Thermodynamic Notes

CHEMICAL THERMODYNAMICS
CHEMICAL THEROMODYNAMICS
1. Thermodynamics
The branch of science which deal with study of different forms of energy and the
quantities
relationship between them is known as Thermodynamics.
When the study of thermodynamics is confined to chemical changes and chemical
substances
only, it is known as chemical thermodynamics.
Energetics. It is that branch of chemistry which deals with energy changes taking place in
areaction.
Application in Chemistry :
Thermodynamics helps in
(a) Determining feasibility of a particular process i.e., whether or not a particular process
will occur under a given set of conditions.
(b)
Determining the extent to which a reaction would proceed before attainment of
equilibrium.
(c)
Most impor tant laws of physical chemistry such as Raoultss law, vant Hoff law,
distribution law, phase rule, law of equilibrium, laws of thermochemistry and expression
for elevation in boiling point and depression in freezing point are in accordance with
laws of thermodynamics.
2. Some fundamental Definitions

1. System :
That part of the univer se which is chosen for thermodynamics considerations is
called system.
2. Surrounding : The remaining portion of the universe which is not chosen for thermodynamic
consideration is called surrounding.
3. Boundary : The imaginary line which separ ates the system from the surrounding is called
boundary.
4. Types of system :
(i) Open system : A system is said to be an open systems if it can exchange both matter
and energy with the surroundings.
(ii) Closed system : If a system can exchange only energy with the surrounding but not
matter is called closed systems.
(iii) Isolated system :
If a system can neither exchange matter nor energy with the
surrounding it is called an isolated systems.
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5. State of a System and state variable :
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(i) The
(ii)
The
first
The
variables
existence
and
pr operties
last e.g.,
state
of awhich
pressure,
of
system
a system
change
under
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volume
are
with
a called
given
and
change
temperature
set
initial
ofinconditions
state
the state
and
etc. of
final
issystem
called
stateaar
respectively.
state
e called
of systems.
as state
6. State function and Path Function :

A physical quantity is said to be state function if its
value depends only upon the state of the system and does not depend upon
the path
this
stateby
haswhich
been attained. For example, a person standing on the roof of a f
ive stor eyed
building
has a fixed potential energy, irrespective of the fact whether he
reached
e by
stairs
or ther
by lift.
Thus the potential energy of the person is a state function. On
the other
work hand,
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.
7. Extensity and Intensive properties :
An extensive proper ty of a system is that which
depends upon the amount of the substance or substances present in the
system. e.g.,
mass,
volume,
energy
etc.
An intensive property of a system is that which is independent of the amount
of the substance
present
in the system e.g., temperature, pressure, density, velocity etc.
8. Thermodynamics P rocesses :
The operation by which a thermodynamic system changes
form one state to another is called is thermodynamic process.
(i) Isothermal process : A process in which although heat enters or leaves the system
yet temperature of the system remains constant throughout the process is
called
an temper ature of the system remains constant throughout the pr
isothermal
ocess isan isothermal pr ocess. For an isothermal process, change in
called
temperature
( T) = 0. Change of state (e.g., freezing, melting, evaporation and
are
allcondensation)
examples of isothermal
process.
(ii) Adiabatic process :
A process during which no heats enter s or leaves the system
during any step of the process is known as adiabatic process. A reaction
carr
out system is an example of adiabatic process. For an adiabatic
in
anied
isolated
process,
change in heat ( q) = 0 or q remain constant.
(iii) Isobaric process : A process during which pressure of the system remains constant
throughout the reaction is called as isobaric process. For example, heating of
water
to point, and its vaporisation taking place at the same atmospheric
its
boiling
pressure.
Expansion of a gas in an open system is an example of isobaric process. For
an
isobar ic pr ocess P = 0.
(iv) Isochoric process : A process during which volume of the system remains constant
throughout the reaction is known as isochoric processes. The heating of a
substance
is a non-expanding chamber or change taking place in a closed system are
examples
of isochoric process. For an isochoric pr ocess, V = 0.
(v) Cyclic process : A process during which system comes to its initial state through a
number of different processes is called a cyclic process. For a cyclic process,
E = 0,
H = 0.
9. Internal energy (E) : The total energy stored in a substance by virtue of tis chemical nature
and state is called its internal energy, i.e., it is the sum of its translation,
vibrational,
rotational,
chemical
bond
energy, electronic energy, nuclear energy of constituent atoms
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due to interaction
withfrom
neighbouring molecules. It is also called
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Inter
change
nal
in
energy
internal
is
energy
a
to
state
remove
(diff
proper
the
between
its absolute
the internal
value cant
energies
be of the
intrinsicEenergy.
= Et + Er + Ev + Ee +erence
Enty+and
E
P
E
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2 of 51
determined.
products
reactants)
Internal
(a)
(c)
the
temperature,
energy
and
can
quantity
However,
that
beofdetermined
of
a of
system
pressure
substance
depends
experimentally
and
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volume.
upon : using
(b) a bomb
its chemical
calorimeter.
nature and
(i)
(ii)
(iii)
(iv)
(v)
(vi)
For a given system, E is directly proportional to its absolute temperature. (E T)

At constant volume, the quantity of heat supplied to a system (isochoric
process)
is increase in its internal energy, i.e., Q = E
equal
to the
V
In the adiabatic expansion of a gas, it gets cooled because of decrease in
internal
In
cyclicenergy.
process the change in inter nal energy is zero ( E = 0) since E is a state
function.
For exothermic reactions, sign of E is negative (E > E ).
R
P
For endothermic reactions, sign of E is positive (E > E ).
P
10. Work :
Work is expressed as the product of two factors, i.e.,

W = Intensity factor capacity factor
where, intensity f actor is a measure of force responsible for work and
capacity extent
factor is
measure
toawhich the wor k is done. Thus,
(a)
Mechanical work = Force Displacement = F d
(b)
Electrical work = Potential difference Charge flown = V Q = EnF
(c)
Expansion work = Pressure change in volume = P V
(d)
Gravitation work = Gravitational for ce Height = mg h
(a) Pressure volume work (Irreversible)

It is a kind of mechanical work. The expression for such a work may be
derived asafollows
Consider
gas enclosed in a cylinder fitter with a weightless and frictionless
piston.
Suppose area of cross reaction of a cylinder = a sq. cm.
Pressure on piston = P which is less than the internal pressure such that the
gas dl
expands.
Let
be the distance covered by the piston when the gas expands. work
done is dW
given
by l.
= Fd
= Force distance
Force
Area
= Pressur e
Force = Pr essure area
dW = P.a.d l
= PdV
Let the volume limits be V and V . Hence integrating the equation dW = PdV
1
dW =
PdV
W=P
V
W = (V
V )
2
1
When expansion takes place
V >V
W = ve
2
1
Hence work is done by the system
When compression of gas takes place then V <, W
V = +ve. Hence work is done on
2
1
the system.
(b) Work
during DEMO
isothermal
Reversible
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We know that
to remove the
dW
=
PdV
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For an ideal
PdW
= gas
=V PV
Pdv
nRT
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nRT
v2 =
w=
v2
nRT
v2
dV
v2
W = nRT
v2
dV
V
n V vv1
= nRT
= nRT
ln
V2
V1
W = 2.303 nRT log V2

V1
Also as V
1
P
W = 2.303 nRT log

W = 2.303 nRT log
(i)
(ii)
P1
P2
P1
P2
Work is not a state function because amount of work performed depends

uponfollowed.
the
path
Positive value of work signif ies that the work has been done on the system
by the
surroundings
and it leads to an increase in the internal ener gy of the system.
On thehand, negative value of work indicates that work has been done by the
other
system
and it leads to decrease in the internal energy of the system.
3. Zeroth Law
It states that Two system in thermal equilibrium separately with the third
system
aremal
saidequilibrium
to
be
in ther
with each other i.e., If system A and B separately
are in thermal
equilibrium
with another system, then system A and B are also in thermal
equilibrium.
st
4. I law
of Thermodynamics
The first law of thermodynamics states that Energy can neither be

created noralthough
be
destroyed
it can be converted f rom one form to another.
Let a system be at state I with internal energy E ,
1
it be change
II with
internal energy E
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2
This
can heat
be achieve
intaking
the ways
: during the change of state of system from
Let the
change
to
remove
place
the
(i)
heat
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(ii)qI and
state
be
or
toby
By
E
E=work
doing
=E
Eq11II
=++transfer
done
qqPW
work
++ W
W
Vbe(either
W. on
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system or by system)
2state
Illustration : 1.
A gas expands by 0.5 litre against a constant pressure one atmosphere.
Calculate
work
donethe
in joule and calorie.
Solution :
Work = P volume change
ex t
= 1 0.5 = 0.5 litreatm
= 0.5 101.328 J = 50.644 J
0.5 lit-atm = 0.5 24.20 cal = 12.10 cal
Illustration : 2.
One mole of an ideal gas is put through a series of changes as shown in
the
graph
inC mark the three stages of the system. At each stage the
which
A, B,
variables
shown
in are
the graph.
(a) Calculate the pressure at three stages of the system.
(b) Name the processes during the following changes:
(i) A to B (ii) B to C (iii) C to A, and
(iv) overall change.
AB
24.0 (L)
12.0 (L)
>
300 K 300 K
T
Solution :
(a) At stage A;
V = 24.0 L; T = 300 K; n = 1 ; R = 0.0821 lit- atm K
Substituting these values in the ideal gas eqation,
P=
1 0.0821
24 .0
300
mol 1
= 1.026 atm
At stage B :Volume remains the same but temperatur e change fr om 300 K to 600 K .
Thus, according to pressure law, the pressure will be double at B with respect
to A.
Pressure at B = 2 1.026 = 2.052 atm
At stage C : Temperature is 300 K and volume is half that of stage A. Thus, according to
Boyles law, the pressure at C will be double with respect to A.
Pressure at C = 2 1.026 = 2.052 atm
(b) (i)
During the change from A to B, volume remains constant, the process is
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isochoric.
During
to remove
the
change
the
from
C to
A, the
temperature
remains
constant,
the is
(ii) During
the
change
f rom
B to
C the
pressure
remains
constant,
the process
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(iii)
(iv)
isobaric.
is
process
Overall,
isothermal.
the process
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is cyclic as it returns to initial state.
Illustration : 3.
The diagram shows a P-V graph of a thermodynamic behaviour of an ideal
gas.form
Findthis graph :
out
(i) work done in the process A
B, B C, C D and D
A
(ii) work done in the complete cycle A
B C D A.
Solution :
12
AB
10
8
6
4
2
C
123456
V (litre)
Work done in the process A B (the process is expansion, hence work is done by the gas)
= P V = 12 10 5 5 10 3
= 6000 J
Work done in the process B C is zero as volume remains constant.
Work done in the process CD (The pr ocess is contraction, hence work is one on the gas)
= P dV = 2 10 5 5 10 3
= 1000 J
Work done in teh process D A is zero a volume remains constant.
Net work one in the whole cycle = 6000 + 1000 = 5000 J
i.e. net work is done by the gas.
Illustration : 4.
Calculate the wor k done wh en 1.0 mole of water at 373K
vaporizes
against
an of 1.0 atmosphere. Assume ideal gas behaviour.
atmospheric
pressure
Solution :
The volume occupied by water is very small and thus the volume change is
equal to the
occupied
by volume
one gram mole of water vapour.
V=
nRT
P
1.0 0.821 373

1.0
= 31.0 litre
W = P V
ex t
= (1.0) ( 31.0) litre-atm
= (31.0) 101.3 J
3140.3 J from
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Illustration : 5.
Calculate w and E f or the conversion of 0.5 mole of water at 100C to steam at
1 atm pressure. Heat of vaporisation of water at 100C is 40670 J mol
1 .
Solution :
Volume of 0.5 mole of steam at 1 atm pressure
=
nRT
P
0.5 0.0821
1.0
373
= 15.3 L
Change in volume = Vol. of steam vol. of water

= 15.3 negligible = 15.3 L
Work done by the system,
w = P volume change
ext
= 1 15.3 = 15.3 litre-atm
= 15.3 101.3 J = 1549.89 J
w should be negative as the work has been done by the system on the
surroundings. w = 1549.89 J
Heat required to convert 0.5 mole of water in 100C to steam
= 0.5 40670 J = 20335J
According to first law of thermodynamics,
E=q+w
= 20335 1549.89
= 18785.11 J
Illustration : 6.
Calculate the work done when 50 g of iron is dissolved in HCl at 25C in :
( i) a closed vessel and
( ii) an open beaker when the atmospheric pressure is 1 atm.
Solution :
(i)
When the reaction is carried in a closed vessel, the change in volume is zero.
Hence,
the work done by the system will be zero.
(ii)
When iron dissolves in HCl, hydrogen is produces.
Fe + 2HCl FeCl
+ H
2
2
56 g 1 mole
1
50 g
56
50 mole
Volume of hydrogen produced at 25C

=
nRT
P
50
56
0.0821
298
= 21.84 L
This is equal to volume change when the reaction is carr ied in open beaker.
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from= P V = 1.0 21.84
Work
done: by
the system
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=www.StudySteps.in
2212.39 J
Illustration : 7.
Calculate the amount of work done by 2 mole of an ideal gas at 298 K in
reversible
isothermal expansion from 10 litre 20 litre.
Solution :
Amount of work done in reversible isothermal expansion
w = 2.303nRT log
V2
V1
Given n = 2, R = 8.314 JK 1 mol 1 , T = 298 K, V = 20 L and V = 10L.

2
1
Substituting the values in above equation
20
w = 2.303 2 8.314 298 log
10
= 2.303 2 8.314 298 0.3010

= 3434.9 J
i.e., work is done by the system.
Illustration : 8.
5 mole of an ideal gas expand isothermally and reversibly from a pressure
of
atmat 300 K. What is the largest mass which can be lif ted through a
to 210atm
1height
metreofin this expansion ?
Solution :
Work done by the system
= nRT log P1 = 2.303 nRT log
e
P2
= 2.303 5 8.314 300 log
P1
10
P2
10
2
= 20.075 10 3 J
Let M be the mass which can be lifted through a height of 1m.
Work done in lifting the mass
= M g h = M 9.8 1J
So M 9.8 = 20.075 103
M = 2048.469 kg
5. Enthalpy
Internally energy changes are usually measured at constant volume. But in
actual practice,
most
processes
are carr
ied out at constant pressure rather than constant volume.
Hence volume
changes
which occurs cause changes in internal energy. To account for these
changes, a new property is introduced called as Enthalpy.
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It
is def ined
sumto
ofisremove
internal
energy
product
of pressure
volume
Enthalpy
of aassystem
also called
the
heatand
content
of system,
because
it is work
the
It
is
donated
by
the
letter
H.
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netaenergy
in
system
H =available
which
E + PV
can be converted
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into heat.
Characteristics :
(a)
It is a state functions
(b)
It is an extensive property
(c)
Change in its value can be determined by relationships H and E
Let a system at state-I be transformed to state-II at constant pressure
condition.
State - I St ate-II
Enthalpy H
H
1
2
Internal energy E
E
1
2
Pressure P P
Volume V
V
1
2
H = E + PV
1
1
1
H = E + PV
2
2
2
H H = H = (E + PV ) ( E + PV )
2
1
2
2
1
1
= (E E ) + P (V V )
2
1
2
1
H= E+P V
Also for an ideal gas PV = nRT
PV = n RT and PV = n RT
1
1
2
2
P(V V ) = n RT
2
1
g
Then H = E + n RT
g
q = q + n RT
p
v
g
When n = 0
H= E
g
When n > 1
H> E
g
When n < 1
H< E
g
Also E = q P V
P
q = E+P V
P
and
H = q (i.e., Enthalpy change = heat exchange at constant pressure condition)
P
also
E = q(i.e., Internal energy change = heat exchange at constant volume condition)
V
H= E+P V
q q = P V = n RT
P
Illustration : 9.
The heat of combustion of ethylene at 18C and at constant volume is
335.8
wh
enkcal
water is obtained in liquid state. Calculate the heat of
combustion
at and at 18C.
constant pressure
Solution :
The chemical equation for the combustion of C H is
2
4
C H (g) + 3O (g) = 2CO (g) + 2H O (l);
E = 335.8 kcal
2
4
2
2
2
1mole 3 mole 2 mole
No. of moles of gaseous reactants = (1 + 3 ) = 4
No. of moles of gaseous products = 2
So
n = (2 4) = 2
Given E = 335.8 kcal, n = 2, R = 2 10 3 kcal
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and T = (18 + 273) = 291 K
H = E + nRT
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= 335.8www.StudySteps.in
+ (2) (210
3 ) ( 291) = 336.964 kcal
Illustration : 10.
The enthalpy of formation of methane at constant pressure and 300 K
75.83 will
kJ. be the heat of formation at constant volume ? [ R = 8.3 JK
What
1 mol 1 ]
Solution :
The equation for the formation of methane is
C( s) + 2H( g) = CH (g) ;
H = 75.83 kJ
2
4
2 mole 1 mole
n = (1 2) = 1
Given
H = 75.83 kJ, R = 8.3 10 3 kJ K 1 mol 1
T = 300 K
Applying
H = E + nRT
75.83 =
E + (1) (8.3 10 3 ) (300)
E = 75.83 + 2.49
So = 73.34 kJ
6. Heat capacity of a system

It is the amount of heat required to raise the temper ature of a system through
1C
If q is the amount of heat supplied to a system and as a result let the
temperature
T to T C. rise from
1
Then, heat capacity = C =
q
T2
T1
q
T
When heat capacity varies with temperature then the value of C has to be
considered
over
nar
row range
ofatemperature.
Then C =
(a)
q
dT
Specific Heat and Molar Heat Capacity at Constant Volume

Specific Heat I:t is the amount of heat required to raise the temperature of 1 gm of a gas
through 1 at constant volume.
Molar heat capacity : It is the amount of heat required to raise the
mole of volume
atemperature
gas throughof1one
at constant
dq = dE + PdV
Molar heat Capacity : C =
dq
dT
dE
PdV
dT
At constant volume dV = 0
C=
E
T
=
V
E
T
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v
dT
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Hence Molecular
Specific heat at constant volume.
C v mass = SV = www.StudySteps.in
(b)
Heat Capacity at Constant Pressure

:
It is defined as the amount of heat required to raise the temperature of one
of gas
throughconstant
o keeping
1mole
pressure
E
T
CP
P
P
V
T
.......(a)
P
We know that H = E + PV
H
T
Differentiating w.r.t. temperature
From ( a) and (b)

CP
M0
CP
H
T
E
T
P
P
H
T
= S = Specific heat at constant pressure

P
C is always greater than C

P
V
When gas is heated at constant volume, the pressure of gas has to increase.
As the gas is not allowed to expand, therefor e in case of C
heat is required f or r aising the
V
temperatur e of one mole of a gas through
. When
1o
gas is heated at constant P. It expands, the
gas has done some work against external pressure. More heat is therefore
supplied to raise
its 1o .
temperature
through
Thus C is heat required for the purpose of
P
(i)
Increasing temperatures of one mole of gas through 1o .
(ii)
For increasing the volume of the gas against external pressure.
C >C
P
V
Relationship between C and C .
P
V
According to I law of thermodynamics.
dq = dq + PdV
C dT = C dT + PdV
p
V
P
V
For one mole of gas
PV = RT PdV + VdP = RdT
Since the gas is being heated at constant pressure dP = 0
PdV = RdT
C dT = C dT + RdT
P
V
Dividing both sides by dT
C =C +R
P
C - C =R
P
CP
CV
Calculation of W , E , H , for Isothermal Expansion of Ideal Gas

(A) (i)
E f or an ideal gas E depends on temperatures. Since temperature is constant
dE = 0
E =0
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According to law
Heat
to is
remove
equal
the
dE = absorbed
dq + dW;
since
dEto
=work
0 done by the system during isothermal
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(iii)
dq = -dW
expansion
ideal
Enthalpy
gas H
change
of= 0 E
++
0HHence,
nR
P= EVwww.StudySteps.in
+
T PV
(Because
= qE
=+
- W(nRT)
H T=0)
=0
(B)
Adiabatic Reversible Expansion of ideal Gas :

(a)
Calculation of E
= f (T , V)
E
T
dE
But
T V
E
dE = T
T
T=0
d
V
Also dE = nC dT for n moles

V
and dE = C dT for one moles
V
E = E - E = nC (T -T )
2
=T
nCV
E or E E = nC ( T T )
2
1
Also
q1 = 0 V 2
E = W = C (T T ) [Because expansion of gas takes place]
W = C (T V T 2) 1
V
2
1
W = nC (T T ) = nC T
V
Illustration : 11.
3
A gas expands from a volume of 3.0 dm 3 to 5.0 dmagainst
a constant pressure of
3.0 atm. The work done during expansion is used to heat 10.0 mole
of water of 290.0 K. Calculate the final temperature of water .
temperature
[ specif ic heat of water = 4.184 JK 1 g 1 ]
Solution :
Work done = P dV = 3.0 (5.0 3.0) = 6.0 litreatm = 6.0 101.3 J =
607.8TJ be the change in temperature.
Let
Heat absor bed = m S T = 10.0 18 4.184 T
Given P dV = m S
T
or
T=
P dV
m
607 .8
10 .0 18 .0 4.184
= 0.807
Final temperature = 290 + 0.807 = 290.807 K

Illustration : 12.
How much heat is required to change 10 g ice 0C to steam at 100C?
Latent and
heatvaporization
of
fusion
for H O are 80cal/g and 540cal/g respectively. Specific heat
2
of water is 1 cal/g.
Solution :
Total heat absorbed
= DEMO
H
+: Purchase
H
+ H
from
fu s i on
t emp . r is e
vap .
to remove
= 10 80 + 10
1 100the
+ 10 + 540 = 7200 cal.
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12 of 51
www.StudySteps.in
7. Corollary
(a)
Adiabatic process
(i)
Adiabatic compression
E = W. ,
E=+P V
(ii)
Adiabatic expansion
E=W
E=P V
Hence during adiabatic compression of an ideal gas internal energy of system
increases
and energy of system decreases.
during
adiabatic
(b)
Isochoric process E = q
v
(i)
Isochoric absorption of heat
E = +q internal energy of system increase
(ii)
Isochoric liberation of heat
E = q inter nal energy of system decreases
(c)
Heat absorbed by system and work done by system

E = +q W
(d)
Heat liberation by system and wor k done on the system

E=q+W
( e)
Isobatic process (expansion)

E = +q P V
P
(i)
when no gases are involved in reaction
E = +q
P
(ii)
When gases are involved but initial and final volumes are not given
E = q n RT where
n =n n
g
I.
Q.1
P ( g)
Instructions : From Question ( 1 to 3) a single statement is made.

Write T ifis true
the & F if the statement is false.
statement
A thermodynamic equilibrium is one when all the three thermal, mechanical
and chemicalare attained by the system.
equilibrium
Q.2
Ice in contact with water constitutes a homogeneous system.
Q.3
The state properties are those which depends on the path f ollowed by a
system in bringing
particular
change. a
Q.4
R (g )
The change in entropy in going from one state to another is independent of

path.
II. Instructions
(7 to 18)from
consist of a problem followed by
PDF Watermark
Remover: Questions
DEMO : Purchase
several answers,
alternative
only each
one of
which
is the
correct.
theorletter
corresponding
to
State
whether
of
to the
remove
following
will Mark
increase
decrease
the total energy
the
answer.
Pagewatermark
13 of 51Q.5
For decreases,
(i)
(iii)
content
(A)
system
(C)
acorrect
hypothetical
heat
work
of the
transferred
done
increases,
incrsystem,
by
eases,
thetoincreases
system.
decreases
the
consider
surrounding
www.StudySteps.in
(D)
these
(B)decreases,
increases,
conditions
decreases,
increases,
(ii)
increases
decreases
work done on the system
Q.6
A well stoppered thermos flask contains some ice cubes. This is an example
of :closed system (B) open system
(A)
(C) isolated system (D) non-thermodynamic system
Q.7
Internal energy change when system goes from state A to state B is 40

kJ/mol.
If the
system
goes
from
A to
B by reversible path and retur ns to state A by irreversible
path,
would
be
netwhat
change
in internal energy ?
(A) 40 kJ (B) > 40 kJ (C) < 40 kJ (D) zero
Q.8
A system X undergoes following changes

The overall process may be called
(A) reversible process (B) cyclic process

(C) cyclic as well as reversible (D) isochoric process
III. A In the adjoining diagram, the P-V graph of an ideal gas is shown.
Answer the
ollowing
question
( 11f to
13) f rom the graph.
Q.9
Q.10
Q.11
Work done in taking the gas from the state A

B
2 J (C) 60 10
(A) 36 10 2 J (B) 36 10
Work done in taking the gas from B

C
2 J (C) 3.0 10
(A) zero (B) 1.5 10
Work done in a complete cycle (1 litre = 10 3 m 3 )
2 J (C) 60 10
(A) 36 10 2 J (B) 36 10
J (D) 60 10
J (D) 3.0 10
J (D) 60 10
III. B For 1 mole of an ideal gas f ollowing V-T graph is given

to questions
remove the
Answer the following
(14 to 18) from the graph
Pagewatermark
14 of 51Q.14
Q.12 (A)
Q.13
The isothermal
0.821
3.284
pressure
process
& which
atm
1.642
at(B)
(B)
A
C and
is1.642
adiabatic
occurs
(B)
: B 1.642
in
atm
in
atmosphere
(C)
going
(C)
&www.StudySteps.in
isobaric
0.821
0.0821
fromare
atm
B(D)
(C)
respectively
(D)
isochoric
1&
C
0.821
is
2 (D)
: atm
: 0.082 & 0.164
Q.15
The work done in going form C to A is :

(A) zero (B ) 1.15 kJ (C ) 2.3 kJ (D) unpredictable
Q.16
The pr ocess A
B ref er to :
(A) isoentropic process (B) reversible process
(C) isochoric process (D) isobaric pr ocess
Q.1
Which one is not a state function ?

(A) internal energy (E) (B) volume
(C) heat (D) enthalpy
Q.2
Which is the intensive property ?

(A) temperature (B) viscosity (C) density (D) all
Q.3
Warming ammonium chloride with sodium hydroxide in a test tube is an

example
ofsystem
:
(A) closed
(B) isolated system (C) open system (D) none of these
Q.4
The work done by a system in an expansion against a constant exter nal

pressure
is (B
: ) P.
(A) P. V
V (C) Q (D) V.
Q.5
An example of extensive property is :

(A) temperature (B) internal energy (C) viscosity (D) surface tension
Q.6
A gas expands isothermally and rever sibly. The work done by the gas is :
(A) zero (B) minimum (C) maximum (D) None
Q.7
A system is changed fr om state A to state B by one path and from B to A by

another
If corresponding changes in internal energy, then :
E
and Epath.
are the
1
2
(A) E + E = +ve (B) E
+ E = ve (C) E
+ E = 0 (D) none
1
Q.8
The maximum work done in expanding 16 g oxygen at 300 K and

a volume
of the volume becomes 25 dm3 is :
5occupying
dm3 isothermally
until
3 J (C ) 2.01 10
3 J (D) +2.01 10
(A) 2.01 10 3 J (B) +2.81 10
Q.9
1 mole of gas occupying 3 litre volume is expanded against a constant

1external
atm to pressure
a volumeofof 15 litre. The work done by the system is :
(A) 1.215 10 3 J (B ) 12.15 10 3 J (C ) 121.5 10 3 J (D) none
Q.10
If 50 calorie are added to a system and system does work of 30 calorie on

surroundings,
the energy of system is :
change
in internal
(A) 20 cal (B) 50 cal (C) 40 cal (D) 30 cal
Q.11 One
mole DEMO
of an ideal
gas at 300
K is expanded isothermally from an initial
PDF Watermark
Remover
: Purchase
from
volume
1 litre
to to
10
litre. of
The
E for
thisremove
processthe
is : [ R = 2 cal K 1 mol 1 ]
(A) 163.7 cal (B) 1381.1 cal (C)www.StudySteps.in
9 litreatm (D) zero
Pagewatermark
15 of 51
Q.12
A thermodynamic process is shown in the following figur e. The pr essure

and volumes to some point in the figure are :
corresponding
P = 3 10 4 Pa , P = 8 10 4 Pa , V = 2 10 3 m 3 , V = 5 10 3 m 3
A
In the process AB, 600 J of heat is added to the system and in BC, 200 J of
heatsystem.
is addedThe
to change in internal energy of the system in the process AC
the
would
(A)
560beJ :(B) 800 J (C) 600 J (D) 640 J
Q.13
The q value and work done in the isothermal reversible expansion of one
molefrom
of ananideal
gas
initial pressur e of 1 bar to a final pressure of 0.1 bar at a
constant
of
273 K aretemperature
:
(A) 5.22 kJ, 5.22 kJ (B) 5.22 kJ, 5.22 kJ
(C) 5.22 kJ, 5.22 kJ (D) 5.22 kJ, 5.22 kJ
Q.14
In a given process of an ideal gas, dW = 0 and dQ < 0. Then for the gas :
(A) the temperature will decrease (B) the volume will increase
(C) the pressure will remain constant (D) the temperature will increase
Q.15
Five moles of a gas is put through a series of changes as shown gr

aphicallyThe
in aprocess
cyclic dur ing A
process.
B, B
C and C
A respectively are :
(A) isochoric, isobaric, isothermal (B) isobaric, isochoric, isothermal

(C) isochoric, isothermal, isobaric (D) isobaric, isothermal, isochoric
Q.16
20 gm of N at 300 K is compressed reversibly and adiabatically from 20 dm

2
Change in internal energy for the process is :
(A) 284.8 J (B) 142.46 J (C) 1424.69 J (D) 3462.89 J
3 10 dm
to
.3
8. Thermochemistry
Thermochemistry is the branch of physical chemistry which deals with the
between or
evolved
a chemical
absorbedto
system
dur
remove
ingand
thethe
its
reaction
surrounding
is called
when
a thermochemical
a change of phase or a
transfer of heat
Pagewatermark
16 of 51
chemical
takes
Thermochemical
equation.
thermochemical
place
reaction
Awith
complete
in
equation
equations
the system.
supplies
A
: Itchemical
www.StudySteps.in
isthe
alsofollowing
termed
r eaction
asinformations.
chemical
which tells
energetics.
about the amount of heat
(i)
(ii)
(iii)
(iv)
It tells about the physical state of the reactants and products. This is done by
inserting
symbols (s), (l) and (g) for solid, liquid and gaseous state respectively with
the
chemical formulae.
It tells about the allotropic from (if any) of the reactant.
The aqueous solution of the substance is indicated by the word aq.
It tells whether a reaction proceeds with the evolution of heat or with the
absorption
of change involved in the system.
heat,
i.e. heat
Exothermic Reactions :
Heat is evolved in these chemical reactions. It is possible when the bond
energy
of reactants
is
less
at constant
pressure
H ( HP H R ) = ve i.e., H P < H R
At constant volume
EEE
= ve i.e, E E
PR
PR
Endothermic Reactions :
Heat is absorbed in these chemical reactions. It is possible when bond energy
of
reactants
greater
than is
the bond energy of products.
At constant pressure
i.e., H
H H H ve
PR
At constant volume
i.e., E
E E E ve
PR
>H
>E
Sign conventions :
H
Exothermic ve ve
Endothermic +ve +ve
9. Heat of Reaction or Enthalpy of Reaction

Enthalpy : Heat content of a system at constant pressure is called enthalpy denoted by
H. From 1st Law of thermodynamics :
Q = E + PV
Heat change at constant pressur e can be
QEPV
Enthalpy of reaction is the difference between the enthalpies of the

products and
thethe quantities of the reactants indicated by chemical reaction
reactants
when
have completely
reacted.
Enthalpy of reaction ( or heat of reaction )
HHH
PR
PDF Watermark For
Remover
DEMO
: Purchase from
example,
the equation
of oxygen at constant
to volume
remove and
the 25C. The heat evolved is 335.8 kcal or
H (g) + Cl (g) = 2HCl ( g) + 44.0 Kcal or
H = 44 kcal
Pagewatermark
17 of 51
Thisinter
the
energy
equation
ofnal
the system
indicates
C22 H4 (g)
decreases
+that
(g)
by
www.StudySteps.in
335.8
= 2CO
haskcal
been
2H carried
335.8
of Ckcal
and
E 1=mole
23O 2reaction
2 +
2 O(l) ; between
2 H4 3 mole
10. Factors which affect the heat of reaction

(a)
Physical State of Reactants and ProductsThe

: heat of reaction varies for a given r eaction
with the change in physical nature of reactants or products e.g.,
C O CO ; H=-94.3 kcal
22
diamond
For reactant
having different
Physical state
C O CO ; H=-97.7 kcal
22
Amorphous
For products having different physical state ;

1
HOg HO
2(g)22
2
1
HOg HOg
2g
2 22
(b)
l ;
H 68.3 Kcal
H 57.0 Kcal
Reaction carried out a constant pressure or constant volume :

From 1st Law of thermodynamics q =
EW
at constant volume q
= E
V
and at constant pressure q
= H
p
Two values are related as
HEPV
where P
: Pressure at which the reaction is carried out

V : Change in volume during the course of reaction.
Alternatively
n
(c)
H E nRT
No. of moles of products No. of moles of reactant (only gas phases)
Temperature : Heat of r eaction also depends upon the temper ature at which reaction is
carried out. The variationvalue
in H with temperature are due to variation in heat capacities
of system with temperature.
Kirchoff s equation
HHCTT
21P21
and
EECTT
21V21
where
C C of produc ts - C of reacta nts

PpP
C C of products - C of reactants
vVV
H,H
21
are change in heat enthalpies at temperature T & T respectively

2
E , E ar e change in heat internal ener gy at temperature T & T respectively

2
(d)
Enthalpies of SolutionEnthalpies
:
of reaction differ when in one case dry substances react
PDF Watermark and
Remover
DEMO
in another
case: Purchase
when the from
same substance react in solution.
e.g.,
H
g 2HI
;2HI
H
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18 of 51
H2 2S
CuSO
S gg 4II.H
aq
O aqSCuSO
H O solution
aq
.5H
www.StudySteps.in
; O aq.
S; ;
H 172
21.9Kcal
15.8
29
3Kcal
Kcal
Kcal
24 42solution
2 CuSO
11. Terms used for Heat of Reactions

(1)
Heat of Formation or enthalpy of Formation :The amount of heat absorbed or evolved

when 1 mole of the substance is directly obtained from its constituent
elements
is called Heat
of
formation.
Standard Heat EnthalpyThe
: heat enthalpy of a compound at 25 C and 1 atm pr essure is
known as standard heat enthalpy and represented by the symbol H .
Thus the standard heat of formation of 1 mole of CO ( g) and 1 mole ofO(Hg) from their
2
2
respective elements can be represented as below :
C( g) + O (g)
CO (g) ;
H 94 Kcal
2
H (g) + 21 O (g)
2
H O( g) ;
2
H 63 Kcal
f
The compounds which have positive enthalpies of formation are called

endothermic
compounds
and
areless stable
than the reactants. The compounds which have negative
enthalpies
are
known of
as formation
exothermic compound are more stable than reactants.
Illustration 13 :
The standard enthalpies of f ormation at 298 K for CCl
are 106.7, 241.8, 393.7 and 92.5 kJ mol
( g), H O(g) , CO
(g) and HCl(g)
2
, respectively. Calculate
for
298K
the reaction, CCl (g) + 2H O(g)

CO ( g) + 4HCl(g)
4
2
2
Solution :
The enthalpy change of the given reaction will be given as
0 HCl,g H CCl 2 H H O,g
H H CO 040 0H
,g,g
ffff
242
= ( 393.7 4 92.5 + 106.7 + 2 241.8 ) kJ mol

(2)
= 173.4 kJ mol
Heat of Combustion or Enthalpy of combustion : It is def ined as the change in heat

enthalpy when one mole of a substance is completely burnt in oxygen.
C+O
CO ;
H 94.3 Kcal
2
2
C + 2S
CS ;
H 22.0 Kcal
2
Calorific Value : The amount of heat produced in calorie or joule when one gram of a
substance (food or fuel) is completely burnt or oxidised.
(3)
Enthalpy of Neutralisation : It is def ined as the heat evolved or decrease in enthalpy

when 1 gm equivalent of an acid is neutralised by 1 gm equivalent of a basein
Strsolution.
ong acid + strong Base
Salt + Water ;
H 13.7 Kcal
HCl (aq.) + NaOH ( aq.)
NaCl ( aq.) + H O(l) ;
H 1 3.75 Kcal
2
11
H 13.7 Kcal
H SO aq. NaOH aq. Na SO aq. H O
l ;
2 224242
PDF Watermark Thus
Remover
: Purchaseof
from
heatDEMO
of neutralisation
a strong acid and a strong base is merely the
strong
or weak
to
acid
remove
and
weak
theWhen
basestrong
are mixed
equivalent
amounts,
the acid and a
heatwater
ofacid
formation
of
f rom
H+ and
OH
- ions.
acidin
and
a weak base
or a weak
Pagewatermark
19 of 51
heat (aq.)
change
HCl
HCN
evolved
(aq.)
in enthalpy
+ +NH
orNaOH
is4 OH
less
(aq.)
(aq.)
than 13.7
www.StudySteps.in
Kcal.
NH
NaCN
eq.(aq.)
(aq.) + HH2 O2 O(l)
(l) ;
H 2.9
1 2.3Kcal
Kcal
4 Cl
(4)
Enthalpy of HydrationIt:is the amount of heat evolved (i.e., change in enthalpy) when
1 mole of anhydrous or a partially hydrated salt combines with required
number
moles
of
water
to of
form
a hydrate.
e.g.,
CuSO + 5 H O (l)
CuSO . 5 H O ;
H = 18.69 Kcal
4
2
4
2
CaCl ( l) + 6 H O (l)
CaCl . 6H O ; H = 18.8 Kcal
2
(5)
Enthalpy of ionisation : It is defined as the amount of heat absorbed when 1 mole of an

electrolyte completely dissociates into ions.
CH COOH
CH COO + H + ;
H = 3 Kcal
3
3
HCN
H + + CN ;
H = 10.8 Kcal
12. Law of Thermochemistry

Levoisier and Laplace Law :
According to this enthalpy of decomposition of a compound is
numerically
equal to of that compound with opposite sign. e.g.,
enthalpy
of formation
C (s) + O (g)
CO ( g) ;
H = 94.3 Kcal
2
2
CO (g)
C ( g) + O ;
H = + 94.3 Kcal
2
Hesss Law of Constant Heat Summation :

For a chemical equation that can be written as the sum of two or mor e steps,
the enthalpy
change
for the overall equation is equal to the sum of the enthalpy changes
for theThus,
individual
steps.
Hesss law enables us to break down a reaction into so many
intermediate
steps
and
passing to
each step an individual enthalpy change. The sum of the
individual
changes
must,
of course,
equal the over all enthalpy change provided the initial and
final
arecase.
the
samestates
in each
H2 (g)
+ O (g)
2
H = - x kJ mol
-1
H2 O(
l) +
2
Route A
H = - y kJ mol-1
1
1
2
O (g)
H2 = - z kJ mol-1
H2 2O ( l)
Route B
For the above example

HHH
12
An energy level diagram for the above reaction cycle is shown in figure
H (g) + O (g)from
PDF Watermark Remover DEMO : Purchase
H = - 187.6 kJ mol
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20 of 51
Fig. HEnergy
www.StudySteps.in
diagram
to illustrat
O( l) +H21O
=level
-(g)
285.9
kJ mol
HH
=O- (e
98.3
)l Hesss
kJ mol L aw
22
-1
22
-1
22
-1
Illustration 14 :
Compute the resonance energy of gaseous benzene from the following
data.
(C H) = 416.3 kJ mol 1
(C C ) = 331.4 kJ mol 1
(C = C) = 591.1 kJ mol 1
C, graphite
= 718.4 kJ m l
su b
H H , g = 435.9 kJ mol
-1
-1
d i ss 2
H benzene,
g = 2.9 kJ mol
8
-1
Solution :
To compute resonance energy, we compare the calculated value ofH (benzene,

g) with the
f
given one. To calculate H (benzene,

g), we add the following reactions.
f
6C(g) 6H(g) C H (g)
H336
66
6C(graphite) C (g)
3H (g) 6H(g)
Add
CCCCCH
H 6 718.4 kJ mol
H 3 435.9 kJ mol
6C(graphite) + 3H ( g)
C H (g)
2
6
6
The corresponding enthalpy change is
f
H 3 3 6 6 718.4 + 3 435.9 kJ mol
CCCCCH
= [ ( 3 331.4 + 3 591.1 + 6 718.4 + 3 435.9] kJ mol

The given
H0 is
f
H0 (benzene, g) = 82.9 kJ mol 1

f
This means benzene becomes more stable by (352.8 82.9) kJ mol

i.e.,269.7 kJ mol 1 . This is its resonance energy.
Experimental Determination of Heat of Reaction

The apparatus used is called calorimeter. There are two types of Calorimeters
:(a)
Bomb Calorimeter
(b)
Water Calorimeter
Bomb Calorimeter
The
: calorimeter used for determining enthalpies of combustion known
as the bomb calorimeter is shown in figure. This apparatus was devised by
Berthelot
(1881)
measure the
heat to
of combustion of organic compounds. A modified form of
the appar
shown
in atus
f igur e consists of a sealed combustion chamber, called a bomb,
containing
a
weighed
quantity
of the substance in a dish along with oxygen under about
20 atm pressure.
Ig n it io n Wi r es
+_
O2

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21 of 51
www.StudySteps.in
I ns ul ati n g
C on ta in er
B omb C al or im et er
Wat
St
ee
S er
amp
l B olemb
Bond Energy
When bond is for med between the two f ree atoms in a gaseous state to for
m a molecular
product
in a gaseous state, some heat is always evolved which is known as
the bond energy or the bond energy. The bone energy may be refer red to as
formation
heat
formation
of
theofbond.
Alternatively, bond energy may be def ined as the average amount of energy
required to(i.e. break bonds) of that type present in one molecule of the
dissociate
compound.
bond
energy
of CThus
H in
methane )(CH
is the average value of the dissociation energies of the four
4
C H bonds .
H
=
re act i o n
Bond energy data used for formation

of bond(to betaken as ve)
H
r eact i o n
= BE
(R )
Bond energy data used for dissociati

on
of bond(to betaken as ve)
- B.E. taking Bond Energies as +ve values.

(P )
Bond Enthalpy :
The average ener gy required to br eak a bond in gaseous molecule to
produce gaseous
species.
Enthalpy of Reaction :
H = (bond energy of bonds br oken)
(bond energy of bonds f ormed)
Bond dissociation Energy. The energy required to break a particular bond in
gaseous
moleculespecies.
to form gaseous
Lattice energy :
Enthalpy change when one mole of gaseous ions condense to form a solid
crystal
eg. Na+lattice.
(g) + Cl (g)
NaCl (s) .
Born Haber's cycle is useful in determination of lattice energy & related problems .
Resonance energy :
(observed heat of formation) (calculated heat of formation) .
Illustration. 15 :
Calculate the heat of f ormation of acetic acid from the following data:
(i) CH
COOH(l) + 2O (g)
(ii) C( s) + O
2CO ( g) +2H O(l) ;
(g)
CO (g)
2
H = 207.9 kcal
H = 94.48 kcal
(iii) H
(g) + 1 O ( g)
H O(l)
H = 68.4 kcal
2 2
2
2
Solution :
First method :The required eqation is
2C(s) + 2H (g) + O (g) = CH COOH( l);
H=?
2
2
3
This equation can be obtained by multiplying Eq. (ii) by 2 and also Eq. (iii)
by 2 and adding
both
finally substracting Eq.(i)
[2CDEMO
+ 2O :+Purchase
2H + Ofrom
CH COOH( l) 2O = 2CO + 2H O 2C O 2H O]
2
2
2 the
3
2
2
2
2
2
www.PDFWatermarkRemover.com to remove
HCH3 COOH
2325.76
(94.48)
+ 2+=(68.4)
(207.9)
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SecondEnthalpy
method
:ofFrom
CO
O
H22 =O
eq.
188.96
=0(ii)
(94.48
68.4
by
www.StudySteps.in
and
convention)
+
kcal
136.8
kcal
207.9
( iii)
207.9
117.86
kcal
(l)
2 =
H of Eq. (i) = Enthalphies of products = Enthalpies of reactants

207.9 = 2 (94.48) + 2(68.4)
H CH
3 COOH
(l)
HCH
3 COOH
(l )
= 188.96 136.8 + 207.9 = 235.76 + 207.9 = 117.86 kcal
Illustration 16. :
) according to
2
the following reaction ?

CaO (s) + 3C( s)
CaC (s) + CO(g)
2
The heats of formation of CaO (s), CaC (s) and CO(g) are 151.6, 14.2 and 26.4
2
kcal respectively.
Solution :
H=
H
H
f(p ro d uct s )
f( rea ct an t s )
=[
H
+ H ] [ H
+ 3 H ]
H ow mu ch h e at w i ll be r e qu i r ed to m ak e 2 k g o f c al ci u m c ar b i d e (C a C
f( Ca C2 )
f( C O)
f (C aO)
f (C )
= [ 14.2 26.4] [151.6 + 3 0]

= 40.6 + 151.6 = 111.0 kcal
For formation of 64 g of CaC 111.0 ckal of heat is required.
2
So, heat required for making 2000 g of
CaC =
2
111 .0
64
2000 = 3468.75 kcal
Example 17. :
Calculate heat of combustion of ethene:
H
H
C=C
+ 3O = O
2O=C=O + 2H OH
H
H
From bond energy data : C= C CH O=O C =O OH
K.E. KJ mol 1
619 414 499 724 460
Solution :
H = sum of bond energies of reactants Sum of bond energies of products
= [
H(C=C) + 4 H(CH) + 3 H( O=O) ] [4 H(C=O) + 4 H ]
( O H)
= [619 + 4 414 + 3 499] [ 4 724 + 4 460]
= 964 kJ mol
1
Illustration 18. :
Calculate the lattice energy for the reaction
Li+ (g) + Cl (g) LiCl (s)
From the following data :
H
s u b (L i )
= 160.67 kJ mol
1
2
( Cl ) = 122.17 kJ mol
1 ; E.A . (C l) = 365.26 kJ mol 1

I.P.DEMO
= 520.07
kJ mol
: Purchase
from
(L i )
and
H
= to
401.66
kJ mol
remove
the 1
f (L i C l )
Pagewatermark
23 of 51Solution
Applying
:
And
U
Q
401.66
=
the=substituting
equation
839.31
H=+160.67
Dmol
+the
+I.P.
122.17
respectrive
www.StudySteps.in
E.A.
+ 1 +
520.07
Uvalues,
365.26 + U
21kJ
Illustration 19. :
1
Bond dissociation enthalpies of H (g) & N (g) are 436.0 kJ mol 1and 941.8 kJ mol
2
2
and enthalpy of formation of NH (g) is 46 kJ mol.What
1
is enthalpy of atomization
3
of NH (g)? What is the average bond enthalpy of NH bond?
3
Solution :
N (g) + 3H (g)
2NH (g) ; H = 2 46 kJ/mol
2
2
3
H = S( B.E.)R S(B.e.)P
= (941.8 + 3 436) (6x) = 2 46 kJ /mol
(here x = B.E. of NH bonds)
x = 380.3 kJ mol 1
NH
N + 3(H)
3
Heat of automization = 3 390.3 = 1170.9 kJ mol 1
Q.1
Which of the following is incorrect about the reaction :

C
+ O (g)
CO (g) ; H = 94.3 kcal at 298 K and 1 atm :
( Di amo n d)
2
2
(A) heat of combustion of C
= 94.3 kcal
D
(B) heat of formation of CO
= 94.3 kcal
2
(C)
H= E
(D) standar d heat of formation of CO
= 94.3 kcal
2
Q.2
At constant P and T which statement is correct for the reaction CO(g) + 21 O (g)
2
(A) H = E
(B)
H < E (C)
(D) H is independent for physical state of reactant
Q.3
H> E
The formation of water from H (g) and O (g) is an exother mic reaction because :
2
2
(A) the chemical energy of H (g) and O (g) is more than that of water
2
2
(B) the chemical energy of H
(g) and O (g) is less than that of water
2
2
(C) not dependent on energy
(D) the temperature of H
(g) and O (g) is more than that of water
2
Q.4
CO
(g)
Equal volume of C H andare

H combusted under identical condition. The ratio of their heat
2
2
2
of combustion is :
H (g) + 21 O (g)
2
C H ( g) + 2 12 O (g)
2
H O( g) ;
H= 241.8 kJ
2CO (g) + H O(g) ;

2
H = 1300 kJ
(A) 5.37/1 (B) 1/5.37 (C) 1/1 (D) none of these

Q.5
Given
N (g)
+ 3H :(g)
(g)H
; =22 kcal. The standard enthalpy of formation of
PDF Watermark
Remover
DEMO
Purchase2NH
from
2
2
3
NH gas is :
to remove the
3
(A)
11
kcal/mol
(B)
11 (C)
kcal/mol
(C)
kcal/mol
(D)94.0
22 kcal/mol
Pagewatermark
24 of 51Q.6
Given
and
CaCO
42
thenenthalpy
kJ
(s)
(B) 202
ofof
CaO(
formation
the
kJ
reaction
s) ++202
CO
ofwww.StudySteps.in
:(g)
kJ
( g)
is22
and
42288
kJ.
CaO(s)
The
kJ enthalpy
are
ofkJformation
and 152ofkJCaCO(s)
respectively
is :
3enthalpy
2CO
2(D)
3
Q.7
1
The enthalpies of for mation of NO and NO are 28 and 90 kJ mol
respectively.
The enthalpy
2
of the reaction , 2N O(g) + O (g)
4NO(g) is equal to :
2
2
(A) 8 kJ (B) 88 kJ (C ) 16 kJ (D) 304 kJ
Q.8
Give standard enthalpy of for mation of CO (110 kJ mol

heat of combustion when one mole of graphite burns is :
(A) 110 kJ (B ) 284 kJ (C ) 394 kJ (D) 504 kJ
Q.9
The H values for the reaction,

C( s) +
O2 (g)
CO( g) +
1
2
CO(g)
O (g)
2
H = 100 kJ
CO (g) ;
H = 200 kJ
1
) and CO (394 kJ mol
). The
2
The heat of reaction for C(s) + O (g)

CO (g) is :
2
2
(A) 50 kJ (B ) 100 kJ (C ) 150 kJ (D) 300 kJ
Q.10
If, S + O
SO
H = 298.2 kJ ........ (i)
SO + 2 1 O
SO ;
SO + H O
H SO ;
H + 21 O
2
H = 98.7kJ ........ (ii)
H O;
H = 130.2 kJ ........ (iii)

H = 227.3 kJ ........ ( iv)
The enthalpy of formation of H SO at 298 K will be :

2
4
(A) 754.4 kJ (B) +320.5 kJ (C ) 650.3 kJ (D) 433.7kJ
Q.11
Standard heat of formation of CH (g) , CO (g) and water at 25 are 17.9 , 94.1 and
4
2
1
68.3 kcal mol
respectively.
The heat change (in kcal) in the following reaction at 25C is :
CH (g) + 2O (g)
CO (g) + 2H O(l)
4
2
2
2
(A) 144.5 (B ) 180.3 (C ) 248.6 (D) 212.8
Q.12
According to the equation ,

C H (l) + 15
2 O ( g)
6
3H O(l) + 6CO ( g)
2
H = 3264.4 kJ/mol, the energy evolved when 7.8 g of benzene is burnt in air
will
be : kJ/mol (B) 326.4 kJ/mol (C) 32.64 kJ/mol (D) 3.264 kJ/mol
(A)
163.22
Q.13
Q.14
When a cer tain amount of ethylene was burnt 6226 kJ heat was evolved.
If heat of of ethylene is 1411 kJ, the volume of
combustion
( atONTP) that entered into the reaction is
2
(A) 296.5 mL (B) 296.5 litre (C) 6226 22.4 litre (D) 22.4 litre
For the reactions ,

H (g) + Cl (g)
2HCl (g) + x kJ . . . . (i)
2
2
1
2HCl(g)
H ( g) + Cl (g) x kJ . . . . (ii)
2
2
2
of the
following
statements
PDF Watermark Which
Remover
DEMO
: Purchase
from is correct :
(A) x and x are numerically
and x are numerically different
to removeequal
the (B) x
1
2
1
2
x108
xkcal
> 0(B
Pagewatermark
25 of 51Q.15 (C)
If , H
(A)
2Na(s)
+(D)
+0.5
Cl
)2HCl(g)
2 x(g)
Cl
1962 (g)
kcal 2HCl
(C www.StudySteps.in
)2NaCl
NaCl(
98
; kcal
Hs)
( s)
=;(D)
44
+H
H54
(=g)
kcal
?1 ; xH2 <
= 0152 kcal then
1 Na(s)
2 2 (g)
2kcal
Q.16
Combustion of carbon forms two oxides CO and CO . Heat of formation of CO

is 94.3 kcal
2
2
and that of CO is 26.0 kcal. Heat of combustion of carbon is :
(A) 26.0 kcal (B) 94.3 kcal (C) 68.3 kcal (D) 120.3 kcal
Q.17
S + 23 O
SO + 2x kcal
SO + 2 1 O
2
SO + y kcal
The heat of formation of SO is :

2
(A) y 2x (B) (2x + y) (C) x + y (D) 2x/y
Q.18
H for CaCO (s)

CaO( s) + CO (g) is 176 kJ mol 1 at 1240 K. TheE for the change
3
2
is equal to :
(A) 160 kJ (B) 165.6 kJ (C) 186.3 kJ (D) 180.0 kJ
Q.19
From the thermochemical reactions ,

C
g rap h i t e
+ 21 O
CO ;
CO + 21 O
H = 110.5 kJ
CO ; H = 283.2 kJ
H f or the reaction , C
+O
CO is :
gr aph i t e
2
2
(A) 393.7 kJ (B) +393.7 kJ (C ) 172.7 kJ (D) +172.7 kJ
Q.20
H (g) + 21 O (g)
2
H O (l) ; H= 68.32 kcal. Heat of vapourisation of water at 1 atm

2
29 8 K
and 25 C is 10.52 kcal. The standard heat of formation (in kcal) of 1 mole
of 25
water
vapour
at
C is
:
(A) 78.84 (B) 78.84 (C) +57.80 (D) 57.80
Q.21
Given that standar d heat enthalpy of CH , C H and C H

are 17.9, 12.5, 24.8 kcal/mol.
4
2
4
3
8
The H for CH + C H
C H is :
4
2
4
3
8
Q.22
For the reaction,

C H ( g) + 5O ( g)
3CO (g) + 4H O(l)
3
8
2
2
2
at constant temper ature, H - E is :
(A) +RT (B) -3RT (C) +3RT (D) - RT
Q.23
The standard enthalpy change for a reaction,

CO (g) + H (g)
CO(g) + H O(g) is 2
2
2
[ Given that
Hf f or CO(g) and H2 O(g) as -110.5 and -241.8 kJ mol
heat of combustion of C(s) is -393.5 kJ/mole ]
(A) 41.2 kJ (B) -41.2 kJ (C) -393.5 kJ (D) +393.5 kJ
-1
and
Q.24 The standard internal energy change ( U) for the reaction,

OFDEMO
( g) + H
O(g)
O (g) + 2HF(g) is PDF Watermark Remover
:2Purchase
from
2
2
Given that standard to
enthalpies
and HF(g) as +23.0,
remove of
theformation Hf of OF 2 (g), HO(g)
2
-1 (B)
Pagewatermark
26 of 51Q.25 (A)
-241.8,
The
-heat
10
standard
393.5
kcal
-268.6
of kJ
mol
dimerisation
enthalpies
(B)
kJ
-318.4
respectively.
of
ofkJ
6.0
formation
NO
(C)
kcal
in
-537.2
gaseous
mol
of- 1kJ
NO(D)
state
(C)
- 320.8
and
is-14
- Nkcal
O4 (g)
mol8-1 and 2(D)
kcal- 6.0
mol
respectively.
kcal
mol-1
-1 mol
2www.StudySteps.in
2 (g)
2kJ
-1
Q.26
Given that , C + O
CO ;
H = x kJ and 2CO + O
2
2
The standard enthalpy of formation of carbon monoxide is :
2x
(A) y 2x (B)
Q.27
(C)
x2
3
3
2
(B) x +
1
x2
3
2
2x
(D) 2x y
Given that , NH
+ 3Cl (g)
NCl (g) + 3HCl(g) ;
3
2
3
N (g) + 3H (g)
2NH (g) ;
2
2
3
H2 (g) + Cl2 (g)
2HCl( g) ;
The heat of formation of NCl3 (g) fr om the above data is (A) -x +
2CO ;H = y kJ.
(C) x 1
x2
2
H=x
1
1
H=x
2
2
H3 = + x 3
3
2
(D) -x 1
x2
2
3
2
Q.28
H of CO (g), CO(g), N O(g) and NO

( g) in kJ /mol are respectively - 393, -110, 81 and
f
2
2
2
34. H in kJ of the following reaction : 2NO 2 (g) + 3CO(g)
N 2 O(g) + 3CO2 (g)
(A) 836 (B) 1460 (C) -836 (D) -1460
Q.29
If E is the heat of reaction,

C2 H5 OH(l) + 3O2 (g)
2CO 2 (g) + 3H2 O(l)
at constant volume, the
H (heat of reaction at constant pressure) at constant temperature is (A) H = E - RT (B)
H = E - 2RT
(C) H = E + 2 RT (D)
H = E + RT
Q.30
Change in enthalpy for the reaction,

2H2 O2 (l)
2H 2 O(l) + O2 (g)
-1
if heat of formation of H2 O2 (l) and H2 O(l) are -188 kJ mol-1 and -286 kJ mol
respectively
is
(A) -196 kJ mol- 1
(B) +196 kJ mol-1
(C) +948 kJ mol -1
(D) -948 kJ mol- 1
Q.31
Enthalpy of CH + 2 1 O
4
CH OH is negative. If enthalpy of combustion of CHand
CH OH are x and y respectively, then which relation is cor rect :

3
(A) x > y (B) x < y (C) x = y (D) x
Q.32
The heat of combustion of graphite and carbon monoxide respectively are

-1 . Therefore the heat of formation of carbon monoxide in kJ mol-1 is :
-393.5kJkJmol
mol
-283
(A) +172.5 (B) - 110.5 (C) -1070 (D) +110.5
Q.33
In a reaction involving only solids and liquids, which of the following is true
(A) H < E (B)
H = E (C)
H > E (D)
H = E + RTn
Q.34
H for the reaction,

CH COOC H (l) + H O(l)
CH COOH( l) + C H OH(l)
3
2
5
2
3
2
5
Given heat of formation of CO (g) H O(l), C H OH(l
) is a, b and c kJ/mole r espectively and
2
2
2
5
heat of combustion of CH COOC H (l) and CH COOH) (lis d and e kJ/mole respectively.
3
-1
and
Q.35
H for the reaction,
C H (g)
+ 29toOremove
( g)Heatthe
CO(g)
+ 2COof
(g)CO(g)
+ 4H is
O(g)
286 kJ/mole
respectively.
of
combustion
283.2 kJ/mole
3
8
2
2
2
Pagewatermark
27 of 51
Given
and
vapourisation
heat
heat
of of formation
of water isof
44.2
CO(g),
kJ/mole.
www.StudySteps.in
C 3 H8 (g), H)2 O(l
is 110.5 kJ/mole, 104.16 kJ/mole and
Q.1
The amount of heat evolved when one mole of H SO reacts with two mole of NaOH is :
2
4
(A) 13.7 kcal (B) less than 13.7 kcal(C) more than 13.7 kcal (D) none
Q.2
Energy r equired to dissociate 4 g of gaseous hydrogen into fr ee gaseous

atom .isThe
208bond
kcal energy
at
25C
of H H bond will be :
(A) 104 kcal (B) 10.4 kcal (C) 1040 kcal (D) 104 cal
Q.3
The heat of neutralisation of HCl by NaOH is 55.9 kJ/mol. If the heat of

neutralisation
ofis 12.1 kJ/mol. The energy of dissociation of HCN is :
HCN
by NaOH
(A) 43.8 kJ (B) 43.8 kJ (C) 68 kJ (D) 68 kJ
Q.4
Bond energies of (H H), (O=O) and ( OH) are 105, 120 and 220 kcal/mol
r espectively
then
H in the reaction,
2H (g) + O (g)
2H O(l)
2
2
2
(A) 115 (B) 130 (C ) 118 (D) 550
Q.5
Heat evolved in the reaction , H + Cl 2HCl is 182 kJ. Bond ener gies of H H and
2
2
Cl Cl are 430 and 242 kJ/mol respectively. The HC l bond energy is :
(A) 245 kJ mol 1
(B) 427 kJ mol1
(C) 336 kJ mol 1
(D) 154 kJ mol 1
Q.6
If the enthalpy change for the reaction

CH (g) + Cl (g)
CH Cl(g) + HCl(g)
4
2
3
1
H = 25 kcal. bond energy of C H is 20 kcal mol
greater
than the bond energy of C C l
and bond energies of H H and HCl are same in magnitude, then f or the
reaction 1: H
1 Cl
HCl( g) ;
H=?
2 2 (g) + 2 2 ( g)
(A) 22.5 kcal/mol (B) 20.5 kcal/mol (C) 32.5 kcal/mol (D) 12.5
kcal/mol
Enthalpy of neutr alization of HCl with NaOH is x. The heat evolved
whenare
500
ml ofwith
2 N 250 ml of 4 N NaOH will be
HCl
mixed
(A) 500 x (B) 100 x (C) x (D) 10 x
Q.7
Q.8
Q.9
The bond energies of C C, C = C, H H and C H linkages are 350,

600,kJ
400
410
perand
mole respectively. The heat of hydrogenation of ethylene is :
(A) 170 kJ mol 1
(B) 260 kJ mol 1
(C ) 400 kJ mol 1
(D) 450 kJ mol 1
The enthalpy change ( H ) of the following reaction,

f
2C H (g) + 5O (g)
4CO (g) + 2H O(g) is
2
2
2
2
2
Given aver age bond energies of various bonds, i.e., C H, CC , O = O, C = O, O H
as 414, 814, 499, 724 and 640 kJ mol 1 respectively
(A) 7632 kJ (B) 186.1 kJ (C ) 2573 kJ (D) 763.2 kJ
Q.10 The bond ener gy oftoCremove
H bond
thein methane from the following data :
(a)
s)
+ 2H
(g)
CH 4www.StudySteps.in
(g)mol
; 1 H
kJ
Pagewatermark
28 of 51
(b) C(
(c)
(A)
C(
H
416
s) kJ
g) 1 2C(g)
2H(g)
(B)
; ; 1664
kJ
H=
= 74.8
435.4
718.4
(C) 217.7
kJ kJ mol 1
(D) 1741 kJ mol 1
2 ( mol
Q.11
For the following reaction,

C
+O
CO (g) ; H = 94.3 kcal
D i amo nd
2
2
C
+O
CO (g) ; H = 97.6 kcal
G rap hi t e
2
2
(i) The heat of transition f or C
C
Di am on d
Gr ap hi t e
(A) +3.3 kcal (B) 3.3 kcal (C) 19.19 kcal (D) 191.9 kcal
(ii) The heat required to change 1g of C
C
is :
d i amo n d
gra ph i t e
Q.12
For the following reaction,

H (g) + 21 O (g)
H O(g) ; H = 57.0 kcal
H (g) + 21 O (g)
H O(l) ; H = 68.3 kcal
(i) The enthalpy of vapourization for water is :

(ii) The heat required to change 1 g of H
O(l)
H O(g) is :
2
2
Q.13
The heat of reaction for N + 3H

2NH
at 27C is 91.94 kJ. What will be its value
2
2
3
at 50C ? The molar heat capacities at constant P and 27C f or N
, H and NH
are
2
2
3
28.45, 28.32 and 37.07 joule respectively
(A) +45.74 kJ (B) +92.84 kJ (C ) 45.74 kJ (D) 92.84 kJ
Q.14
Enthalpy of neutralization of HCl by NaOH is 57.32 kJ mol 1 and by NH

OH is 51.34 kJ
4
mol 1 . The enthalpy of dissociation of NH OH, is :
4
(A) 4.98 kJ mol 1
(B) 108.66 kJ mol1 (C ) 108.66 kJ mol1 (D) 5.98 kJ mol 1
Q.15
1 enthalpy of neutralisation of a
The enthalpy of formation of H O (l) is 285.83 kJ mol
and
2
str ong acid and a strong base is 55.84 kJ mol1 . The enthalpy of formation of OH
ions
is :
(A) 341.67 kJ mol 1 (B) 229.99 kJ mol1 (C ) 229.99 kJ mol1 (D) 341.67 kJ mol1
Q.16
H for the r eaction,

f
Ag+ (aq) + Cl (aq)
AgCl(s)
1
at 25C. Given H (Ag + , aq) = 105.58 kJ mol 1 , H (Cl , aq) = 167.16 kJ moland
f
f
H ( AgCl, s) = 127.07 kJ mol 1 .
f
(A) 65.49 kJ mol 1 (B) 65.49 kJ mol1
(C) 188.65 kJ mol 1 (D) 188.65 kJ mol1
Q.17
The change in state is

HCl(g) + aq
H + (aq) + Cl (aq)
Given H (HC l, g) = 92.31 kJ mol 1 and H (Cl , aq) = 167.16 kJ mol 1 , then
f
f
The enthalpy change when one mol of HCl(g) is dissolved in a very large
amount
25C
is :of water at
(A) 259.47 kJ mol 1 (B) 74.85 kJ mol1
(C ) 259.47 kJ mol1 (D) 74.85 kJ mol 1
PDF Watermark
Remover
Q.18 Given
: DEMO : Purchase from
Enthalpy of combustion of methane
H = 890.36 kJ mol 1
Pagewatermark
29 of 51
H2 (g)
Enthalpy
The
(A)
415.85
bond
+ 21of
enthalpy
O2sublimation
combustion
dissociation
kJ
(g)molof
C
(B)
of
O(l)
C
415.85
H(g)
H
from
www.StudySteps.in
kJthe
mol
f ollowing
(C)
=data
393.51
285.85
435.93
716.68
at 298
kJmol
kJKmol
is
(D) 166.339 kJ mol1
1 H
2of
2 (graphite)
1
rr H1663.39
1 : 1
Q.19
The enthalpy changes of the following reaction at 25C are

Na( s) + 21 Cl (g)
NaCl(s) ;
H (g) + S(s) + 2O (g)

2
2
2Na(s) + S( s) + 2O (g)
2
H SO (l)
2
4
Na SO (s) ;
2
H = 411.0 kJ mol 1
H = 811.3 kJ mol 1
H = 1382.3 kJ mol 1
1 H (g) + 21 Cl (g)
HCl(g) ;
H = 92.3 kJ mol 1
2 2
2
r
From these data, find the heat change of reaction at constant volume at 25C
for the process
2NaCl(s)
+ H SO (l)
Na SO ( s) + 2HCl(g)
2
4
2
4
(A) 57.1 kJ mol 1
(B) 60.92 kJ mol 1 (C) 60.92 kJ mol 1
(D) 57.1 kJ mol 1
Q.20
Energy required to dissociate 4g of H

(H H) will be :
(A) x kJ M1
(B) x/2 kJ M1
(g) into free gaseous atoms is x kJ. The value of

H
(C) x/3 kJ M 1
(D) 0.25 x kJ M 1
Q.21
For the reaction,

2Cl(g)
Cl (g). The sign of H and S respectively are :
2
(A) + and (B) + and + (C ) and (D) and +
Q.22
1
The enthalpy of atomisation of CH and C H are 360 and 620 k cal molrespectively.
The
4
2
6
C C bond energy is expected to be :
(A) 210 k cal mol 1
(B) 130 k cal mol1
(C) 180 k cal mol 1
(D) 80 k cal mol 1
Q.23
1 enthalpy
The enthalpy of neutralization of NH OH and CH COOH is 10.5 k cal mol
and
4
3
1
of neutralization of CH COOH with str ong base is 12.5 kcal mol . The
enthalpy of
3
ionization of NH OH will be :
4
(A) 4.0 k cal mol 1
(B) 3.0 kcal mol1
(C) 2.0 kcal mol 1
(D) 3.2 kcal mol 1
Q.24
Polymerisation of ethene to polyethene is represented by the equation,

n(CH = CH )
( CH CH )
2
2
2
2
n
Given that average enthalpies of C = C & C C bonds at 298 K are 590 and
331 k J mol predict the enthalpy change when 56 g of ethene changes to
respectively,
polyethylene.
(A) 72 kJ (B) 72 kJ (C) 144 kJ (D) 144 kJ
13. Limitations of First Law of Thermodynamics

Though the first law of thermodynamics gives us the exact equivalence of
heat
and work,
whenever
there is a change of heat into work or vice versa, but it suffers from
the following
limitations
: two
(i)
No indication is available as regards the direction in which the change will
proceed.
(ii)
It
gives no idea about the extent to which the change takes place.
These limitations can be understood from the following examples :
(iii)
This law can easily explain the heating of a bullet when it str ikes a block
PDF Watermark conversion
Remover
: Purchase
fromheat, but it fails to explain as to why heat in
due
to the DEMO
of kinetic
energy into
be
When
from
It
no
changed
answer
practically
flowing
a vessel
tointo
this
from
of
kinetic
found
observation.
water
towater
remove
that
energy
is placed
whole
into
Thus,
the
ofthe
bullet
of
over
first
fire,
heat
fire,
and
law
and
canheat
make
fails
thereby
never
flows
to
it be
fly
tell
cooling
converted
into
back
extent
the
from
the
vessel.
tointo
water
which
inside
work.
What
and
the
of
theis
block
cannot
Pagewatermark
30 of 51(v)
(iv)
the block.
prevents
ultimately
The
interchange
into
ice.
work
first Thus
the
law
and
converting
of
heat
has
direction
vice
heat versaofis(flow)
possible.
www.StudySteps.in
change is not known from first law.
14. Spontaneous and Non-Spontaneous Processes

1. Spontaneous Process
: In our daily life, we come across a large number of physical and
chemical processes which occur in a widely varying conditions. For example,
(i)
Some processes proceed on their own, e.g. Water always flows down a hill,
heat flows
fromtemperature
a
body
at higher
to a body at lower temper atur e.
(ii)
Some processes require proper initiation but once properly initiated they
continue
on their
own ignited continues to burn till whole of it has been
e.g.
Kerosene
oil once
consumed
or exhausted.
(iii)
Some
processes
proceed only so long as the external energy is availably. e.g.
Electrolysis
of so long as current is passed and stops as soon as cur rent is
water
continues
cut off . which
The can take place by itself or after proper initiation, under the
process
given
setaofspontaneous
conditions, process. the term Spontaneous simply means that
is called
given process
is
feasible
or possible.
Therefore, Spontaneous processes are also called as
feasible or Spontaneous
probable
processes.
process may or may not be instantaneous. But all
instantaneous
process
are
spontaneous.
It may be pointed out that the term Spontaneous should not mean that the
process occurs
instantaneously.
It simply implies that pr ocess has an ur ge to proceed or it
is paretically
possible.
e.g. (i) Processes which occur on their own without proper initiation.
(a) HCl(g) + NH
(g)
NH Cl(s)
3
4
(b) H
O(l)
H O(g)
2
2
Water keeps on evaporating from ponds and rivers etc.
(c) Sugar dissolves in water and forms a solution.
(d) 2NO(g) + O
(g)
2NO (g)
2
2
(ii) Processes which require initiation
(a) In domestic oven, once coal (carbon) is ignited it keeps on burning
C( s) + O (g)
2
CO (g)
2
(b) CH
(g) + 2O (g)
CO ( g) + 2H O(l)
4
2
2
2
From the above discussion we conclude that spontaneous process is the one
which hastonatural
tendency
occur.
2. Non-Spontaneous Process : A process which has no tendency to occur or which is made to
occur only if energy from outside is continuously supplied e.g.
(i)
Decomposition of water into H and iOs non-spontaneous. However, water can be
2
2
decomposed by passing an electric current through it, in a process called
electrolysis.
H O(l) Electricit y 2H (g) + O (g)
2
2
2
The process will continue as long as electric current is supplied , and as soon
as the of electricity is cut off the decomposition stops.
supply
(ii)
Water cannot be made to flow up the hill, without the help of a machine.
Gold
ornaments
do not
get tarnished in air even after a number of years. This
PDF Watermark (iii)
Remover
DEMO
: Purchase
from
shows
that gold does
not
combine
with oxygen
the air.
occur spontaneously
toindicated
remove
that
the there
must beinsome
driving force behind
Driving
Force
f
or
a
Spontaneous
Process:
the
natural
tendency of various processes to
Pagewatermark
31 of 51
them.
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15. Entropy
It may be defined as the measure of degree of randomness in the molecule. It
is represented
the
symbol S. by
Characteristic of Entropy
(i)
It is a state of function
(ii)
It is an extensive property
(iii)
The exact value may be determined by applying the III law of
thermodynamics
The change
in entropy during a pr ocess when a system undergoes char ge
from
oneisstate
to
another
represented
as S.
Thus S = S - S
fi n al
i n i t i al
and f or chemical reaction S = S
-S
p ro du ct
R eact a nt
Calculation of Changes in Entropy

(a) Reversible Process at Equilibrium
S
(i)
(ii)
qRe v
T
In a reversible reaction heat gained in the forward reaction is equal to heat

lost in the
reverse
reaction.
Hence in a reversible cyclic process the net charge in entropy is zero. This is
called
Clausius Theorem
S
=
S
+ S
un iv er s e
sy s t em
s y st em
=T
S ur ro un di n g
qRe v(system )
su rr ou nd i n g
=T
qRe v(surroundin g )
Heat gained by system = heat lost by surrounding

S
= Q
R ev( s ys t em)
un iv er s e
=T
R ev (s u rro u nd i ng )
qRe v(system )
q
+ T Re v (surroundin g )
q
q
= T Re v (system ) - T Re v(system )
Hence
(iii)
(iv)
u ni v ers e
(Rev)=0
S > 0 for ir reversible process

u ni v
Entropy change for an isothermal process
E=q+w
E = 0 (Isothermal process)
V
q = -w
V
ButDEMO
w = 2.303
nRT log
q=2.303 nRT log 2
: Purchase
from2
V
V1
www.PDFWatermarkRemover.com to remove the1
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32 of 51
orSfor
Also
= VqaReTreversible
process
www.StudySteps.in
nRT
q log V12 ),
S==2.303
2.303nRT
nR log
log PVV211212
1 T
1 (2.303
v P
r ev
(v)
Entropy change in an isobaric process

dq
dS = T Re v (P) also dq
R ev( P )
= dH
But dH = C dT
p
Integrating both sides
S
dS = C dT/T
p
T2
dS = Cp,
T1
dT
T
T1
ln T
1
T2
S = 2.303 Cp log
(vi)
T2
=n TCT2
S=C
T1
Entropy change for Isochoric process

dq
dS = T Re v(V ) Also dq (Rev)(v) = dE
But dE = CvdT
Integrating both sides one get
dq = CvdT
v
T2
S = V =n Cvln
T TT2
T1
T2
S = 2.303 Cv log
(vii)
Entropy change during mixing of ideal gas

S = R
n nx
mi x
= R [n
ln x + n ln x + n ln x ......]
S = R
n= m
ni
mi x
n xi
ni no.
n xof
moles of the gas
i
(viii)
T1
n = mole fraction of the gas

i
Entropy changes during phase transformation
S=
q Re v
T
(a) Ent ropy of fusion :

The entropy changes taking place when 1 mole of a solid
substance change into liquid form, at the melting temperature.
S
fus i o n
H fusion
= T
fusion
Entropy
of:vaporization
is the entropy change when one mole of a liquid
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changes
into
vapours
point.the
Entropy at
of boiling
sublimation
to remove
is the entropy change when one mole of a solid
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(c)
changes at
vapours
into
Ssvapsublimation
Stemperature.
THboiling
THsubsub
vapourisat
point
ion
ub = S vap
l www.StudySteps.in
i qu i d=
(d)
Hence for any physical transformation

S
t ran s i t i on
(ix)
H transition
Ttransition
Let a given mass of a liquid be heated from temperature T to. T

Assuming specific
1
2
heat of liquid to be constant between T and Tand that no change occurs the
1
2
amount of heat required to raise the temperature by dT is given by
dq = mCdT
T2
S = mC ln T
1
16. Second Law of Thermodynamics

It can be defined in number of ways as follows
1.
All spontaneous processes (or naturally occurring processes) are
thermodynamically
irreversible.
2.
Without the help of the an external agency, a spontaneous process cannot
be
reversed e.g., heat cannot by itself flow from a older to hotter body.
3.
The complete conversion of heat into work is impossible without leaving
some effect
elsewhere.
4.
All spontaneous processes are accompanied by a net increase of entropy.
5.
The entropy of the universe is increasing.
6.
The entropy is a time arrow.
17. Gibbs Free energy

It is defined as, the energy available in the system for conversion into useful
work.
It is that thermodynamic quantity of a system, the decrease in whose value
duringtoa the
process
is work done by the system.
equal
useful
G = H TS
where H is the that content, T is the absolute temperature and S is the entr
opybefore,
of the system.
As
for the isothermal processes, we have
G = H T S (Gibbs Helmotz equation)
H = H H is the enthalpy change of the system
2
1
Deriving the criteria for spontaneity from Gibbs-Helmholtz equation. Accor
ding to GibbsHelmholtz
equation
G= HT S
The equation combines in itself both the factor which decide the spontaneity
of
a process,
namely
theDEMO
energy :factor,
H from
(ii)
the entropy factor, T S
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Depending upon thetosigns
of Hthe
and
S and
T their relative magnitudes, the following different
remove
possibilities
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34 of 51
1.
Whenarise.
randomness
(i)
(ii)
(iii)
both
If H
factor
H=
> and
<
T opposes
ST, www.StudySteps.in
the
S are
it,
prThen
process
negative
ocessisisin
spontaneous
non-spontaneous
i.e.,
equilibrium
energy factor
and
andand
favours
GGisisG
negative.
zero.
the
is positive.
process but
2.
3.
When both H and T S are positive i.e., energy factor opposes the process but
randomness factor favours it. Then
(i)
If H > T S , the process is non-spontaneous and G is positive.
(ii)
If H < T S, the process is spontaneous and G is negative.
(iii)
IF H = T S, the process is in equilibrium and G is zero.
When H is negative butS Tis positive i.e., energy factor as well as the randomness
factor favour the process. The process will be highly non-spontaneous and
G will be
highly positive.
An important advantage of free energy criteria over the entropy criteria lies
in thethefact
that
former requires free energy change of the system only whereas the
latter
requires
the total
entropy change for the system and the surroundings.
Physical significance of Gibbs free energy :

S=q+w
E=q+w
+w
exp an s i on
n on ex pan s i on
E=qP V=+w
n on ex pan s i on
E+P V=q+w
n on ex pan s i on
H=q +w
R ev
(because w
ex pa ns i o n
= P
V)
n on ex pan i s on
(For a reversible process taking place at constant temperature.
S=
q Re v
T
Re v
= TS)
As q = T S and E + P V = H we get
Re v
H=T S+w
[ w
=w
]
u s efu l
no ne xp ans i o n
u s efu l
HT S=w
u s efu l
G=w
us ef ul
(i)
When useful work is done by the system
w
= ve value
us ef ul
G = ve value and G = w
us e ful
G
G
= ve
p ro du ct
reac t ant
G
G
p ro du ct
re act i o n
Capacity to do useful work by product is less than the capacity to do useful
work by reactant
Product more stable than reactant.
Hence according to II law of thermodynamics the process is a spontaneous
process
as
every
substance
wants to be in the state of maximum stability.
(ii)
When work is done on the system
w
= +ve
G = +ve
G >G
u se fu l
P
R
Capacity to do useful work by product is more than the capacity to do useful
work by reactant
Reactant more stable than product
Process non-spontaneous according to II law of thermodynamics
Relationship between G to
and
Equilibrium
constant
remove
the
G =between
2.303
RTGlog
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35 of 51
Relationship
where
nFE
K = equilibrium
andKstandard
constant
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cell potential
18. Third Law of Thermodynamics

It states that, Entr opy of all per fectly crystalline solids may be taken as zer
o as the
absolute
zero
of temperature.
Third law of thermodynamics may also be defined as
(i)
The entropy of a solid is zero at the absolute zero of temperature.
(ii)
It is impossible to reduce the temperature of any system to absolute zero by
anyany
process.
(iii)
At
pressure, the entropy of every crystalline solid in thermodynamic
equilibrium
absolute
zeroatis zero.
(iv)
At the absolute zero, increment in entropy for isother mal process in
crystalline
approaches zero as the limit.
(v)
At absolute zero, every crystal becomes ideal crystal.
Q.1
In which case, a spontaneous reaction is possible at any temperature

(A) H < 0, S > 0 (B)
H < 0, S < 0
(C) H > 0, S > 0 (D) in none of the cases
Q.2
In a chemical reaction H = 150 kJ and S = 100 JK 1 at 300 K. The

G f or the reaction is
(A) zero (B) 300 kJ (C) 330 kJ (D) 120 kJ
Q.3
For reaction at 25 C enthalpy change ( H) & entropy change ( S) are 11.7 10J3mol- 1
and 105 J mol1 K 1 respectively. The reaction is :
(A) spontaneous (B) nonspontaneous
( C) instantaneous (D) none
Q.4
The temper ature at which the reaction,

Ag O(s)
2Ag(s) + 1/2 O (g)
2
2
is at equilibrium is ............... ; Given
H = 30.5 kJ mol1 and
(A) 462.12 K (B) 362.12 K (C) 262.12 K (D) 562.12 K
S = 0.066 kJ K1 mol 1
Q.5
3
1
The enthalpy and entropy change for a chemical reaction are 2.5 10cal
and 7.4 cal deg
respectively. Predict that nature of reaction at 298 K is
(A) spontaneous (B) reversible (C) irreversible (D) nonspontaneous
Q.6
Which is not correct ?

(A) in an exothermic reaction, the enthalpy of products is less than that of
reactants
(B)
H = H
H
fus i o n
s u bl i ma i t on
v ap or i s at i on
(C) a reaction for which
H < 0 and S > 0 is possible at all temperature
(D)
H is less than E for the reaction C(s) + (1/2) O (g)
CO ( g)
2
Q.7
For the reaction :

2NO(g) + O (g)
2NO (g)
2
2
-1
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DEMO
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fromare -113.0 kJ mol -1 and -145 J K-1 mol
enthalpy
and entropy
changes
respectively.
Find
The
enthalpy change
tof remove
or a given
thereaction
reaction is
at spontaneous
298 K is -x cal/mol. If the
the temperature
above
which
the
Pagewatermark
36 of 51Q.8
reaction
spontaneously
(A)
(B)
(C)
(D)
can
cannot
432.3
be
occur
Knegative,
negative
be(B)
negative
positive
sat 570.5
298but
but
K,K
numerically
numerically
the
(C)entropy
1035.7
www.StudySteps.in
larger
change
smaller
K (D)than
779.3
atthan
that
x/298
x/298
Ktemperature
calcal
K K - 1-- 1
Q.9
The favorable condition for a process to be spontaneous is :

(A) T S > H, H = +ive, S = -ive (B) T
S > H, H = +ive, S = +ive
(C) T S = H, H = - ive, S = -ive (D) T
S = H, H = +ive, S = +ive
Q.10
At 300 K, the reaction which have the following values of thermodynamic

parameters, occur
spontaneously
(A) G = -400 kJ mol -1
(B) H = 200 kJ mol -1 , S = -4 JK- 1 mol-1
(C) H = -200 kJ mol -1 , S = 4 JK-1 mol - 1 (D) H = 200 kJ mol - 1 , S = 40 JK-1 mol-1
Q.11
Which of the following statement(s) is/are correct ?

(A) the system of constant entropy and constant volume will attain the
equilibrium
in a stateenergy
of minimum
(B) the entropy of the universe is on the increase
(C) the process would be spontaneous when (
S) < 0, ( E) > 0
E, V
S, V
(D) the process would be spontaneous when (
S)E, V > 0, ( E)S, V < 0
Q.12
-1
For melting of ice at 25C the enthalpy of fusion is 6.97 kJ, mol
, entropy
of fusion is 25.4 J
K-1 mol -1 and free energy change is -0.6 kJ mol -1 . Predict whether the melting of ice is
(A) non spontaneous (B) spontaneous (C) at equilibrium (D) not pr edicted
Q.13
For a process at H and TS both are positive in what conditio, the process is spontaneous
(A) H > T S (B)
H < T S (C)
H = T S (D) not pr edicted
Q.14
At 0C, ice and water are in equilibr ium and H = 6.0 kJ mol-1 for the process
H O(s) H
O(l)
2
2
The value of S and G for the conversion of ice into liquid water are
-1 mol -1 and 0
(A) -21.8 J K -1 mol -1 and 0 (B) 0.219 J K
-1 mol -1 and 0
(C) 21.9 J K -1 mol - 1 and 0 (D) 0.0219 J K
Q.15
The entropy change at 373 K for the transformation

1
H2 O(l)
H 2 O(g) is : [ Given :
H = 40.668 kJ mol.- Pressure
= 1 bar ]
va p
(A) 128.17 J K- 1 mol -1
(B) 109.03 J K- 1 mol -1
(C) 19.15 J K -1 mol -1
(D) 98.35 J K- 1 mol -1
Q.16
The entropy change for the conversion of one gram of ice to water at 273 K
and one
atmospheric
pressure is : [
H
= 6.025 kJ mol -1 ]
fu s i on
(A) 7.30 J K-1 mol -1 (B) 1.226 J K -1 g -1
(C) 1.226 J K -1 mol -1 (D) 7.30 J K - 1 g -1
Q.17
In a reaction A+ + B
A +, ther
B+ e is no entropy change. If enthalpy change is 22 kJ
for the reaction G for the reaction is :
(A) 22 kJ mol-1
(B) 11 kJ mol-1
(C) 33 kJ mol-1
(D) 44 kJ mol-1
Q.18
-1
H and S f or Br (l) + Cl (g)
2BrCl(g) and 29.37 kJ and 104.0 J K respectively.
2
2
Above what temperature will this reaction become spontaneous ?
(A) T > 177.8 K (B) T > 354.1 K (C) T > 282.4 K (D) T > 141.2 K
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Q.19 Remover
H and SDEMO
for the: system
H 2from
O(l) H
O(2g) at 1 atmospheric pressur e are 40.63 kJ
to
remove
the
-1
mol-1 and 108.8 J K - 1 molrespectively.
The temperature at which the rates of f orward and
Pagewatermark
37 of 51Q.20 (A)
backward
The
373.4
2.577
equilibrium
2NOCl(g)
K
r eactions
10
(B)-4[ 256.2
constant
Given
2NO(g)
will
(B)
K be
(C)
K1.958
H
same,
for
316.8
Cl
=www.StudySteps.in
the
77.2
is10
following
K:kJ
(D)
and
( g)reaction
(C)
SisK=
28.4
: 122at
J10
400
K --31 K
at 400 K(D)
] 1.466 10 -2
c+
-4
2278.5
Problem 1 :
C( s) + O(g)
CO (g) + 394 kJ
2
2
C( s) + 1/2 O (g)
CO + 111 kJ
2
(a) In an oven using coal (assume the coal is 80% carbon in weight),
insufficient
oxygen is supplied such that 60% of carbon is converted to O and 40% carbon
2
is converted to CO.
Find out the heat generated when 10 kg of coal is burnt in this f ashion.
(b) Calculate the heat generated if a more efficient oven is used such
that only
CO is formed.
2
(c) Calculate the percentage loss in heating value for the inefficient oven.
Solution :
(a)
C( s) + O(g)
CO (g) + 394 kJ ............ (i)
2
2
C( s) + 1/2 O(g)
CO + 111 kJ ............. (ii)
2
Weight of C in 10 kg coal = 10000 0.8 = 8000 g
Weight of C converted into CO = 8000 0.6 = 4800 g
2
weight of C converted into CO = 8000 0.4 = 3200 g
12 g (1 mole) C on conversion into CO liber ates = 394 kJ
2
4800 g of c on conversion into CO liberates = 153,600 kJ
2
12 g(1 mole) C on conversion into CO liberates = 111 kJ
3200 g of c on conversion into CO liberates =
(b)
3200
12
= 29600 kJ
Total heat liberated = 153600 + 29600 kJ = 183200 kJ

C( s) + O( g)
CO ( g) + 294 kJ
2
2
12 g car bon liberates heat = 394 kJ
8000 g of carbon liber ates heat =
(c)
111
294
8000
12
= 262666.67 kJ
Heat lost by oven = 26266.67 183200 = 79466.67 kJ

% lost of heat =
79466 .67 100

262666 .67
= 32.25%
Problem 2 :
the standard
internal
energy change f or the following reaction
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Remover DEMO
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at
2H25C.
O (l)
2H to
O (l)
+ O (the
g)
remove
2
2
2
2
t 1s) , H2 O
(l)
188
kJ
( l) = 286 kJ
kJ mol 1
Pagewatermark
38 of 51Solution H
: f at 25C
n(g)
H =for
==1H
2(286)
196
E
572
H
=2+1
+
1(p ro376
+
n=du( g)08.314
RT
=www.StudySteps.in
2196
(188)
10
Hmol
= 198.4775
20O
ct
)
(rkJ
eac3
t an298
Problem 3 :
A s ample of argon gas at 1 atm pressure and 27C o expands reversibly and
adiabatically from 125 dm 3 to 250 dm
. Calculate
3
the enthalpy change in this
process. C . for argon is 12.48 JK - 1 mol - 1 .
V
Solution :
For adiabatic expansion, we have
Cv
R
ln
12 .48
8 .314
ln
T2
300
T2
T1
ln
=
= ln
T2
300
V2
V1
= ln2
0.3010
8.314
12 .48
V2
V1
=2
12 .48
8 .314
In
T2
300
ln
T2
300
= 0.3010
= 0.200
T = 300 1.586 =475.8 K or 202.8 o C

2
T = T -T = 475.8 -300 =175.8K
2
1
C =C +R
P
V
C = 12.48 + 8.314 = 20.794 JK -1
P
Now, PV = nRT
1 1.25 = n 0.0821 300
n=0.05
We know
H = nCp T = 0.05 20.794 175.8 = 182.77 J
Problem 4 :
Calculate the heat of neutralization from the following data 200 ml of 1

M HClwith
is 400 ml of 0.5 M NaOH. The temperature rise in calorimeter
mixed
was4.4
found
to equivalent of calorimeter is 12 g and specif ic heat is 1
o C. Water
be
cal/ml/degree
for solution.
Solution :
The heat pr oduced ( H) dur ing neutralization of 200 Meq. of NaOH and HCl each
1
(Meq. = N V) is taken up by calorimeter and solution in it.
H = Heat taken up by calorimeter + solution
1
H= m S
T+m S T
1
1
1
2 2
= 12
[ total solution = (200 + 400) ml.] =2692.8 cal
Neutralization of 200 Meq. gives heat =-2692.8 cal
Neutralization of 1000 Meq. gives heat = -2692
5 = -13464 cal
= - 13.464 k cal
Problem 5 :
The thermochemical equation for the combustion of ethylene gas, C

H , is
2
4
DEMO
Purchase
CH
(g) + :3O
( g) from
2CO (g) + 2H O(1) ;
H = -337 KCAL
2
4
2
2
remove
the 2 the weight
Assuming 70% eff to
iciency,
calculate
of water at 20
C othat can be
Pagewatermark
39 of 51
converted into
vaporization
ofsteam
wateratat100
20 o oCCwww.StudySteps.in
and
by burning
100Co are11.00
m 3 of
kcal/kg
C2 H
gas
measured
540 kcal/kg
at S.T.P.
respectively.
Heat of
4 and
Solution :
No. of moles in 1 m3 of ethylene = 44.6 mol
H for 1 m3 of ethylene (44.6 mol of ethylene) = n(C H )
H (1 mole)
2
4
= 1.50
10 4 kcal
The useful heat = 1.05
10 4 cal
For the overall process, consider two stages :
H O (1) 20o C
H O(l) 100o C ;
H = (1.00 kcal/kg, K) ( 80 K) =80 kcal/kg
2
2
H O( 1) 100o C
H O(g) 100o C ;
H = 540 kcal/kg
2
2
H (total ) =620 kcal/kg
Wt. of water converted into steam =
Amount of heat available

Heat required / kg
1.05 10 4
620
= 16.9 kg
Problem 6 :
Calculate the heat of formation of anhydrous aluminium chloride, Al

,Cl
from the
2
6
following data.
(i) 2Al(s) + 6HCl(aq.)
Al Cl (g) ; 3H ( g) ;
H =- 240 kcal
2
6
2
(ii) H
(g) + Cl ( g) 2HCl(g) ;
H=-44.0 kcal
2
2
(iii) HCl(g) + aq .
HCl(aq.) ;
H=-17.5 kcal
(iv) Al
Cl (s) + aq.
Al Cl (aq) ;
H=-153.7 kcal
2
Solution :
The required equation is
2Al(s) + 3Cl (g)
Al Cl (s) ;
H=?
2
2
6
For obtaining this ,
Multiply (ii) by 3, (iii) by 6 and add the resulting equations to (i)
(i)
2Al (g) + 6HCl(aq.) Al Cl (aq.) + 3H (g) ; H = 240.0 kcal
2
6
2
Subtract (iv) from (v) and rearrange the product
2Al ( s) + 3Cl (g) + aq.
A Cl ( aq.) ; H = - 477.0 kcal
2
2
6
-Al Cl (s) - aq.
-Al Cl (aq);
H = +153.7 kcal
2
6
2
6
2Al ( s) + 3Cl (g) - Al Cl (s)
; H = -323.3 kcal
2
2
6
or 2Al(s) + 3Cl
(g)
Al Cl ; H=- 323.3 kcal
2
2
6
Hence the heat of formation of anhydrous aluminium chloride = -323.3 kcal
Problem 7 :
10 g of argon gas is compressed isothermally and reversibly at a

temperature
from 10L to 5ofL.27Calculate q, W and
E for this process. (At wt. of Ar =40)
Solution :
10
Co
No. of moles of argon =

= 0.25 mole and V
= 10 litre, V= 5 litres, T = 300 K
1
2
40 from
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Now we know that during
to remove
isothermal
the reversible process, internal energy
V2
Pagewatermark
40 of 51
For isothermal
Amount
remains
throughout
=constant
of
2.302
heat
the reversible
process,
absorbed
2.5 hence
2compression
=103.6
300
the
www.StudySteps.in
cal
change
logW 10
in
=5 energy
=2.303
103.6(nRT
calE)log
will be zero.
V1
Problem 8 :
Calculate the maximum work done when pressure on 10 g of hydrogen

is reduced
from
20 to 1 atm at a constant temperature of 273 K. The gas behaves
ideally.
there
beWill
any change in internal energy. Also calculate Q.
Solution :
W = 2.303 nRT log
P1
10
= 2.303
P2
273 log
20
= 8180 calories
Since the change is taking place constant temperature, internal energy will
notEchange,
i.e.
=0
Q = E + W = 0 + 8180 = 8180 calories
Problem 9 :
The heat of combustion of glycogen is about 476 kJ/mol of carbon.
Assume heat
that loss by an adult male is 150 watt. If we were to assume that
average
all
the from
heat oxidation of glycogen, how many units of glycogen (1 mole
comes
carbon
perbe oxidised per day to provide for this heat loss ?
unit)
must
Solution :
Total energy required in the day
2460 60 kJ
(1 watt = J sec
1000
Units of glycogen required =
) = 12960 kJ
12960 27.22
476
Problem 10 :
The heat of total cracking of hydrocarbons
101.325 kPa f or the process below :
TC
units.
is defined as Hat 298.15 K and
m
C H + 2n - H nCH
n m 2( g ) 4 g
2
Given that H
TC
is 65.2 kJ f or C H and 87.4 kJ for C

2
H , calculate
8
H for
CH g + C H g 2C H g
43826
Solution :
of CH = 0
4
CH (g) + C H (g)
H
TC
4
2C H ( g)
2
H 2 H C HT.C.H2 C
H
6 T.C. 3 8
= 2 ( 65.2 ) ( 87.4 ) = 43 kJ
Problem 11 :
A constant pressure calorimeter consists of an insulated beaker of mass
92
gofmade
PDF Watermark up
Remover
DEMO
Purchase
from0.75 J K 1 g .1 The beaker contains 100 mL of 1 M
glass
with :heat
capacity
HCl of 22.6C
reaction
? Assume
to which
that
to remove
the
100heat
mL1
thecapacities
M NaOHofatall
23.4C
solutions
is added.
are equal
The final
to that
Pagewatermark
41 of 51
af same
temperature
of
volumes
ter theofreaction
water. is complete www.StudySteps.in
is 29.3C. What is
H per mole for this neutralization
Solution :
Initial average temperature of the acid and base
=
22.6 23.4 23.0 C

2
Rise in temperatur e = (29.3 23.0) = 63C

Total heat produced = ( 92 0.75 + 200 4.184) 6.3
= (905.8) 6.3 = 5706.54 J
Enthalpy of neutralisation =
57065.54 1000 1
100
= 57065.4 J = 57 kJ
Problem 12 :
Find bond enthalpy of S S bond from the f ollow ing data :
C H SC H
2
1
H = - -147.2
kJ mol
C H SSC H
2
1
H = - -201.9
kJ mol
f
S(g)
1
H = - 222.8
kJ mol
f
Solution :
H
4C(s) + 5H + S
CCSCC
H
4C(s) + 5H + 2S
HS
CCSCC
H B.E. B.E.
(i)
(ii)
RP
147.2 = Heat of atomization of 4C , 10H, 1S

B.E. of 10(C H), 2( C S), 2(C C)
201.9 = Heat of atomization of 4C, 10H, 2S
B.E. of 10( C H), 2(C S), 2(C C), ( S S)
Subtracting (i) from (ii)
201.9 + 147.2 = Heat of formation of 1S B .E. of (S S)
= 222.8 kJ B .E. of (S S)
B.E. of ( S S) = 277.5 kJ
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ProblemRemover
13 :
to remove
the
From the data at 25C
:
Pagewatermark
42 of 51
Calculate
Fe2standard
FeO(s)
C(
graphite)
O3 (s)+ C(graphite)
+ 3C(graphite)
heat
+ O 2of
( g)formation
www.StudySteps.in
ofCO
2Fe(s)
CO
FeO(22 +
(g)
s)3CO(
and, Fe
g) ,2 O3 ( s). H = -282.98
492.6 kJ/mol
155.8
kJ/mol
Solution :
Fe(s) + CO(g)
FeO(s) + C(graphite)
C( graphite) + O (g)
2
H 158.88 kJ / mol
CO (g)
H 393.5 kJ / mol
CO (g)
CO(g) + 1/2 O ( g)
H 282.98 kJ / mol
2
2
On adding Fe(s) + 1/2 O (g)
FeO(s) ;
H 393.5 kJ / mol
2
Similarly we may calculate heat of formation of FeO .
2
Problem 14 :
Show that the reaction, CO(g) + ( 1/2 ) O
(g)
CO (g)
2
2
at 300 K is spontaneous and exothermic, when the standard entropy
change
0,094 is
kJ mol 1 K 1 . The standard Gibbs f ree energies of f ormation of CO and CO
2
are 394.4 and 137.2 kJ mol 1 respectively.
Solution :
The given reaction is ,
CO( g) + (1/2) O (g)
CO (g)
2
(for r eaction) = GCO

G CO
GO
22
1
2
= 394.4 ( 137.2 ) 0
= 257.2 kJ mol 1
G = H T S
257.2 = H
298 (0.094)
or
H = 288.2 kJ
G is ve, hence the process is spontaneous, and
H is also ve, hence the process is
also exothermic.
Problem 15 :
Assume that for a domestic hot water supply 150 kg of water per day must
be heated
from
10C to 65C and gaseous fuel propane C H
is used for this purpose. What moles
3
8
& volume of propane (in litre at STP) would have to be used for heating
1 specific heat of water is
domestic
water. H for combustion of propane is 2050 kJ mol
&
4.184 10 3 kJ/g.
Solution :
Heat taken up by water = m S T
= 150 103 4.184 10 3 55 = 34518 kJ
2050 kJ heat is pr ovided by 1 mole C H
3
8
34158 kJ heat is provided by = 34518/2050
= 16.838 mole of C H
3
8
Volume of C H at NTP = 16.838 22.4 litre
3
8
= 3.77 102 litre
to remove the
Problem 16 :
Pagewatermark
43 of 51
Using
of
C the
C
H2&
C(
+
data
s)C+21(OH
O
all
bonds.
values
; ;CO
H in
cal
; mol
; at
) given
kcal
kcal
below, calculate bond energy
H =C-94.0
172
104
-68.0
22H
2 C(g)
2 O(l)
2 k www.StudySteps.in
1 25
Solution :
For C H : 3C + 4H
3
8
For C H : 2C + 3H
2
C H;
3
8
C H;
2
2
H=?
H=?
H 2 C C 8 C H 3C 4 H H
. . . . . (1)
H2 1s g C C 6 C H 2C 3 H H
. . . . . (2)
1sg
Also given C + O
H+
2
1
2
CO ;
k cal . . . . . (5)
H 94.0
H O; H = 68.0 k cal . . . . . (6)

2
C2 6H2 2 27/ 2 O 2CO 3H O ;
H 530 kcal
. . . . . (7)
C H + 5O
3CO + 3H O ;
H = 530 kcal . . . . . (8)
3
8
2
2
2
By inspection method : 2 (5) + 3 ( 6) (7) gives
2C + 3H
C H
;
H 20 k cal
2
2
6
and 3 (5) + 4 (6) (8) gives
3C + 4H
C H
;
24 k cal
2
3
8
By equation (3), (4), (9) and (10)
a + 6b = 676
2a + 8b = 956
a = 82 k cal and b = 99 k cal
Bond energy of C C bond = 82 k cal
and Bond energy of C H bond = 99 k cal
2
. . . . . (9)
. . . . (10)
Problem 17 :
The standard enthalpy of combustion at 25C of hydrogen, cyclohexene
)Hand
6
10
(C
cyclohexane
(C H ) are 241, 3800 and 3920 kJ/mole respectively. C alculate the
6
12
heat of hydrogenation of cyclohexane.
Solution :
The required reaction is
CHH CH, H?
6 10 2 6 12 1
Cyc lohe xen e
. . . . . (1)
Cycl ohe xane
Let us write the given facts

H + 21 O
2
6 CO + 5 H O ;
17
C6 10H2 2O
6CO 5H O,
2
2
C H + 9O
6
12
H = - 241 kJ/mole . . . . . (2)

H
= 3800 kJ/mole . . . . . (3)
= 3920 kJ/mole . . . . . (4)
6CO + 6H O,
The required reaction (1) can be obtained by adding equations (2) and (3)
andfrom
subtracting
(4)
the sum of (2) and (3).
C H +H
C H .
6
10
2 to remove
6
1 the
2
=
(
+
)
H
H
H
Pagewatermark
44 of 51
= ( 241
4041 +3800)
= 3920
[ 241
=( + 3920)
( 3800)www.StudySteps.in
]H
4( 3920)
121 kJ/mole
1
Problem 1 :
If 1.00 kcal of heat is added to 1.2 L of oxygen in a cylinder at constant

pressure
ofthe volume increases to 1.5 L, Hence
1.000
atm,
E for this process is:
(A) 0.993 kcal (B) 1.0073 kcl (C) 0.0993 kcal (D) 1.00073 kcal
Solution : (A)
H= E+P V
1.00 =
E+
1(1.5 1.2) L atm

0.082 L atm
2 10 3 kcal
E = 0.993 kcal
Problem 2 :
Using only the following data:

(I) Fe
O (s) + 3CO (g) 2Fe(s) + 3CO
2
3
(II) Fe(s) + CO(g) FeO(s) + CO( g) ;
the H value, in kilojoules, f or the reaction Fe
CO (g) is calculated to be:
2
(A ) 43.3 (B ) 10.3 (C) +6.2 (D) +10.3
Solution : (C)
fr om equation (I) + (2 II) ;
H = 6.2 kJ
( g) ; H = 26.8 kJ
H = + 16.5 kJ
O (s) + CO(g) 2FeO( s) +
3
Problem 3 :
Enthalpy change when 1.00 g water is f rozen at 0C, is : (

H = 1.435 kcal mol )1
fus
(A) 0.0797 kcal (B ) 0.0797 kcal (C) 1.435 kcal (D) 1.435 kcal
Solution : (B)
H (per g) =
1.435
18
kcal
= 0.0797 kcal g
Problem 4 :
1
Heat of neutralisation of CsOH with all strong acids is 13.4 kcal mol . the
heat
1
released on neutralization of CsOH with HF ( weak acid) is 16.4 kcal mol
H of ionisation of HF is:
Solution : (B)
CsOH + H+ = Cs + H O
2
H = 13.4 kcal
Heat of ionisation of CsOH = 13.7 13.4 = + 0.3 kcal
DEMO
: Purchase
CsOH
+ HF
CsF + Hfrom
O
2
to
remove
the
H = 16.4 kcal
Pagewatermark
45 of 51
HeatH+ofand
(of
neutralization
ionisation
13.9
OH+ )x +
of0.3
HF
CsOH
= =13.7
=1.64
x=kcal
0.3
www.StudySteps.in
kcal
x = 3.0 kcal
Problem 5 :
The C Cl bond energy can be calculated from:

(A)
H (CCl , l) only (B)
(CCl , l) and D( Cl )
f
4
f
4
2
(C)
H (CCl , l) D(Cl )
f
4
2
(D)
H ( CCl , l) D(Cl ), H (C, g) and H (CCl )
f
4
2
f
va p
4
Solution : (D)
C(s) + 2Cl (g)
CCl (l)
2
4
H (CCl , l) = H[C(s)
C(g)] + 2( BE) [ H (CCl ) + 4(BE)
]
f
Cl C l
vap
C l C l
Problem 6 :
Enthalpy of fusion of a liquid is 1.435 kcal mol

5.26 cal mol 1 K 1 . Hence melting point of liquid is :
(A) 100C (B) 0C (C) 373 K (D) 273
Solution : (B)
S=
T=
1435 cal
5.26
and molar entropy change is
= 273 K
0C
Problem 7 :
For the reaction

X O (l) 2XO
( g)
2
4
2
E = 2.1 kcal. S = 20 cal/K at 300 K
Hence G is :
Solution : (B)
H = E + n RT = 2.1 + 2 0.002 300 = 3.03 kcal
g
G = H T S = 3.3 300 ( 0.02) = 2.7 kcal
Problem 8 :
If
G=
H T S and
G=
H+T
d( G )
then variation of EMF of a cell E,
dT
P
with temperature T, is given by :

H
(A) nF
G
(B) nF
S
(C) nF
S
(D) nF
Solution : (C)
On compar ison :
Problem 9 :
S=
d( G )
dT
S=
d( nFE )
dT
= nF
dE
dE
dT
dT
PDF Watermark 1Remover

from
g H gasDEMO
at S.T.P.: Purchase
is expanded
so that volume is doubled. Hence work done is:
2
to remove
the11.2 L atm (D) 44.8 L atm
(A) 22.4 L atm (B) 5.6
L atm (C)
Pagewatermark
46 of 51Solution
V21:(volume
(C) W =ofP 1 V
gH
= 11.2
= 11.2
L22.4
atmLLwww.StudySteps.in
at NTP
2 ) =
S
nF
Problem 10 :
Following reaction occurs at 25C :

2NO(g, 1 10 5 atm) + Cl (g, l 10 2 atm) 2NOCl(g, l 10
2
G is:
(A ) 45.65 kJ (B ) 28.53 k J (C ) 22.82 kJ (D) 57.06 kJ
Solution : (A)
G = 2.303 RT log K
2
PNOCl
K =
eq
2 P
PNO
Cl
eq
= 108 Hence
atm)
G = 45.65 kJ
Problem 11 :
1 mol of NH gas at 27C is expanded under adiabatic condition to make volume 8

3
times ( = 1.33). Final temperature and work done respectively are:
(A) 160 K, 900 cal (B) 150K, 400 cal (c) 250 K, 1000 cal (D) 200 K, 800 cal
Solution : (A)
T =T
2
V1
V2
= C
1
8
= 300
T = C v(T T )
2
1.33 1
= 150 K
(
for adabatic pr ocess w = q)
= 3 2 (150 300) = 900 cal (
Cv
Cv
= 1.33
Problem 12 :
Temperature of 1 mol of gas is increased by 1 at constant pressure. Work

done is:
R
(A) R (B) 2R (C)
(D) 3R
2
Solution : (A)
W = P ( V)
PV = RT
P(V + V) = R(T + 1)
PV + P V = RT + R
P V=R
Problem 13 :
The gas absorbs 100 J heat and is simultaneously compressed by a

constant
pressure external
of 1.50 atm from 8 L to 2L in volume. Hence
E will be:
(A ) 812 J (B) 812 J (C) 1011 J (D) 911 J
Solution : (C)
H= E+P V
1.5

100DEMO
= E:+Purchase from
8.314
0.0821
E = 1011.4 J
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www.StudySteps.in
= 3 R)
Problem 14 :
The standard heat of combustion of solid boron is equal to:

(A)
1 H (B O ) (C) 2
2
f
2
3
H (B O ) (B)
f
1 H (BOP)
2
f
2 3
H (B O ) (D)
f
Solution : (B)
Problem 15 :
C C = R . This R is :
P
v
(A) Change in K.E. (B) Change in rotational energy
(C) work done which system can do on expanding the gas per mol per
degree increase in temperature
(D) All correct
Solution : (C)
PV = RT at temp T for one mol
P(V + V) = R( T + 1) at temp. (T + 1) for one mol
P V=R
Problem 16 :
For A
B,
H = 4 kcal mol 1 ,
S = 10 cal mol 1 K1 .
Reaction is spontaneous when temperature can be :
(A) 400K (B) 300K (C) 500K (D) none is correct
Solution : (C)
G = ve for spontaneous charge
G= HT S
T S > H, T >
H
S
T >
4000
10
T > 400 K
Problem 17 :
If a process is both endothermic and spontaneous , then :

(A) S > 0 (B)
S < 0 (C)
H < 0 (D)
Solution : (A)
As
G= HT S
For spontaneous process, G = negative
For endothermic process, H = positive
Ther efor e S > 0
Problem 18 :
For which change
HE
(A) H + I
2HI (B) HCl + NaOH
2
(C) C( s) + O (g) CO
( g) (D) N
+ 3H
2
2
2
2
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G>0
NaCl + H O
2NH
Problem 19 : .
If a chemical change is brought about by one or more methods in one
or more
steps,
then the amount of heat absorbed or evolved during the complete
course ofis same, which ever method was followed. This law is known as
reaction
(A ) Le Chatelier s principle (B ) Hesss law
(C) Joule Thomson ef fect (D) Troutons law
Solution : (B)
The statement is definition of Hesss law
Problem 20 : .
The Kirchhoff s equation gives the effect of ..... on heat of reaction.
(A) Pressure (B) Temperature (C) Volume (D) Molecularity
Solution : (B)
Kirchhoff s equation is :
H
H = C (T T )
2
Problem 21 : .
The heats of neutralisation of f our acids A , B , C , D are 13.7, 9.4,
11.2 and
12.4
kcal respectively when they are neutralised by a common base.
The acidicobeys the order :
character
(A) A > B > C > D (B) A > D > C > B (C) D > C > B > A (D) D > B > C > A
Solution : (B)
Lower is heat of neutralisation , more is dissociation energy, weaker is acid
Problem 22 : .
1
The H f or CO (g), CO(g) , and HO( g) are 393.5, 110.5 & 241.8 kJ mol
2
2
respectively. The standard enthalpy change (in kJ) f or the reaction ,
CO (g) + H (g)
H O(g) is :
2
2
2
(A) 524.21 (B) 41.2 (C ) 262.5 (D) 41.2
Solution : (B)
Given
C+O
CO
;
H = 393.5 kJ . . . . (i)
2
2
C + ( 1/2)O
CO ;
H = 110.5 kJ . . . . (ii)
2
H + (1/2) O
H O;
H = 241.8 kJ . . . . (iii)
2
2
2
By (ii) + (iii) (i),
CO + H
CO + H O ;
H = + 41.2
f
1. Daily Practice Problem Sheet

1. T 2. F 3. F 4. T 5. A 6.toCremove
7. D the
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8. CB 9.
16.DC10. A 11. B 12. A 13. B 14.www.StudySteps.in
C

1. C 2. D 3. C 4. B 5. B 6. C 7. C
8. A 9. A 10. A 11. D 12. A 13. A 14. A
15. A 16. C

1. D 2. B 3. A 4. A 5. A 6. D 7. D
8. C 9. D 10. A 11. D 12. B 13. B 14. A
15. C 16. B 17. A 18. B 19. A 20. D 21. D
22. B 23. A 24. D 25. C 26. C 27. D 28. C
29. A 30. A 31. B 32. B 33. B
34. d + c - e - 2a - 3b 35. - 1539.94 kJ

1. C 2. A 3. B 4. D 5. B 6. A 7. C
8. A 9. C 10. A 11. A 12. (i) A , ( ii) (D) 13. D
14. A 15. C 16. A 17. D 18. B 19. B 20. B
21. C 22. D 23. C 24. B

1. A 2. D 3. B 4. A 5. A 6. D 7. D
8. B 9. B 10. A C 11. A B D 12. B 13. B 14. C
15. B 16. B 17. A 18. C 19. A 20. B

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CHEMICAL THERMODYNAMICS

2. Some fundamental Definitions

6. State function and Path Function :

For a given system, E is directly proportional to its absolute temperature. (E T)

Work is expressed as the product of two factors, i.e.,

(a) Pressure volume work (Irreversible)

Force = Pr essure area

W = 2.303 nRT log V2

W = 2.303 nRT log

Work is not a state function because amount of work performed depends

The first law of thermodynamics states that Energy can neither be

1.0 0.821 373

Change in volume = Vol. of steam vol. of water

Volume of hydrogen produced at 25C

Given n = 2, R = 8.314 JK 1 mol 1 , T = 298 K, V = 20 L and V = 10L.

w = 2.303 2 8.314 298 log

= 2.303 2 8.314 298 0.3010

= 2.303 5 8.314 300 log

6. Heat capacity of a system

Then, heat capacity = C =

Specific Heat and Molar Heat Capacity at Constant Volume

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Heat Capacity at Constant Pressure

Differentiating w.r.t. temperature

From ( a) and (b)

= S = Specific heat at constant pressure

C is always greater than C

Calculation of W , E , H , for Isothermal Expansion of Ideal Gas

Adiabatic Reversible Expansion of ideal Gas :

Also dE = nC dT for n moles

Final temperature = 290 + 0.807 = 290.807 K

Heat absorbed by system and work done by system

Heat liberation by system and wor k done on the system

Isobatic process (expansion)

Instructions : From Question ( 1 to 3) a single statement is made.

Ice in contact with water constitutes a homogeneous system.

The change in entropy in going from one state to another is independent of

Internal energy change when system goes from state A to state B is 40

A system X undergoes following changes

(A) reversible process (B) cyclic process

Work done in taking the gas from the state A

Work done in taking the gas from B

III. B For 1 mole of an ideal gas f ollowing V-T graph is given

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The work done in going form C to A is :

Which one is not a state function ?

Which is the intensive property ?

Warming ammonium chloride with sodium hydroxide in a test tube is an

The work done by a system in an expansion against a constant exter nal

An example of extensive property is :

A system is changed fr om state A to state B by one path and from B to A by

The maximum work done in expanding 16 g oxygen at 300 K and

1 mole of gas occupying 3 litre volume is expanded against a constant

If 50 calorie are added to a system and system does work of 30 calorie on

A thermodynamic process is shown in the following figur e. The pr essure

Five moles of a gas is put through a series of changes as shown gr

(A) isochoric, isobaric, isothermal (B) isobaric, isochoric, isothermal

20 gm of N at 300 K is compressed reversibly and adiabatically from 20 dm

9. Heat of Reaction or Enthalpy of Reaction

Enthalpy of reaction is the difference between the enthalpies of the

10. Factors which affect the heat of reaction

Physical State of Reactants and ProductsThe

For products having different physical state ;

Reaction carried out a constant pressure or constant volume :