@.04 0. m
4. 0.

$III + /@@.04 0.
;3
!4.;0" 0.
3
$III + 7.45.75 >.
$ total + $I , $II , $III
+ 44/3.5,6035.?.?,7.45.75 + :;;:<7=; 97
!iii" :or reversible process
$ + /.4.4 n<T log
0
/
1
1
+ /.4.4
0. 0..
7.406 6.. log
6 0
_ _


, ,
1 > 534<=743 9ules
Exercise 2.
Calculate the inal $olume o one mole o an i!eal gas initially at %C an! 1 atm
&ressure, i it absorbs 1%%% cal o heat !uring a re$ersible isothermal ex&ansion.
Exercise #.
Carbon monoxi!e is allowe! to ex&an! isothermally an! re$ersibly rom 1%m
#
to 2%
m
#
at #%% K an! wor" obtaine! is '.(5' KJ. Calculate the number o moles o carbon
monoxi!e.
!ii" Adi$ti! Re#ersi$le E"pnsion of n Idel gs2
Q
q + .
&+ ;w.
Total change in the internal energy is equal to external wor# done by the system.
$or# done by the system + &+ 8vT.
and 8p;8v + <
An dividing all the terms by 8v.
p
v
v v v
8
8 <
8 8 8

p
v
8
8

v
<
! 0"
8

and 8v
<
! 0"

/
0
T
T
<
w dT
! 0"




/ 0
<
w !T T "
! 0"


and ' + & , 12.
Thus if T/BT0, w + ,ve i.e. wor# is done on the system.
Thus if T/CT0, w + ;ve i.e. wor# is done by the system.
+imittions of t%e first l'7 Need for t%e se!ond l'
maDor limitation of the first law of thermodynamics is that its merely indicates that in any
process there is an exact equivalence between the various forms of energies involved, but it
provides no information concerning the spontaneity or feasibility of the process. :or example, the
first law does not indicate whether heat can flow from a cold end to a hot end or not.
The answers to the above questions are provided by the second law of thermodynamics.
Spontneous nd non ? spontneous pro!ess
If in the expansion of a gas the opposing pressure is infinitesimally smaller than the pressure of
the gas, the expansion ta#es place infinitesimally slowly i.e. reversible. If however, the opposing
pressure is much smaller than the pressure of the gas the expansion ta#es place rapidly i.e.
irreversibly. Eatural processes are spontaneous and irreversible.
SECOND +A1 O0 T.ERMOD-NAMICS
The second law of Thermodynamics helps us to determine the direction in which energy can be
transformed. It also helps us to predict whether a given process or chemical reaction can occur
spontaneously or not.
A!!ording to @el#in2 FIt is impossible to use a cyclic process to extract heat from a reservoir and
to convert it into wor# without transferring at the same time a certain amount of heat from a hotter
to colder part of the bodyG.
Entropy C%nge2 &ntropy change is the state function and it is the ratio of heat change in a
reversible process by the temperature.
% +
rev
q
T
Thermodynamically irreversible process is always accompanied by an increase in the entropy of
the system and its surroundings ta#en together while in a thermodynamically reversible process,
the entropy of the system and its surroundings ta#en together remains unaltered.
Illustration '. Calculate entroy change for #aori,ation of 1 mole of li'uid water to steam at
1))C if *- . $)./ +0mol

1
.
Solution: :or entropy change of vaporization
2
2
'
%
T

4
0 0
2
6..7 0.
% 0.?.47 ># mol
4@4

Illustration 5. A system changes its state irre#ersi!ly at %)) 1 in which it a!sor!s %)) cals of
heat. 2hen the same change is carried out re#ersi!ly the amount of heat
a!sor!ed is 3)) cals. The change in entroy of the system is e'ual to
(A) 1 cal 1
41
(B) % cals 1
41
(C) 2 cal 1
41
(D) 1." cals 1
41
Solution: (B)
)%ysi!l Signifi!n!e of Entropy2 &ntropy is the measure of disorderness because
spontaneous processes are accompanied by increase in entropy as well as increase in the
disorder of the system. Thus, increase in entropy implies increase in disorder.
Illustration ). 2hich of the following statement is true5
(i) A closed system shows exchange of mass and not energy with surroundings.
(ii) 6ntroy change for fusion reaction is ositi#e.
(iii) *eat is a measure of 'uantity of energy whereas temerature is a measure of
intensity of energy.
Solution: !i" :alse !ii" True !iii" True
Some Ot%er Stte 0un!tion2 :or a spontaneous process entropy change is positive and if it is
zero, the system remains in a state of equilibrium. Two other functions are also there to decide
the feasibility of the reactions li#e wor# function and free energy change H.
+ & - T%II.!i"
H + ' - T%II.!ii"
nd + & ; T%II!iii"
H + ' ; T%III...!iv" !for a finite change at constant temperature"
%ince, % + qrev.=T 'ence from eq. !i"
+ & - qrevIIIIII..!v"
and according to first law of Thermodynamics
& ; qrev + wrev. IIIII.!vi"
If during the change, wor# is done by the system, it would carry a negative sign,
;wrev + & - qrevIIIII.!vii"
8omparing the equation !v" and !vii"
; + wrev
%ince the process is carried out reversibly where w represents the maximum wor#. It is thus clear
that decrease in function gives maximum wor# done that can be done by the system during the
given change. The wor# function is also called as 'elmholtz function.
:rom equation !iv"
H + ' ; T%
and ' + & , 12
H + & , 12 ; T%
8omparing it with eq. !iii"
H + , 12
%ince, is equal to - w, hence.
H + ; w , 12.
; H + w; 12
'ence decrease in free energy gives maximum wor# obtainable from a system other than that
due to change of volume at constant temperature and pressure. This is called as Eet $or#.
Eet $or# + w;12 + ;H
The Eet $or# may be electrical wor# or chemical wor#.
8riterion of spontaneity9 :or a spontaneous process H should be ;ve
,IBBS 0REE ENER,-
This is another thermodynamic quantity that helps in predicting the spontaneity of a process, is
called Hibbs energy !H".
It is defined mathematically by the equation.
H + ' T%
$here ' + heat content, % + entropy of the system, T + absolute temperature
Illustration (. 2hich of the following will fit into the !lan+5
2hen two hases of the same single su!stance remain in e'uili!rium with one
another at a constant 7 and T8 their molar 999999999 must !e e'ual.
(A) :nternal energy (B) 6nthaly
(C) 6ntroy (D) ;ree energy
Solution: (D)
0ree energy !%nge
:or isothermal process.
/ 0
H H H ' T %
H + change in Hibbs free energy of the system.
It is that thermodynamic quantity of a system the decrease in whose value during a process is
equal to the maximum possible useful wor# that can be obtained from the system.
Illustration *. Calculate free energy change when one mole of <aCl is dissol#ed in water at
2"=C. >attice energy . 7)) +0?mol. % at 2"=C . 2&."
0
>mol

8 *ydration energy
of <aCl . &3& +0?mol.
(A) %.3 +0 (B) /+0
(C) 12+0 (D) 1&+0
Solution: (A)
RE+ATIONS.I) BET1EEN 0REE ENER,- AND EAUI+IBRIUM CONSTANT
The free energy change of the reaction in any state, H !when equilibrium has not been attained"
is related to the standard free energy change of the reaction, H
.
!which is equal to the difference
in free energies of formation of the products and reactants both in their standard states"
according to the equation.
.
H H <TlnJ +
$here J is the reaction quotient
$hen equilibrium is attained, there is no further free energy change i.e. H + . and J becomes
equal to equilibrium constant. 'ence the above equation becomes.
( )
.
eq.
H <TlnK
or
( )
.
eq.
H /.4.4 <T logK
In case of galvanic cells. Hibbs energy change H is related to the electrical wor# done by the
cell.
H + n:&!cell" where n + no. of moles of electrons involved
: + the :araday constant
& + emf of the cell
If reactants and products are in their standard states
. .
cell
H n:&
Illustration +. Calculate @
)
for con#ersion of oxygen to o,one ( ) ( )
2 3
3
O g O g
2
at 23/
18 if 1 for this con#ersion is 2.$7 1)

23
.
Solution:
.
p
H /.4.4<TlogK
$here < + 7.406 >=K mol, Kp + /.6@ 0.

/?
, T + /?7K
H
.
+ 054.. >=mol + 054 K>=mol
T.IRD +A1 O0 T.ERMOD-NAMICS
The entropy of a pure crystalline substance increases with increase of temperature, because
molecular motion increases with increase of temperature and vice ; versa.
Ar the entropy of a perfectly crystalline solid approaches zero as the absolute zero of
temperature is approached. This is third law of thermodynamics.
T.ERMOC.EMISTR-
The branch of chemistry which deals with energy changes involved in chemical reactions is called
thermochemistry. The energy change that occurs in a chemical reactions is largely due to change
of bond energy.
C%nge of internl energy in !%emi!l re!tion
(et us consider a chemical reaction ta#ing place at constant temperature and at constant volume.
In such a case, w + . and hence from the first law
) + qv
$here qv is the heat exchanged at constant volume, or heat or enthalpy of reaction at constant
volume.
C%nge of Ent%lpy in !%emi!l re!tion
(et q1 be the heat exchanged in the chemical reaction ta#ing place at constant pressure, Then
evidently,
' + q1 + 'eat or &nthalpy of reaction at constant pressure.
E"ot%ermi! nd Endot%ermi! re!tion
<eaction that give out heat, i.e. which are accompanied by evolution of heat, are called
exothermic reaction. In such reactions ' is negative. An the other hand, reaction that inta#e
heat, i.e. which are accompanied by absorption of heat are called endothermic reactions. In these
reactions ' is positive.
Illustration 1%. ;ill in the !lan+s with aroriate word in followingA
(i) Com!ustion of reactions are usually BBBBBBBB..
(ii) Com!ustion of ;2 in oxygen is BBBBBBBB..
Solution: !ii" &xothermic
!iii" &ndothermic
Ent%lpy of re!tion
It is the enthalpy change ta#ing place during the reaction when the number of moles of reactants
and products are same as the stoichiometric coefficient indicates in the balanced chemical
equation. The enthalpy change of the reaction depends upon the conditions li#e temperature,
pressure etc under which the chemical reaction is carried out. Therefore, it is necessary to select
the standard state conditions. ccording to thermodynamics conventions, the standard state
refers to 0 bar pressure and /?7 K temperature. The enthalpy change of a reaction at this
standard state conditions is called standard enthalpy of the reaction( )
.
'
.
Different types of ent%lpy
!i" Ent%lpy of formtion9 &nthalpy change when one mole of a given compound is formed
from its elements.
'/!g" , 0=/A/!g" /'/A!l", ' + -7?..45 #> = mol
Exercise '.
Calculate
0
f
H or chlori!e ion rom the ollowing !ata:
( ) ( ) ( )
2 2
1 1
H g + Cl g HCl g H =-92.4 KJ
2 2
( ) ( ) ( )
+ -
2
HCl g +nH O H aq +Cl aq H =-74.8 KJ
( ) ( )
0 +
f
H H aq =0.0 KJ
!ii" Ent%lpy of !om$ustion2 &nthalpy change when one mole of a substance is burnt in
oxygen.
8'6 , /A/!g" 8A/ , /'/A!l", ' + -7?..45 #> = mol
Exercise 5.
,he heat liberate! on com&lete combustion o (.* g ben-ene is #2( KJ. ,his heat has
been measure! at constant $olume an! at 2(C. Calculate heat o combustion o
ben-ene at constant &ressure at 2(C.
!iii" Ent%lpy of NeutrliBtion2 &nthalpy change when one equivalent of an acid is neutralized
by a base or vice - versa in dilute solution. This is constant and its value is -04.@ #cal for
neutralization of any strong acid by a base since in dilute solutions they completely dissociate
into ions.
'
,
!aq" , A'
-
!aq" '/A!l", ' + -04.@ #cal
:or wea# acids and bases, heat of neutralization is different because they are not dissociated
completely and during dissociation some heat is absorbed. %o total heat evolved during
neutralization will be less.
e.g. '8E , EaA' Ea8E , '/A, ' + -/.? #cal
'eat of ionization in this reaction is equal to !-/.? , 04.@" #cal + 0..7 #cal
Illustration 11. *eat of neutrali,ation of a strong acid !y a strong !ase is e'ual to * of
(A) *
C
C D*

*2D
(B) *2D C *
C
*%D
C
(C) 2*2 C D2 . 2*2D
(D) C*%CDD*C <aD* . C*%CDD<a C *2D
Solution: !" %ince heat of neutralization of strong acid and strong base is equal to the
heat of formation of water.
i.e., EaA' , '8l Ea8l , '/A , J
$ere J + heat of neutralization
Ea
,
, A'
-
, '
,
, 8l
-
Ea
,
,8l
-
, '/A , J
'
,
, A'
-
'/A , J
!iv" Ent%lpy of %ydrtion2 &nthalpy of hydration of a given anhydrous or partially hydrated salt
is the enthalpy change when it combines with the requisite no.of mole of water to form a
specific hydrate. :or example, the hydration of anhydrous copper sulphate is represented by
8u%A6!s" , 3'/A !l" 8u%A63'/A!s", ' + -07.5? #cal
Illustration 12. :onisation energy of Al . "1%7 +0 mole
41
(*) hydration of Al
%C
. 4 $&&" +0
mole
41
. (*)hydration for Cl
4
. 4 %/1 +0 mole
41
. 2hich of the following statement is
correct
(A) AlCl% would remain co#alent in a'ueous solution
(B) Dnly at infinite dilution AlCl% undergoes ionisation
(C) :n a'ueous solution AlCl% !ecomes ionic
(D) <one of these
Solution: If l8l4 is present in ionic state in aqueous solution, therefore it has l
4,
L 48l
-
ions
%tandard heat of hydration of l
4,
L 48l
;
ions
+ - 6553 , 4 !-470" #> mole
-0
+ ;37.7 #>=mole
<equired energy of ionisation of l + 304@ #> mole
-0
'ydration energy overcomes ionisation energy
l8l4 would be ionic in aqueous solution
'ence (C) is the correct answer.
!v" Ent%lpy of Trnsition2 &nthalpy change when one mole of a substance is transformed
from one allotropic form to another allotropic form.
8 !graphite" 8!diamond", ' + 0.? #>=mol
Illustration 1#. The heat of transition for car!on from the following is
CDiamond C D2(g) CD2(g) * . 4 3$.% +cal
CAmorhous C D2(g) CD2(g) * . 4 37.& +cal
(A) %.% +0 ? mol (B) %.% +cal ? mol
(C) 4%.% +0 ? mol (D) 4 %.% +cal ? mol
Solution: Hiven
8M , A/!g" 8A/!g" ' + -?6.4 #cal=mole I!0"
8 , A/!g" 8A/!g" ' + - ?@.5 #cal=mole I!/"
NNNNNNNNNNNNNNNNNNNNNNNNNNN
%ubtracting equation !/" from equation !0"9
8M - 8 .O ' + ,4.4 #cal=mole
8M 8 ' + ,4.4 #cal=mole
(B)
Illustration 1'. ;rom the reaction 7(white) 7 (Eed)A * . F 1/.$ +08 :t follows that
(A) Eed 7 is readily formed from white 7
(B) 2hite 7 is readily formed from red 7
(C) 2hite 7 can not !e con#erted to red 7
(D) 2hite 7 can !e con#erted into red 7 and red 7 is more sta!le
Solution: (D)
.ESSCS +A1
This law states that the amount of heat evolved or absorbed in a process, including a chemical
change is the same whether the process ta#es place in one or several steps.
%uppose in a process the system changes from state to state * in one step and the heat
exchanged in this change is q. Eow suppose the system changes from state to state * in three
steps involving a change from to 8, 8 to M and finally from M to *. If q0, q/ and q4 are the heats
exchanged in the first, second and third step, respectively then according to 'esss law
q0 , q/ , q4 + q
'esss law is simply a corollary of the first law of thermodynamics. It implies that enthalpy change
of a reaction depends on the initial and final state and is independent of the manner by which the
change is brought about.
Illustration 15.

A
*
D
B
*
2

*
1

C
*
%

:n this case exress * in terms of *18 *28 *% .
Solution: ' + '0 , '/ , '4
Illustration 1). *2D (l) *2(g) C
1
2
D2(g) * . C /3).%& +0 ? mole
2hat is * for *2D (l) from its constituent elements
Solution: '/A!l" '/!g" ,
/
0
A
/
!g" ' + , 7?..45 #> = mole
'/!s" ,
0
/
A/!g" '/A!l" ' + - 7?..45 #> = mole

( )
/
f
' A
! '
+ -7?..45 #> = mole
Exercise ).
.i/ C 0 12 C12.g/ 2 3 4+' Kcals
C 0
1
2
12 C1.s/ 2 3 42).' Kcals
C1 0
1
2
12 C12.g/ 2 35
.ii/ 6hat is heat e$ol$e! using neutralisation o 2C7 by a strong base5 2eat o ioni-ation
o 2C7 is 1%.* Kcal.
A))+ICATION O0 .ESSCS +A1
:7 Cl!ultion of ent%lpies of formtion
There are large number of compounds such as 85'5, 8A, 8/'5 etc whose direct synthesis from
their constituent element is not possible. Their '
.
f values can be determined indirectly by 'esss
law. e.g. let us consider 'esss law cycle for 8A/ !g" to calculate the '
.
f of 8A!g" which can not
determined otherwise.
( ) ( ) ( ) ( )
/ / 0
0
8 s A g 8A g A g '
/
+ + + P
( ) ( ) ( )
/ / /
0
8A g A g 8A g ' /74K>= mole
/
+
( ) ( ) ( )
/ / 4
8 s A g 8A g ' .4?4K>= mole +
ccording to 'esss law,
4 0 /
' ' ' +
or
0 4 /
' ' '
+ 4?4 !/74" 00. K>=mole
47 Cl!ultion of stndrd Ent%lpies of re!tions
:rom the #nowledge of the standard enthalpies of formation of reactants and products the
standard enthalpy of reaction can be calculated using 'esss law.
ccording to 'esss law
( ) ( )
. . .
f f
' 1 ' < ' +


( ) ( )
. . .
f f
' ' 1 ' <

.
sum of standard enthalpies of sum of standard enthalpies
'
formation of products of formation of reac tants
1 1

1 1
] ]
57 In t%e !l!ultion of $ond energies
BOND ENER,-
*ond energy for any particular type of bond in a compound may be defined as the average
amount of energy required to dissociate one mole, viz vogadros number of bonds of that type
present in the compound. *ond energy is also called the enthalpy of formation of the bond.
Cl!ultion2
:or diatomic molecules li#e '/, A/, E/, '8l, ': etc, the bond energies are equal to their
dissociation energies. :or polyatomic molecules, the bond energy of a particular bond is found
from the values of the enthalpies of formation. %imilarly the bond energies of heteronuclear
diatomic molecules li#e '8l, ': etc can be obtained directly from experiments or may be
calculated from the bond energies of homonuclear diatomic molecules.
Illustration 1(. Calculate the !ond energy of *Cl. @i#en that the !ond energies of *2 and Cl2 are
$%) 10mol

1
and 2$2 10 mol

1
resecti#ely and *
)
f for *Cl is 31 10 mol

1
.
Solution: ( ) ( )
0
/
' g /' g ' 64. K>mol ...!i"

+

( ) ( )
0
/
8l g /8l g ' /6/ K>mol ...!ii"

+
( ) ( ) '8l ' g 8l g ' P ...!iii" +
:or the reaction !iii"
' + ( ) ( )
. .
f f
' product ' reac tant

+ ( ) ( ) ( )
. . .
f f f
' ' ' 8l ' '8l 1 1 +
] ]
+ ( )
0 0
64. /6/ ?0
/ /
+
' + 6/@ K> mol

0

Illustration 1*. @i#en that
2*2(g) C D2(g) *2D(g) 8 * . 411".$ +cal the !ond energy of *4* and D . D
!ond resecti#ely is 1)$ +cal and 113 +cal8 then the D4* !ond energy in water
#aour is
(A) 11).& +cal ? mol (B) 411).& +cal
(C) 1)" +cal ? mol (D) <one
Solution: $e #now that heat of reaction
' + *.&. !reactant" - *.& !product"
:or the reaction,
/'-'!g" , A + A !g" /' - A-'!g"
' + -003.6 #cal, *.&. of '-' + 0.6 #cal
*.&. of A+A + 00? #cal
%ince one '/A molecule contains two A-' bonds
-003.6 + !/ 0.6" , 00? - 6 !A-'" bond energy
6 !A-'" bond energy + !/ 0.6" ,00?,003.6
i.e., A-' bond energy +
( ) / 0.6 00? 003.6
6
+ +
+ 00..5 #cal mol
-0
'ence, (A) is correct.
Illustration 1+. @i#en the !ond energies of < <8 * 4 * and < 4 * !onds are 3$"8 $%& and %31
+0?mol resecti#ely8 the enthaly of the reaction.
<2(g) C %*2(g) 2<*%(g) is
(A) 4 3%+0 (B) 1)2+0
(C) 3)+0 (D) 1)"+0
Solution: (A)
Exercise (.
Estimate the a$erage S 4 8 bon! energy in
6
SF
. ,he $alues o stan!ar! enthal&y o
ormation o ( ) ( ) ( ) 6 g g g
SF , S and F
are 11%%, 2(5 an! *% KJ9mole res&ecti$ely.
+ATTICE ENER,- O0 AN IONIC CR-STA+ (BORN?.ABER C-C+E)
Q!s" ,
2
1
R
/
!g" QR!s"
%tep 0 %tep /
Q!g" R!g"
%tep3
%tep 4 %tep 6
Q
,
!g" , R
-
!g"
Born ? .$er !y!le
The change in enthalpy that occurs when 0 mole of a solid crystalline substance is formed from
its gaseous ions, is #nown as (attice energy.
Gte 1A 8onversion of metal to gaseous atoms
Q!s" Q!g" , '0 + sublimation
Gte 2A Missociation of R/ molecules to R atoms
R/!g" /R !g", '/ + Missociation energy
Gte %A 8onversion of gaseous metal atom to metal ions by losing electron
Q!g" Q
,
!g" , e
-
, '4 + !Ionization energy"
Gte $A R!g" atoms gain an electron to form R
-
ions
R!g" , e
-
R
-
!g", '6 + &lectron affinity
Gte "A Q
,
!g" and R
-
!g" get together and form the crystal lattice
Q
,
!g" , R
-
!g" QR!s" '3 + lattice energy
pplying 'esss law we get
'0 , 0=/ '/ , '4 , '6 , '3 + 'f !QR"
An putting the various #nown values, we can calculate the lattice energy.
Illustration 2%. 2hat is the exression of lattice energy (() of CaBr2 using Born*a!er cycle5
Solution:
8a!s"
'f
%
8a!g"
I&0 , I&/
8a
/,
, *r/
M
/*r
/&.
/*r
-
8a*r/!s"
/
8a*r
)
,
+ % , I&0 , I&/ , M ; /&. -
/
8a*r
)
Illustration 21. 2hat is the relation !etween * and 6 in this reaction5
C*$(g) C 2D2(g) CD2(g) C 2*2D(l)
Solution: ' + & , n<T
n + no. of mole of products ; no. of moles of reactants + 0- 4 + -/
' + & - /<T
Illustration 22. 2hat is the exression of lattice energy (() of CaBr25
(sing Born *a!er cycle5
Solution:
8a!s" '
f

%
8a!g"
I&
0
, I&
/

8a
/,
!g"
, *r
/
!g"
M
/*r !g"
/&.
/*r
-
!g"
8a*r
/
!s"
/
8a*r
)
,

f
'
+ % , I&0 , I&/ , M ; /&. -
/
8a*r
)
Illustration 2#. The lattice energy of solid <aCl is 1/) +cal?mole. The dissolution of the solid in
water in the forms of ions is endothermic to the extent of 1 +cal?mol. :f the
solution energies of Ea
+
and 8l

are in the ratio &A"8 what is the enthaly of

hydration of Ea
+
ion5
(A) /".& +cal?mol (B) 37." +cal?mol
(C) /2.& +acl?mol (D) C1)) +cal?mol
Solution: (B)
Exercise *.
.i/ 8or a system C.s/ 0 12.g/ 3 C12.g/ which o the ollowing is correct:
.a/ 2 3 E .b/ 2 > E .c/ 2 < E .!/ 2 3 %
.ii/ C)2).l/ ,
15
2
12.g/ #221 0 )C12.g/ 2 3 4#2)'.' "J mole
41
.
6hat is the energy e$ol$e! when (.* gm o ben-ene is burnt in air5
BOMB CA+ORIMETER
The bomb calorimeter used for determining change in internal energy at constant volume if
reaction for the combustion is #nown than enthalpy of combustion can be estimated by using
formula9 ' + & , n<T.



















+
O
4

IHEITIAE
$I<&%
IE%)(TIEH
8AETIE&<
$T&<
%T&&( *AQ*
%Q1(&
Bom$ Clorimeter
This apparatus was devised by *erthelot !0770" to measure the heat of combustion of organic
compounds. modified form of the apparatus shown in :igure consists of a sealed combustion
chamber, called a bomb, containing a weighed quantity of the substance in a dish alongwith
oxygen under about /. atm pressure. The bomb is lowered in water contained in an insulated
copper vessel. This vessel is provided with a stirrer and a thermometer reading up to 0=0..
th
of a
degree. It is also surrounded by an outer Dac#et to ensure complete insulation from the
atmosphere. The temperature of water is noted before the substance is ignited by an electric
current. fter combustion, the rise in temperature of the system is noted on the thermometer and
heat of combustion can be calculated from the heat gained by water and the calorimeter. *y
#nowing the heat capacity of calorimeter and also the rise in temperature, the heat of combustion
can be calculated by using the expression
.et e"!%nge > D T
S-'eat capacity of calorimeter system
T- rise in temp
'eat changes at constant volumes are expressed in & and 'eat changes at constant pressure
are expressed in '. lso, ' + & , n<T
n + Qoles of gaseous product- Qoles of gaseous reactant.
Illustration 2'. A samle of ).1& g C*$ was su!Hected to com!ustion at 27C in a !om!
calorimeter. The temerature of the calorimeter system (including water) was
found to rise !y )."C. Calculate the heart of com!ustion of methane at
(i) constant #olume and (ii) constant ressure. The thermal caacity of
calorimeter system is 17.7 10 1

1
I E . /.%1$ 01

1
mol

1
.
Solution: 'eat of combustion at constant volume, & + 'eat capacity of calorimeter
system rise in temperature
Qol. mass of compound
mass of compound

+
05
0@.@ ..3 773
..05

& + 773 #> mol

0
( ) ( ) ( ) ( )
6 / / /
8' g /A g 8A g /' A + + l
n + 0 - 4 + /, T + 4.. K, < + 7.406 0.

4
#> K

0
mol

0

' + & , n<T
( )
4 0 0
773 / 7.406 0. #># mol

+
' + & , n<T
( )
4
773 / 7.406 0. 4..

+
0
773 6.?77 77?.?77 #>mol

Appli!tion of $ond energies
(i) Determintion of ent%lpies of re!tions
%uppose we want to determine the enthalpy of the reaction.
8 8
'
' '
'
!g" ' '!g"
8 8 '
' '
' '
' !g"
T' P
If bond energies given for 8 8, 8 + 8, 8', and ' ' are 46@.4, 503.., 605./ and
643.0K> mol

0
respectively.
( )
C=C H-H C-H C-C C-H
H= H + H +4 H - H +6 H
+ !503.. , 643.0" !46@.4 , 74/.6" 0/?.5 K>
(ii) Determintion of ent%lpies of formtion of !ompounds
8onsider the formation of acetone.
48!g" 5'!g"
A!g" ' 8 8 8 '
' A '
' '
T' P
( ) ( )
[ ]

1
]
s g
f H-H O-O C-C C-H C=O
C C
1
H = 3 H + H +3 H 2 H +6 H + H
2
by putting the value of different bond energies you can determine the 'f.
(iii) Determintion of resonn!e energy
If a compound exhibits resonance, there is a considerable difference between the enthalpies of
formation as calculated from bond energies and those determined experimentally. s an example
we may consider the dissociation of benzene.
( ) ( ) ( )
5 5
8 ' g 58 g 5' g +
ssuming that benzene ring consists of three single and three double bonds !Ke#ules structure"
the calculated dissociation energy comes out to be 3476.0 K> from bond energies data.
d 8 8 8 8 8 '
' 4 ' 4 ' 5 '

+ +

The experimental value is #nown to be 3343.0 K>=mol. &vidently, the energy required for the
dissociation of benzene is 030 K> more that the calculated value. The difference of 030 K> gives
the resonance energy of benzene.
Exercise +.
Calculate the entha&y o combustion o ben-ene .l/ on the basis o the ollowing.
.i/ :esonance energy o ben-ene .l/ 3 4 152 "J mole
41
.ii/ Enthal&y o hy!rogenation o cyclohexene .l/ 3 4 11+ "J mole
41
.iii/ .2
%
/C)212 3 4 15) "J mole
41
.i$/ .2
%
/221 3 4 2*5.* "J mole
41

.$/ .2
%
/C12 3 4 #+#.5 "J mole
41
.EAT CA)ACIT- AND S)ECI0IC .EAT
The heat capacity !8" of a sample of substance is the quantity of heat needed to raise the
temperature of the sample of substance by one degree 8elsius !or Kelvin".
q + ct
'eat capacity is directly proportional to the amount of substance.
The specific heat capacity is the quantity of heat required to raise the temperature of one gram of
a substance by one degree 8elsius at constant pressure.
q + s m t
where q is the heat required to raise temperature
m + mass in grams
s + specific heat of the substance
t + temperature difference
*ARIATION O0 .EAT O0 REACTION 1IT. TEM)ERATURE
The heat of reaction depends on the temperature. The relation between the two is #nown as
1irchoffJs e'uation.
!i"
/ 0
/ 0
' '
T T

+ 81 !ii"
/ 0
/ 0
& &
T T

+ 82
81 + molar heat capacity of products - molar heat capacity of reactants !at constant pressure"
8v + molar heat capacity of products - molar heat capacity of reactants !at constant volume"
Illustration 25. The standard heat of formation listed for gaseous <*% is 11.)2 +cal?mol at
23/ 1. @i#en that at 23/ 18 the constant ressure heat caacities of gaseous <28
*2 and <*% are resecti#ely &.3&8 &./38 /.%/ cal?mol. Determine *
)
23/1 and
*77% 1 for the reactions8
( ) ( ) ( )
/ / 4
0 4
E g ' g E' g
/ /
+
Solution: ( ) ( ) ( )
/ / 4
0 4
E g ' g E' g
/ /
+
( ) ( ) ( )
/?7K f :
1 <
' ' ' 00../ .

> ::764 (!l mol

:

/ 0
p
/ 0
' '
8
T T

( )
/ 4
' 00../
0 4
7.47 5.?5 5.7? 0.
@@4 /?7 / /


_

,
.4 > :578 (!l mol

:
Exercise 1%.
,he s&eciic heats o io!ine $a&our an! soli! are %.%#1 an! %.%55 cals9g res&ecti$ely.
I heat o sublimation o io!ine is 2' cals9g at 2%%C, Calculate its $alue at 25% C.
ANS1ERS TO E/ERCISES
Exercise 1:
6 #>
Exercise 2:
04?.@ litre
Exercise #:
/.@3
Exercise ':
05@./ K>
Exercise 5:
4/54.@5 K>
Exercise ):
!i" 5@.5 #cal
!ii" /.? #cal

Exercise *:
!i" !a"
!ii" 4/5.66 K>
Exercise +:
, '
/
' + - 00? #> mole
-0
, '
/
'+ 4 !-00?" #> mole
-0
+ ;43@ #> mole
-0
- 43@ + !'f
.
"1roduct !'f
.
"<eactant
+ - 035 - !'f
.
"*enzeene
!'f
.
"*enzene + !- 035 , 43@"K> mole
-0
+/.0 K> mole
-0
<esonance energy U!'f
.
"*enzeneVctual - U!'f
.
"*enzeneVTheoretical
or, - 03/ + U!'f
.
"*enzeneVctual ;/.0
or U!'f
.
"*enzeneVctual + 6? #> mole
-0
85'5!l" ,
/
03
A
/
!g" 58A/!g" , 4'/A!l"
!'
.
"reaction + ( ) ( )
/ /
. .
f f
8A ' A
5 ' 4 ' +
- !'f
.
"*enzene
+ 5 !- 4?4.3" , 4!-/73.7" - 6?
+ 548E7= (9 mole
?:
Exercise 1%:
%olid I/ is converted in I/ vapour
I/!s" + I/!g" ' + /6 cal=g at /..8
8p + !81"I/!g" !8p"I/!s" + ...40 - ...33 + - ../6 cal g
-0
:rom Kirchoffs equation
( )
p
/3. 8 /.. 8 /3. 8 /.. 8
' ' 8 T T
o o o o
/3. 8
'
o + /6 - .../6 !3/4 - 6@4" + /6 - 0./ + //.7 cals g
-0
MISCE++ANEOUS E/ERCISES
Exercise 1: Gtate8 whether the following statements are True or ;alse5
(i)
fusion sub vap
' ' '
(ii) Bond formation is always exothermic
(iii) 6nthaly of neutralisation of
6
E' A'
with *Cl is higher than enthaly of
<aD* with *Cl.
(i#) *eat of reaction is indeendent of temerature.
(#) *eat of com!ustion of a fuel . caloric #alue of fuel
Exercise 2: A solution of " gm of *aemoglo!in (molecular weight . &$)))) in 1)) cc of
solution shows a temerature raise of
o
...40 8 for comlete oxygenation. 6ach
mole of haemoglo!in !inds $ mole of oxygen. :f the heat caacity of the solution
is
0 4
6.07 # cm ,

calculate ' er gm mole of oxygen !ond.
Exercise #: At
o
/3 8, the enthaly change for the reaction
/ 6 / / 6 /
' %A 3' A ' %A .3' A !all liquids" +
is F"/).%2 +0 ? mole. Calculate the
temerature change if 1 mole of
/ 6
' %A
is droed into " mole of
o
/
' A at /3 8.

Assume no heat loss to the surroundings and that the secific heat caacity of
solution is
0 0
6.076 ># g .

Exercise ': The
o
f
' 60.76 #>= mol for the neutralisation reaction
4 / 4
'8A !aq" A' !aq" ' A! " 8A !aq"

+ + l
Comute ( ) / 5 q
8 ' .
for the reaction
/
8A
Exercise 5: The
o
f /
' !8a*r !s"" 5@3 #>= mole . The first and second ioni,ation energies of
Ca are "3) and 11$" +0 ? mole. The enthaly of formation of Ca is 17/ +0 ? mol.
The !ond enthaly of
/
*r
is 13% +0 ? mole and enthaly of #aourisation of
/
*r
is
%1 +0 ? mole. The electron affinity of Br(g) is %2" +0 ? mole. Calculate the lattice
energy of
/
8a*r !s".
Exercise ): The heats of com!ustion of yellow hoshorus and red hoshorous are 43.13
+0 and 4 /.7/ +0 resecti#ely8 and then calculate the heat of transition of yellow
hoshorus to red hoshorous.
Exercise (: Calculate the enthaly change when infinitely dilute solutions of CaCl2 and
<a2CD% mixed
o
F.
f
for Ca
2C
(a')8
4
CO
5
(a') and CaCD%(s) are 4 123./)8
4 1&1.&"8 4 2//." +cal mole
41
resecti#ely.
Exercise *: Calculate the heat of formation of ethyl acetate from ethyl alcohol and acetic
acid. @i#en that heat of com!ustion of ethyl alcohol is %$ +cal and of acetic acid8
it is 21 +cal and of ethyl acetate8 it is "".$ +cal.
Exercise +: ;or the gi#en heat of reaction8
(i) C(s) C D2(g) . CD2(g) C 37 +cal
(ii) CD2(g) C C(s) . 2CD(g) 4 %3 +cal
Calculate the heat of com!ustion of CD(g).
Exercise 1%: 1 mole of an ideal gas undergoes re#ersi!le isothermal exansion from an initial
#olume -1 to a final #olume 1)-1 and does 1) 10 of wor+. The initial ressure
was 1 1)
7
7a.
(i) Calculate -1
(i) :f there were 2 mole of gas8 what must its temerature ha#e !een5
ANS1ER TO MISCE++ANEOUS E/ERCISES
Exercise 1: !i" True
!ii" True
!iii" :alse
!iv" :alse
!v" :alse
Exercise 2: ;60.6@ #>
Exercise #:
o
@4.@ 8
Exercise ': 06.. #> = mol
Exercise 5: ;/05/ #> = mole
Exercise ): !i" 16 !yellow" ,3A/!g" 16A0. , ?.0? #>
!ii" 16!red" , 3A/!g" 16A0. , 7.@7 #>
NNNNNNNNNNNNNNN
subtracting, 16!yellow" - 16 !red" + 0.04 #>
16!yellow" + 16!red" , 0.04 #>
%o, heat of transition of yellow to red phosphorus is - 0.04 #>
Exercise (: An mixing 8a8l/ !aq" and Ea/8A4
8a8l/ , Ea/8A4 8a8A4, /Ea8l
%olutions are very dilute and thus 0..W dissociation occurs
8a
/,
!aq",/8l

!aq",/Ea
,
!aq" ,
/
4
8A

!aq" 8a8A4, /Ea

,
!aq" ,/8l

!aq" or 8a
/,
!aq"
,
, 8A4
/-
!aq" 8a8A4!s"
' + 'Xproducts - 'Xreactants
or ' +
/ /
4
4
o o o
f 8a8o
f 8a f 8A
' U ' ' V
+
+
Q
'X of a compound + 'X formation + -/77.3 - !-0/?.7 - 050.53"
> 47<; (!lGmole
Exercise *: ;6.. cals
Exercise +: %ubtracting equation !ii" from equation !i", we get
8!s" , A/!g" + 8A/!g" , ?@ #cal
8A/!g" , 8!s" + /8A!g" - 4? #cal
NNNNNNNNNNNNNNNNNNNNNNNN
or, -8A/!g" , A/!g" + 8A/!g" - /8A!g" , 045 #cal
or, /8A!g" , A/ + /8A/!g" , 045 #cal
or, 8A!g" , 0=/ A/!g" + 8A/!g" , 57 #cal
<equired value + 57 #cal
Exercise 1%: !i"
6 4
6.46 0. m

!ii"
/50.04 K
SO+*ED )ROB+EMS
Sub;ecti$e:
Bord Type Auestions
<rob 1. 2hy standard entroy of an elementary su!stance is not ,ero whereas standard
enthaly of formation is ta+en as ,ero5
Sol. substance has a perfectly ordered arrangement of its constituent particles only at
absolute zero. 'ence entropy is zero only at absolute zero. &nthalpy of formation is the
heat change involved in the formation of one mole of the substance from its elements. n
element formed from itself means no heat change.
<rob 2. Dut of car!on (diamond) and car!on (grahite)8 whose enthaly of formation is ta+en as
,ero and why5
Sol. The enthalpy of formation of graphite is ta#en as zero because it is a more commonly
found stable form of carbon.
<rob #. 0ustify8 an exothermic reaction is always thermodynamically sontaneous.
Sol. &xothermic reactions are generally thermodynamically spontaneous because even if it is
accompanied by decrease of randomness, the heat released is absorbed by the
surroundings so that the entropy of the surroundings increases to such an extent that
total
%
is positive.
<rob '. :s ' always greater than '#5 6xlain why or why not5
Sol. qp is not greater than qv always. It depends upon whether ng is ,ve or ve.
<rob 5. 0ustify8 many thermodynamically feasi!le reactions do not occur under ordinary
conditions.
Sol. )nder ordinary conditions, the average energy of the reactants may be less than
threshold energy. They require some activation energy to initiate the reaction.
IIT +e#el Auestions
<rob ). The standard heats of formation at 23/ 1 for CCl$ (g)8 *2D (g)8 CD2 (g) and *Cl (g) are
2"."8 "7./8 3$.1 and 22.1 1cal?mole. Calculate the
.
/?7
'
for the reaction.
( ) ( ) ( ) ( )
4 2 2
CCl g +2H O g CO g +4HCl g
* . 5
Sol. ' +
/ 6 /
8A '8l 88l ' A
' 6 ' ' / ' 1 1 + +
] ]
+ [ ] [ ] ?6.0 6 //.0 /3.3 / 3@.7 + +
,043.6 Kcal
<rob (. The molar heats of com!ustion of C2*2 (g)8 C(grahite) and *2 (g) are %1).&2 1cal8
3$.)" 1cal and &/.%2 1cal resecti#ely. Calculate the standard heat of formation of
C2*2 (g).
Sol. The required equation is
/ / /
/8 ' 8 ' O ' P +
$riting the thermochemical equation of the given data
/ / / / /
3
!i" 8 ' A /8A ' A ' 40..5/#cal
/
+ +
/ /
!ii" 8 A 8A ' ?6..3#cal +
/ / /
0
!iii" ' A ' A ' 57.4/#cal
/
+
!iii" , / !ii" !i"
/ / /
/8 ' 8 ' ' 36./.#cal +
<rob *. The molar heat of formation of <*$<D% (s) is %&7."$ 10 and those of <2D (g) and *2D
( ) l
are /1.$& and 2/"./ 10 resecti#ely at 2"C and 1 atmosheric ressure.
Calculate * and 6 of reaction.
( ) ( ) ( ) l
4 3 2 2
NH NO s N O g +2H O
Sol.
p <
' ' '
+ 0//.5. K>
' & n<T +
0//5.. + & , 0 7.406 /?7
& + 0/3..@ K>
<rob +. Determine the #alue of * and 6 for the re#ersi!le isothermal e#aoration of 3).) gm
of water at 1))C. Assume that water #aour !eha#es as an ideal gas and heat of
e#aoration of water is "$) cal?gm.
Sol. ' + ?. 36. + 67.5 Kcal
' & 1 2 +
2olume of liquid is negligible as compared to volume of vapour
%o 2 + 2vapour
' & n<T +
& +
?.
675.. / 4@4
07

+ 66.7@ #cal
<rob 1%. An athelete is gi#en 1)) gm glucose of energy e'ui#alent to 1"&)) +0. *e utili,es ")K
of this gained energy in an e#ent. :n order to a#oid storage of energy in !ody8 Calculate
the wt of water he would need to resire. 6nthaly of
/
' A
for e#aoration is $$ +0 ?
mole.
Sol. &nergy gained by athelete + 035. #>
&nergy utilized in event
3.
035. @7. #>
0..

&nergy left + 035. - @7. + @7. #>
%ince 66 #> energy used to evaporate + 07 gm
/
' A

@7. #> energy used to evaporate

/
07 @7.
40?..? of ' A
66

<rob 11. The secific heat at constant #olume for a gas ).)7" cal ? g and at constant ressure is
).12" cal ? gm. CalculateA
(i) The molecular weight of the gas
(ii) Atomicity of gas
(iii) <um!er of atoms in its 1 mole
Sol. !i" %pecific heat at constant pressure
1
8 ..0/3cal = gm
%pecific heat at constant volume,
2
8 ...@3 cal = gm
s we #now,
1 2
<
8 8
Q

or,
1 2
< /
Q 6.
8 8 !..0/3 ...@3"


!ii" :or atomicity,
1
2
8 ..0/3
Y 0.55
8 ...@3

'ence gas is mono atomic.
!iii" %ince gas is mono atomic. 'ence 0 mole of gas contains
/4
5../4 0. atoms
<rob 12. 2hen 1 mole of ice at
o
. 8 and $.& mm of *g is con#erted to water #aours at a
constant temerature and ressure. ;ind
' and &,
if the latent heat of fusion of ice is
/) cal ? gm and latent heat of #aorisation of li'uid water at
o
. 8 is
"3& cal ? gm. The #olume of ice in comarison to #olume of #aours may !e neglected.
Sol. Ice vapour
f 2
' ' ' +
7. 07 3?5 07 +
+ 0/057 cal = mole
' & 1 2 +
2 2olume of vapours at 6.5 mm and
o
. 8 !as
ice
2 neglible"
Eow applying 12 + n<T
0 7.406 /@4
1 2 n<T cal
6.07

+ 364 cal
& ' 1 2
+ 0/057 - 364
+ 005/3 cal
<rob 1#. Calculate the standard enthaly of reaction
( ) ( ) ( ) ( )
/
SnA s 8A g Sn s 8A g + +
@i#en ( ) ( )
. 0 . 0
f f /
' SnA, s 467./7#>mol O ' 8A , g 4?4.30#>mol


( )
. 0
f
' 8A, g 00..34 #>mol

Sol. $e have ( ) ( ) ( ) ( )
. . . . .
f f f / f f
' ' Sn, s ' 8A , g ' SnA,s ' 8A, g +
+ ( ) ( ) ( ) { }
0 0
. 4?4.30 467./7 00..34 #> mol 53.4 #>mol

+
<rob 1'. Calculate the enthaly of #aori,ation for water from the following
*2(g) C 1?2 D2(g) *2D (g) * . 4 "7.) +cal
*2(g) C 1?2 D2(g) *2D(l) * . 4 &/.% +cal
Also calculate the heat re'uired to change 1 gm *2D (l) to *2D (g).
Sol. '/!g" , 0=/ A/!g" '/A !g"O ' + -3@.. #cal ;;;;;;;;;;;;;;;;; !0"
'/!g" , 0=/ A/!g" '/A !l"O ' + - 57.4 #cal;;;;;;;;;;;;;;;;;;!/"
%ubtracting !/" from !0"
'/A !l" '/A !g" O ' + 00.4 #cal
&nthalpy of vaporization for '/A + 00.4 #cal
lso 07 g '/A requires enthalpy of vaporization + 00. 4 #cal
0 g '/A requires
00.4
07
#cal + 67843 (!l
<rob 15. The standard enthaly of com!ustion of *28 C&*1) and Cyclohexane (C&*12) are 4 2$18
4 %/))8 4 %32) +0 mole
41
at 2"=C resecti#ely. Calculate the heat of hydrogenation of
cyclohexene.
Sol. $e have to find ' for
85'0. , '/ 85'0/
Hiven '/ , 0=/ A/ '/A ' + - /60 #> ;;;;;;;;;;;;;;; !0"
85'0. ,
0@
/
A/ 58A/ , 3'/A ' + - 47.. #> ;;;;;;;;;;;;;;;!/"
85'0/ , ?A/ 58A/ , 5'/A ' + - 4?/. #> ;;;;;;;;;;;;;;;!4"
dding equation !0" and !/" and then subtracting equation 4
85'0. , '/ 85'0/ ' + - 0/0 #>
'eat of hydrogenation of cylohexene + ? :4: (9
1b;ecti$e:
<rob 1. A system is ta+en from state A to state B along two different aths 1 and 2. The heat
a!sor!ed and wor+ done !y the system along these aths are L1 and L2 and 21 and
22 resecti#ely. Then
(A) L1 . L2 (B) 21 C L1 . L2 C 22
(C) 21 . 22 (D) L1 21 . L2 22
Sol. !M"
<rob 2. :n which of the following rocess does the entroy decrease5
(A) dissol#ing of <aCl in water (B) e#aoration of water
(C) con#ersion of CD2(g) into dry ice (D) none
Sol. !8"
<rob #. Calculate the enthaly change when ") ml of ).)1 M Ca(D*)2 reacts with 2" ml of ).)1
M *Cl. @i#en that *
)
neut of a strong acid and strong !ase is 1$) cal? e'ui#alent
(A) 1$.) cal (B) %" cal
(C) 1).) cal (D) 7." cal
Sol. !*"
<rob ' :n a re#ersi!le adia!atic change G is
(A) infinity (B) ,ero
(C) e'ual to C#dT (D) e'ual to nEln -2?-1
Sol. !*"
<rob 5 At constant temerature and ressure which one of the following statements is correct
for the reaction5
CD(g) C 1?2D2(g) CD2(g)
(A) * . 6
(B) * N 6
(C) * O 6
(D) * is indeendent hysical state of reactant
Sol. !*"
<rob ) ;or the reaction8
C7*/(l) C 3D2(g) 7CD2(g) C $*2D(l)8 the calculated heat of reaction is 2%2 +0?mol and
o!ser#ed heat of reaction is ").$ +0?mol8 then the resonance energy is
(A) 4 1/2.2 +0 ? mol (B) C 1/2.2 +0 ? mol
(C) 172 +0? mol (D) <one
Sol. !" s we #now that,
<esonance energy + 'X !observed" - 'X !calculated"
+ !3..6 - /4/.5" #> = mol
+ - 07/./ #> mol
-0
0ill in t%e Bln(s
<rob ( An isolated system is one which neither shows exchange of BBBB.. nor
BBBBBB. with surroundings.
Sol. !heat, mass"
<rob * During fusion8 the entroy of the system BBBBBBBB.
Sol. !increases"
<rob +
2 2
< CD 2<D8 shows an BBBBBBB.. of heat.
Sol. !absorption"
<rob 1% ;or sontaneous reaction
P@ is
BBBBBBBBB
Sol. !negative"
<rob 11 Bom! calorimeter used for determining change in internal energy at
constantBBBBBBBB
Sol. 2olume
True nd 0lse
<rob 12. Gecific heat is an intensi#e roerty.
Sol. True
<rob 1#. A thermodynamic e'uili!rium reresents the state when all the three e'uili!rium (i.e.
chemical8 thermal and mechanical e'uili!rium) are attained at a time.
Sol. True
<rob 1'. The rocess is isothermal if temerature of the system remains constant throughout
the course of studies.
Sol. True
<rob 15. Ei#ers flowing from mountain to field shows decrease in entroy.
Sol. :alse
<rob 1). 6nthaly of com!ustion at a gi#en temerature is defined as the enthaly change for
the comete com!ustion of 1 gm of su!stance.
Sol. ;alse
ASSI,NMENT )ROB+EMS
Sub;ecti$e:
+e#elH O
:7 $hy is the enthalpy of sublimation is equal to the sum of enthalpy of fusion and enthalpy of
vaporizationP
47 )nder what conditions of
H, ' or %,
a reaction will be spontaneous at all temperaturesP
57 $hy is the heat of neutralisation of a strong acid by a strong base is constant as 3@.. #> =
moleP
=7 $hen does entropy increases in a reaction.
;7 &ntropy of the solution is higher than that of pure liquid, whyP
87 The
H at m. pt.
of ice is zero.
E7 t temperature T, the endothermic reaction * proceeds almost to completion. $hy
% is veP +
37 $hy standard heat of formation of diamond is not zero though it is an elementP
<7 8an the absolute value of internal energy be determinedP $hy or why notP
:67 %ame mass of diamond and graphite !both being carbon" are burnt in oxygen. $ill the heat
produced be same or differentP $hyP
::7 $hy in chemical reactions generally heat is either evolved or absorbedP
:47 $hy is the enthalpy of sublimation equal to the sum of enthalpy of fusion and enthalpy of
vaporisationP
:57 $hen an ideal gas expands in vacuum, there is neither absorption nor evolution of heat.
$hyP
:=7 8alculate the heat change for the following reaction9
( ) ( ) ( ) ( )
6 / / /
8' g /A g 8A g /' A + + l
.
f
' for 8'6, '/A and 8A/ are 0@.7?, 57.4 and ?6..3 #cal=mole
:;7 The heat of reaction ( ) ( ) ( )
/
0
8 s A g 8A g
/
+ at 0@8 and at constant volume is /?./?
#cal. 8alculate the heat of reaction at constant pressure.
:87 Thermochemistry is the study of relationship between heat energy L IIIIIIIII..
:E7 Mefine Hibbs free energy.
:37 Total energy for a reversible isothermal cycle isIIIIIIIIIII
:<7 :ind out the value of equilibrium constant for the following reaction at /?7 K.
( ) ( ) ( ) ( )
4 / / / /
/E' g 8A g E' 8AE' aq. ' A + +

%tandard Hibbs energy change r H

at the given temperature is 04.5 #>=mol.

467 $hat you can conclude from this graph

,
i
$
$
s

e
n
e
r
g
y

Re!tn
t
)rodu!t
s
E
&
u
i
l
i
$
r
i
u
m



+e#el ? I
:7 $hich of the following can be determinedP bsolute internal energy, absolute enthalpy,
absolute entropy
47 $hy would you expect a decrease in entropy as a gas condenses into liquidP 8ompare it with
the entropy decrease when a liquid sample is converted into solid.
57 )nder what conditions will the reaction occur, if both % and ' are positiveP
=7 >ustify, the entropy of a substance increases on going from liquid to vapour state at any
temperature.
;7 Ane mole of an ideal gas is heated at constant pressure from .8 to 0..8.
!a" 8alculate wor# done.
!b" If the gas were expanded isothermally L reversibly at .8 from 0 atm to some other
pressure 1t, what must be the final pressure if the maximum wor# is equal to the wor#
involved in !a".
87 ir contains ??W E/ and A/ gases. Then why do not they combine to form EA under the
standard conditionsP Hiven that the standard free energy of formation of EA!g" is
75.@ K> mol

0
.
E7 8alculate the heat of following reaction
/ / 4
E 4' /E' +
Hiven the bond energies of E E, ' ' and E ' bonds are //5, 0.6 and ?4 #cal
respectively.
37 $hen / moles of 8/'5 are completely burnt 40/? K> of heat is liberated. 8alculate the heat of
formation, 'f for 8/'5O 'f for 8A/ and '/A are 4?3 and /75 K> respectively.
<7 8alculate the heat of formation of ethane at /38. The bond enthalpies for ' ', 8 8 and 8
' bonds are 0.6./ #cal, 7. #cal and ??.3 #cal respectively. 'eat of vaporization of carbon is
0@0.@ #cal.
:67 Mefine the following terms9
!a" Internal energy !b" &ndothermic reaction
!c" 'ess law !d" 8alorific value
::7 3 mole of an ideal gas expand isothermally L reversibly from a pressure of 0. atm to / atm at
4.. K. $hat is the largest mass which can be lifted through a height of 0 mitre in this
expansionP
:47 The equilibrium constant for the reaction9
( ) ( ) ( ) ( )
/ / /
8A g ' g 8A g ' A g + +

at /?7 K is @4. 8alculate the value of the standard

free energy change !< + 7.406 >K

0
mol

0
".
:57 n insulated container contains 0 mole of a liquid molar volumes 0.. ml at 0 bar. $hen liquid
is steeply passed to 0.. bar, volume decrease t. ?? ml, find ' L ) for the process.
:=7 *, / L */ are diatomic molecules. If the bond enthalpies of /, * L */ are in the ratio
0909..3 L the enthalpy of formation of * from / L */ is 0.. K> mol

0
. $hat is the bond
enthalpy of /P
+e#el ? II
:7 8alculate the 8 ' bond energy in methane at /38 from the data. 'eat of formation of
methane is 0@.? #cal, heat of vaporization of carbon is 0@0.0 cal and heat of formation of
hydrogen atoms is 3/.0 #cal=mol.
47 The heats of combustion of hydrogen, ethane and ethylene are 57.6, 4@..6 and 4?4.3 #cal
per molecule respectively. 8alculate the energy when ethylene is reduce to ethane.
57 The molar heat of formation of E'6EA4 is 45@.36 K> and those of E/A!g" and '/A( ) l
are
70.65 K> and /73.@7 K>, respectively at /38 and 0.. atm pressure. 8alculate ' and & for
the reaction.
( ) ( ) ( )
6 4 / /
E' EA s E A g /' A + l
=7 Hiven that
( ) ( ) ( )
/ /
' g I g /'I g ' 0/.65 #cal +
( ) ( )
/
I g /I g ' 43.7 #cal
( ) ( )
/
' g /' g ' 0.4.@ #cal
8alculate the bond energy of ' - I
;7 8alculate the maximum wor# done when pressure on 0. g of hydrogen is reduced from /. to
0 atm at a constant temperature of /@4 K. The gas behaves ideally. 8alculate J.
87 %tandard heat of formation of 'gA!s" at /?7 K and at constant pressure is ;?..7 #> = mole.
&xcess of 'gA!s" absorbs 60.76 #> of heat at constant volume, calculate the amount of 'g
that can be obtained at constant volume and /?7 K, tomic weight of 'g + /...
E7 8alculate the heat of formation of anhydrous
/ 5
l 8l
from
/ 5 /
/l!s" 5'8l!aq" l 8l !aq" 4' !g", ' /4?.@5 #cal + +
/ /
' !g" 8l !g" /'8l!g", ' 66.. #cal +
'8l!g" q '8l!aq", ' 0@.4/ #cal +
/ 5 / 5
l 8l !s" q l 8l !aq", ' 034.5? #cal +
37 8alculate the heat of formation of
/
g A
from following data9
!i"
4 4 /
1b /gEA !aq" 1b!EA " !aq" /g 3.? cals + + +
!ii"
4 4 / /
1bA /'EA !aq" 1b!EA " !aq" ' A 0@7 cals + + +
!iii"
/
0
1b A 1bA 3.4 cals
/
+ +
!iv"
/ 4 / 4
g A /'EA !aq" ' A gEA !aq" 0.6 cals + + +
<7 8alculate resonance energy of
4
8' 8AA'
from the following data if the observed heat of
formation of
4
8' 8AA'
is ;64?.@ #>.
Bond Energy .et of tomistion ((9)
8 - ' + 604 8 + @05.@
8 - 8 + 467 ' + /07..
8 + A + @4/ A + /6?.0
8 - A + 430
A - ' + 654
:67 :or a reaction ( ) ( ) ( )
/ /
0
Q A s /Q s A g
/
+ , ' + 4. K> mol

0
and % + ...@ K> K

0
mol

0
at
0 atm. 8alculate upto which temperature, the reaction would not be spontaneous.
1b;ecti$e:
+e#el ? I
:7 n intensive property is that property which depends upon
!" the nature of the substance
!*" the amount of the substance
!8" both the amount and nature of the substance
!M" neither the nature nor the amount of the substance
47 ( ) ( ) ( ) ( )
.
f / / /
' of 8A g , 8A g , E A g and EA g
in K>=mol are respectively 4?4, 00., 70 and 46.
8alculate ' in K> of the following reaction.
( ) ( ) ( ) ( )
/ / /
/EA g /8A g E A g 48A g + +
!" 745 !*" 065.
!8" 745 !M" 065.
57 Temperature of 0 mole of a gas is increased by 0 at constant pressure wor# done is
!" < !*" /<
!8" <=/ !M" 4<
=7 $hich of the following thermodynamic quantities is an outcome of the second law of
thermodynamicsP
!" enthalpy !*" internal energy
!8" wor# !M" entropy
;7 The difference between heats of reaction at constant pressure and constant volume for the
reaction
( ) ( ) ( ) ( )
5 5 / / /
/8 ' 03A g 0/8A g 5' A + + l l
at /38 in K> mol

0
is
!" @.64 K>mol

0
!*" @.64 K>mol

0
!8" /.6@@ K>mol

0
!M" /.6@@ K>mol

0
87 :or a reaction at equilibrium
!"
.
H H . !*"
.
H .
!8"
.
H H . !M"
.
H ., H .
E7 $hen 0 mole gas is heated at constant volume, temperature is raised from /?7 to 4.? K.
'eat supplied to the gas is 3.. >. Then which statement is correctP
!" q + w + 3.. >, u + . !*" q + u + 3.. >, w + .
!8" q + w + 3.. >, u + . !M" u + ., q + w + 3.. >
37 In thermodynamics a process is called reversible when
!" surroundings and system change into each other
!*" there is no boundary between system and surroundings
!8" the surroundings are always in equilibrium with the system
!M" the system changes into the surroundings spontaneously
<7 $hat is true for the reactionP
( ) ( ) ( )
3 4 /
18l g 18l g 8l g +
!" ' & !*" ' & >
!8" ' & < !M" none
:67 8alculate the wor# done when 0 mol of an ideal gas is compressed reversibly from 0... bar
to 3.. bar at a constant temperature of 4.. K
!" 06..0 K> !*" 05../ K>
!8" 6..0 K> !M" 7../ K>
::7 The factor that does not influence the heat of reaction is
!" the physical state of reactants and products
!*" the temperature
!8" the pressure or volume
!M" the method by which the final products are obtained
:47 !' &" for the formation of E'4 from E/ and '/ is
!" <T !*" /<T
!8" ;<T !M" ;/<T
:57
( ) ( )
0 atm
vap g
, ' 65..5 cal = mol
l

boiling point + 3. #, what is boiling point at 0. atmP
!" 03. K !*" @3 K
!8" 0.. K !M" none
:=7 'eat of neutralization of '/8/A6 !oxalic acid" is ;/5 Kcal=mole. The dissociation energy of
!" '/8/A6

/'
,
,
/
/ 6
8 A

is
!" 0/.4 Kcal=mole !*" 0.6 Kcal=mole
!8" ;04.@ Kcal=mole !M" ;0.6 Kcal=mole
:;7 The heats of combustion of yellow phosphorus and red phosphorous are -?.0? #> and - 7.@7
#> respectively, then heat of transition of yellow phosphorus to red phosphorous is
!" - 07.5? #> !*" ,0.04 #>
!8" ,07.5? #> !M" ..60 #>
:87 The enthalpies of formation of organic compounds are conveniently determined from their
!" boiling points !*" melting points
!8" enthalpies of neutralization !M" enthalpies of combustion
:E7 Thermodynamic equilibrium involves
!" chemical equilibrium !*" thermal equation
!8" mechanical equation !M" all the three
:37 &vaporation of water is
!" a process in which neither heat is evolved nor absorbed
!*" a process accompanied by chemical reaction
!8" an exothermic change
!M" an endothermic change
:<7 The heat content of the system is called
!" internal energy !*" enthalpy
!8" free energy !M" entropy
467 The apparatus used for measuring the heat changes of a reaction is called
!*" thermometer !*" a colorimeter
!8" a calorimeter !M" none of these
The questions given below consist of statements AssertionC (A) nd IResonC (R)7
!a" If both and < are correct and < is correct reason for .
!b" If both and < are correct but < is not the correct explanation for .
!c" If is true but < is false.
!d" If both and < are false.
4:7 !" &nthalpy of graphite is lower than that of diamond.
!<" &ntropy of graphites lower than that of diamond.
447 !" $hen a gas at high pressure expands against vacuum the wor# done is maximum.
!<" $or# done in expansion depends upon the pressure inside the gas L increase in volume.
457 !" Qolar entropy of vaporization of water is different form ethanol.
!<" $ater is more polar than methanol
4=7 !" reaction which is spontaneous L accompanied by decrease of randomness must be
exothermic.
!<" ll exothermic reaction are accompanied by decrease of randomness.
4;7 !" The enthalpy of formation of ( )
/
' A l is greater than that of '/A!g".
!<" &nthalpy change is negative for the condensation reaction.
( ) ( )
/ /
' A g ' A l


+e#el ? II
:7 &vaporation of water is a spontaneous process although it
!" Is an exothermic reaction
!*" is an endothermic reaction
!8" Is a photo chemical reaction
!M" proceed without heat loss or heat gain
47 :or the two reactions given below
( ) ( ) ( )
/ / / 0
0
' g A g ' A g R K>
/
+ +
( ) ( ) ( )
/ / / /
0
' g A g ' A R K>
/
+ + l
%elect the correct answer
!" R0 B R/ !*" R0 C R/
!8" R0 + R/ !M" R0 , R/ + .
57 $hich of the following is wrongP
!" change in internal energy of an ideal gas on isothermal expansion is zero
!*" in a cyclic process w J
!8" for an ideal gas
T
'
.
1
1

]
!M" all
=7 The heats of neutralization of four acids a, b c and d when neutralized against a common
base are 04.@, ?.6, 00./ and 0/.6 Kcal respectively. The wea#est among these acids is
!" c !*" b
!8" a !M" d
;7 The bond energies of 8 8, 8 ', ' ' and 8 + 8 are 0?7, ?7, 0.4, 063 Kcal
respectively. The enthalpy change of the reaction
/ / /
8' 8' ' 8' 8' +
is
!" 03/ Kcal !*" ?5 Kcal
!8" 67 Kcal !M" 6. Kcal
87 $hich plot represents for an exothermic reactionP
!"

.
Time
R
)
!*"

.
Time
R
)
!8"

.
Time
R )
!M"

.
Time
R )
E7 The molar heat capacity of water in equilibrium with ice at constant pressure is
!" negative !*" zero
!8" infinity !M" 6..63 K>K

0
mol

0

37 &nthalpy of
6 / 4
0
8' A 8' A'
/
+ is negative. If enthalpy of combustion of 8'6 and
8'4A' are x and y respectively. Then which relation is correctP
!" x B y !*" x C y
!8" x + y !M" x y
<7 $hen 0. ml of a strong acid are added to 0. ml of an al#ali, the temperature rises 38. If 0..
ml of each liquids are mixed, the temperature rise would be
!" ..38 !*" 0.8
!8" @.38 !M" same
:67 R is a metal that forms an oxide R/A
/ /
0 0
R A R A O ' 0/.Kcal
/ 6
+
$hen a sample of metal R reacts with one mole of oxygen, what will be the ' in that caseP
!" 67. #cal !*" /6. #cal
!8" 67. #cal !M" /6. #cal
::7 *, / and */ are diatomic molecules. If the bond enthalpies of /, * L */ are in the ratio
0909..3 and enthalpy of formation of * from / and */ - 0.. #>=mol
-0
. $hat is the bond
enthalpy of /P
!" 6.. #>=mol !*" /.. #>=mol
!8" 0.. #>=mol !M" 4.. #>=mol
:47 $hich of the following corresponds to the definition of enthalpy of formation at
/?7 KP
!" 8!graphite" , /'/!g" , 0=/ A/!l" 8'4A'!g"
!*" 8!diamond" , /'/!g" , 0=/ A/!g" 8'4A' !l"
!8" /8!graphite" , 6'/!g" , A/!g" /8'4A' !l"
!M" 8!graphite" , /'/!g" , 0=/ A/!g" 8'4A'!l"
:57 The heat of neutralisation of '8l by EaA' is -0/.0#>=mole, the energy of dissociation of '8l
is
!" -64.7 #> !*" 64.7 #>
!8" 57 #> !M" -57 #>
:=7 The dissociation energy of 8'6 and 8/'5 are respectively 45. L 5/. #. cal=mole. The bond
energy of 8-8 is
!" /5. #cal=mole !*" 07. #cal=mole
!8" 04. #cal=mole !M" 7. #cal=mole
:;7 Identify the intensive property from the following9
!" &nthalpy !*" Temperature
!8" 2olume !M" <efractive index
:87 $hich of the following expression is not correctP
!"
. .
H n:&
!*"
. .
eq
H <T lnK
!8" ( )
. .
1
& <T = n: lnK !M"
.
1
H H <T lnJ +
:E7 :or a reaction ( ) ( ) g * g

at equilibrium, the partial pressure of * is found to be one

fourth of the partial pressure of . The value of H
.
of the reaction * is
!" <T ln6 !*" <T ln6
!8" <T log6 !M" <T log6
:37 :or an irreversible isothermal expansion of an ideal gas
!"
sys surr
% %
!*"
sys surr
% %
!8"
sys surr
% % >
!M"
sys surr
% % <
:<7 ( ) ( )
/
' g /' g
!" ' atom has higher entropy !*" hydrogen molecule has entropy
!8" both have same entropy !M" none
467 n endothermic reaction is spontaneous only if
!" the entropy of the surrounding increases !*" entropy of the system increases
!8" total entropy decreases !M" none


ANS1ERS TO ASSI,NMENT )ROB+EMS
Sub;ecti$e:
+e#el H O
:7 %ince sublimation involves the process
s
'
%olid 2apour

IIIIIIIIII.. !0"
or
f v
' '
%olid (iquid 2apour

III.!/"
*y !0" and !/",
s f v
' ' ' +
47 t all temperature conditions,
' . and % ., so that H .. < > <
57 It is so because only '
,
and A'
-
react in every case and it is the enthalpy of formation of
water.
=7 !i" $hen number of molecules of products are more than number of molecules in the
reactants.
!ii" $hen solid state changes to liquid state.
!iii" $hen liquid state changes to gaseous state.
!iv" $hen solid changes to gaseous state.
;7 %olute molecules also set free to move in solution and thus disorder increases.
87 The system9
ice water,

at m. pt., is in equilibrium and thus H ..

E7
H ' T %O Q
since the reaction proceeds to completion that is irreversible or
spontaneous and thus
H ve. Therefore, since ' ve. ' T % ve or % +
should
be ,ve.
37 The standard state chosen for carbon is graphite and not diamond.
<7 Eo, because it is the sum of different types of energies and some of which can not be
determinedP
:67 'eat evolved will be different. This is because they have different crystal structure.
::7 *ecause all chemical reactions are accompanied by bond rearrangements. The total bond
energy of reactants is not equal to the total bond energy of products hence heat is either
evolved or absorbed.
:47 %ublimation is a process which is assumed to ta#e place in two step9
:irst a solid converts into liquid and second a liquid converts into vapours hence the sum of
enthalpy of fusion and enthalpy of vapourisation is equal to enthalpy of sublimation.
:57 In an ideal gas, there are no intermolecular forces of attraction. 'ence no energy is required
to overcome these forces. Qoreover, when a gas expands against vacuum, wor# done is zero
!because 1ext + .". 'ence internal energy of the system does not change i.e. there is no
absorption or evolution of heat.
:=7 /0/.@5 #cal
:;7 /?... #cal
:87 8hemical energy
:37 Sero
:<7 /.6 0.
/
467 t equilibrium products are much more in abundance than the reactants !# B B 0".
+e#el ? I
:7 bsolute entropy
47 In liquid, the molecules have much less freedom of motion as compared to the molecules of
the gas. $hen a liquid changes into solid the entropy becomes very low because in a solid
the molecular motion almost stops !except vibrational motion"
57 H ' T % . :or a reaction to occur, H should be negative.
If both ' and % are positive, H can be negative only if T % ' > in magnitude. Thus
either % has large positive value so that even if T is low, T% is greater than ' or if % is
small, T should be high so that T% B '.
=7 The molecules in the vapour state have greater freedom of movement and hence greater
randomness than those in the liquid state. 'ence entropy increases in going from liquid to
vapour state.
;7 !a" $or# done during heating of gas form .8 to 0..8 is
$ + 12 + 1!2/ 20" + 1U!n<T/=1"!n<T0=1"V
( ) ( )
/ 0
n< T T 0 0.?7@ 4@4 /@4
+ 0?7.@ cal
!b" If wor# equivalent to 0?7.@ cal is used for gas at .8, causing its isothermal expansion,
from 0 atm to pressure 1t
$< + /.4.4n<Tlog!10=1/"
( )
t
0?7.@ /.4.4 0.?7@ /@4log 0= 1
1t + ..5?6 atm
87 %tandard free energy of formation !H

f" for the reaction

( ) ( ) ( )
/ /
0 0
E g A g EA g
/ /
+ is positive !+ ,75.@ K> mol

0
". 'ence the reaction is
non - spontaneous under the standard conditions.
E7 /. #cal=mol
37 74.3 K>
<7 /0 #cal
::7 $or# done by the system
0 0
e 0.
/ /
1 1
n<Tlog /.4.4n<Tlog
1 1

+
4
0.
/.4.4 3 7.406 4.. log /...@3 0. >
/

(et Q be the mass
$or# done in lifting the mass
+ Qgh + Q ?.7 0 >
Q ?.7 + /...@3 0.
4

Q + /.67.65? #g
:47
c
H /.4.4<TlogK
o
0.
H /.4.4 7.406 /?7 log @4
o
+ 0..54/ #>
:57 ' + ??.. bar ml
) + 0.. bar ml
:=7 6.. K> mol

0
+e#el ? II
:7 ??.43 #cal 47 ,?0.3 #cal
57 73@.56 K>, 75..00@3 K> =7 @3.?7 #cal
;7 707. cal 87 ?4.4@ gm
E7 4/0.?? #cal
37 57 cals
<7 00..4 #> = mole
:67 T C 6/7.3@ K
1b;ecti$e:
+e#el ? I
0. D /. C 4. A
6. D 3. A 5. D
@. B 7. C ?. B
0.. C 00. D 0/. D
04. C 06. D 03. D
05. D 0@. D 07. D
0?. B /.. C /0. B
//. D /4. B /6. C
/3. A
+e#el ? II
0. B /. A 4. B
6. B 3. D 5. A
@. C 7. B ?. D
0.. C 00. A 0/. D
04. C 06. D 03. B J D
05. C 0@. A 07. C
0?. A /.. B