CHEMICAL

THERMODYNAMICS

By: PSR
 CHEMICAL THERMODYNAMICS

This topic deals with energy changes between the

system & surroundings in any process and it
introduces parameters like
 Internal energy( E/U )
 Enthalpy( H )
 Entropy( S ) – which helps to explain the
spontaneity of any physical & chemical
process.
 Helmholtz free energy function( A )
 Gibbs free energy function( G )
 This topic introduces three fundamental laws of
thermodynamics, purely based on human
experiences about processes occurring in nature
or in laboratory.
These laws are applicable to -
-Macroscopic systems
-Closed & isolated systems

Time is not a thermodynamic variable i.e it does

not talk about the time required to undergo a
particular process.
 SYSTEM
Any specified portion of universe under
investigation is called system and the rest of
the universe is called surroundings.

TYPES OF SYSTEM
1. OPEN SYSTEM

It is defined as a system, which

can exchange matter as well as
energy with the surroundings. For
example, a liquid kept in an open
flask. The walls may or may not
be conducting.
2. CLOSED SYSTEM
It is defined as a system which
can exchange energy with the
surroundings but not the matter.
For example, a liquid in a closed
vessel. The walls of the system are
conducting (diathermal).
3. ISOLATED SYSTEM
It is defined as a system which
can neither exchange matter nor
energy with the surroundings.
For example, a thermally insulated
flask.The walls of the system are
non-conducting (adiabatic).
 SURROUNDINGS
That portion of the universe excluding the system.
System + Surrounding = Universe
During any process, the changes in the system may be
small or large but changes in the surrounding is always
extremely small.

BOUNDARY
Boundary is a region separating the system and the
surroundings.

It may be real or imaginary, rigid or non- rigid,

conducting or non-conducting.
 THERMODYNAMIC PROCESS
IT IS AN OPERATION BY WHICH A SYSTEM
UNDERGOES A CHANGE FROM ONE STATE TO
ANOTHER UNDER A GIVEN SET OF CONDITIONS.

ISOTHERMAL PROCESS
A process in which the temperature remains
constant throughout its course i.e. T = 0,so U = 0
& H = 0.

ADIABATIC PROCESS
A process during which no heat is exchanged
between the system and the surroundings is called
adiabatic process. i.e. q = 0. P, V & T will vary.
 ISOCHORIC PROCESS
A process during which volume of the system
remains constant is called isochoric process. i.e. V
= 0, so w = 0.
ISOBARIC PROCESS
A process during which pressure of the system
remain constant is called isobaric process.i.e. P= 0.

CYCLIC PROCESS
A process during which state of the system does
not change is called cyclic process.
i.e. U = 0 , H = 0, G = 0 and also S = 0 .
REVERSIBLE PROCESS
A process in which the driving force is
infinitesimally greater /smaller than the opposing
force is called reversible process.

p ext = pgas - dp (Expansion)

p ext = pgas + dp (Compression)

Eqlb between system & surrounding is maintained.

Since changes in surroundings are extremely small,
so all processes wrt surroundings are always
reversible.
The external pressure does not remain constant
through out the process.

The process is quasistatic, taking place in infinite

no. of steps & take infinite time to occur.

These processes are imaginary & hypothetical.

IRREVERSIBLE PROCESS

A process in which direction can not be

reversed/altered by small changes in variables like
P, V, T etc. is called irreversible process.
 p ext = pgas - p (Expansion)

p ext = pgas + p (Compression)

Eqlb between system & surrounding is maintained

only initially & finally.
Large change in external parameter causes
irreversible process.

External pressure remain constant throughout the

process.
The process occurs rapidly in finite no. of steps &
in finite time. They are the real processes.
EXTENSIVE & INTENSIVE PROPERTIES
Properties which depend on the amount of matter
are called extensive properties.
e.g. mass, length, volume, internal energy, enthalpy,
entropy, Gibbs free energy, resistance,
conductance etc.
Properties which do not depend on the amount of
matter are called intensive properties.
e.g. Pressure, temperature, density, specific heat,
specific volume, surface tension, viscosity,
refractive index, M.P,B.P, conc, colour, molar
volume, electromotive force, resistivity,
conductivity etc
STATE FUNCTIONS OR STATE VARIABLES
Those fundamental properties which determine
the state of a system are called state variables
or state functions or thermodynamic parameters.
The change in the state function is dependent on
the initial and final states of the system and not on
the path followed.
State variables are:1. Pressure (P) 2. Volume (V)

3. Temp(T)4. Internal energy(E) 5. Enthalpy(H)

6.Entropy(S) 7. Gibbs Free energy(G) 8. Helmholtz
Free energy(A) 9.Number of moles(n).

ESHA is a PG WATCHInG TV.

PATH FUNCTIONS OR PATH VARIABLES
Those properties which depends on the path
taken by a system are called path variables or
path functions.
The change in the path function has no meaning and
path functions comes into action only when the
process is carried out.

Some Path functions are 1. Work(w) 2. Heat(q)

Work can be a state function when the process is

carried out adiabatically and heat can also be a
state function when it is added to the system at
constant volume or constant pressure.
EXACT & INEXACT DIFFERENTIALS

A state function is a property that depends solely

on the state of the system. It does not depend on
how the system was brought to that state.

When a system is brought from an initial to a final

state, the change in a state function is independent
of the path followed.

An infinitesimal change of a state function is an

exact differential.
Internal energy ( U ) is a state function & dU is an
exact differential.
f

 dU  U
i
f  U i  U Independent of state.

Work and heat are not state functions and do not

correspond to exact differentials.
Any substance is characterized by five
thermodynamic variables like composition, n , P, V
& T. The composition gets fixed, once we decide
it’s a solid, liquid or a gas & ‘n’ gets fixed as fixed
moles are taken.
Of the 3 thermodynamic variables left, P, V & T,
only 2 are independent as third can be determined
using equation of state for that substance.
 LET  BE A FUNCTION AND d BE ITS
EXACT DIFFERENTIAL.
The integral of d between any two points will
be a function of the end points only and will be
independent of the path.
B

 d  
A
B   A  

The term  is then just B   A  . Its value is

dependent on the difference B   A  and not on
the path in between.
B A
The cyclic integral becomes  d   d   d  0
B A A B

Thus d    d
A B
The essential criteria of a state function are
1.The change in the value of a state function
depends only on the initial & final states & not on
the path of the process carried out in going from
initial to final state.
2.The cyclic integration involving a state function
is zero.

3. Euler’s reciprocity condition must be valid.

4.The state function has an exact differential i.e
if p = f(T,V) is a state function, then
  p     p  
      
V  T V T T  V T V
Q. Show that the volume of a fixed amount of an
ideal gas is a state function.
Soln: For an ideal gas V = nRT/p, thus

Differentiate V wrt temperature keeping

pressure constant.  V  nR ……(1)
  
 T  p p

Differentiate eqn (1) wrt pressure keeping

temperature constant.    V     nR
 p  T  p T p2

Differentiate V wrt pressure keeping temp

constant.  V  nRT
    2 ……(2)
 p T p
Differentiate eqn (2) wrt temperature keeping
pressure constant.    V   nR
     2
 T  p T  p p
   V      V  
        
 p  T  p T  T  p T  p

Since Euler’s reciprocity condition is valid, so

volume is a state function.

INTERNAL ENERGY

Every substance possesses a definite amount of

energy which depends upon factors such as
composition of the substance, n,T and pressure.
This is called intrinsic or internal energy (E/U).
E = ET + ER + EV + EPE + EB + EE + EN ….

where ET = Translational energy,

ER = Rotational energy, EV = Vibrational energy,

EPE = Potential energy, EB = Bonding energy,

EE = Electronic energy & EN = Nuclear energy.

Internal energy of a system is state function and

When the system undergoes a change in its state,
the internal energy change is given by E or U.
U = E2 E1
 When heat is given to the system at constant
volume, so FLOT can be written as
U  qV  w  qV  pV
As Volume remain same, so w = 0.
 U  qV
Thus, heat given to the system at constant volume
is equal to increase in internal energy of the
process. This leads to increase in temp. of system.

Thus, heat is taken out from the system at const.

volume , it decreases the internal energy of
system. This leads to decrease in temp. of system.
Internal energy is an extensive quantity.
U=f(V,T) ….(1), U=f(p,T) ….(2), U=f(p,V) …..(3)

If U is a state function, so dU will be an exact

differential.

Thus, from eqn (1)  U   U 

dU    dT    dV
 T V  V T
 U 
dU  nCv dT    dV ……..(4)
 V T

This can be used for any substance

under any state.
(1) Ideal gas undergoing any process
 U 
  0 dU  nCv dT
 V T
(2) Real gas undergoing isochoric process

dV  0 dU  nCv dT
(3) Real gas undergoing any other process

 U 
dU  nCv dT    dV
 V T
(4) Solid or Liquid undergoing any process
dU  nCdT
ENTHALPY (H)
Heat content of a system at constant pressure
is called enthalpy.
It is related with internal energy by the equation,
H = U + PV
Every substance has a definite value of enthalpy
in a particular state.
It is also a state function like internal energy. The
change in enthalpy accompanying a process can be
determined as H = H2  H1 .
where H1 = Enthalpy of a substance in the initial
state and H2 = Enthalpy of a substance in the final
state.
Most of the processes in laboratory take place at
constant pressure, so FLOT can be written as
U  q p  w  q p  pV
q p  U  pV  U 2  U1   pV2  V1 

q p  U 2  U1   pV2  pV1  U 2  pV2   U1  pV1 

The term U + pV has been defined as a new
thermodynamic term as enthalpy (H).
U + pV = H
q p  U 2  pV2   U1  pV1   H 2  H1  H

Thus, heat given to the system at constant

pressure is equal to increase in enthalpy of the
process.
Enthalpy is also an extensive quantity.
H=f(p,T) ….(1), H=f(p,V) ….(2), H=f(V,T) …..(3)

If H is a state function, so dH will be an exact

differential.

Thus, from eqn (1)  H   H 

dH    dT    dp
 T  p  p T
 H 
dH  nC p dT    dp ……..(4)
 p T
This can be used for any substance
under any state.
(1) Ideal gas undergoing any process
 H 
   0 dH  nCp dT
 p T
(2) Real gas undergoing isobaric process

dp  0 dH  nCp dT
(3) Real gas undergoing any other process

 H 
dH  nC p dT    dp
 p T
(4) Solid or Liquid undergoing any process

dH  nCdT
 RELATION BETWEEN H & U FOR
PHYSICAL & CHEMICAL PROCESSES

H = U + pV H  U   ( pV )
(a)PHYSICAL PROCESSES( Expansion &
Compression) The no. of moles remain same.
(i)H  U  ( p f V f  piVi )
(ii) When diff. in temp is given & gas is ideal
H  U   pV   U  nRT
(iii) When temp’s are different & gas is real
pV  ZnRT
H  U   pV   U  ZnRT   U  nRZT 
 (iv) For Pure Solids or Liquids

 pV  term is very small and can be neglected.

H  U
(b)CHEMICAL
(b) CHEMICALPROCESSES
PROCESSES

 U   U   U 
dU    dT    dV  nCv dT    dV
 T V  V T  V T
 H   H   H 
dH    dT    dp  nC p dT    dp
 T  p  p T  p T

Whenever a chemical reaction is carried out, temp

generally remain constant but P & V may vary.
(i) H  U   ( pV )  U  ( p f V f  piVi )
(ii) When the reaction is done at constant volume
H  U  V p rxn

(iii) When the Rx is done at constant Pressure

H  U  pV rxn
(iv) When the temp is constant & gases involved
are ideal
H  U   pV   U  nRT   U  ng RT
(v) For Rx’s involving only Pure Solids or Liquids

 pV  term is very small and can be neglected.

H  U

Q. 1 mole of a non-ideal gas undergoes change of

state from (2 atm, 3 L, 95 K) to (4 atm, 5 L, 245 K)
with a change in internal energy of 30 L.atm. The
change in enthalpy for the process is

(a) 40 L.atm (b) 44 L.atm

(c) 48 L.atm (d) Not defined as P is not
constant
Q. An ideal gas is expanded from(10 atm,1 L) to(5
atm,4 L) against a constant external pressure of 1
atm. If the initial temperature of gas is 300 K and
heat capacity for the process is 50 J/0C, the
change in enthalpy for the process is (use: 1L.atm =
100 J)

(a) 15 kJ (b) 15.7 kJ

(c) 14.7 kJ (d) 14.3 kJ

Soln. H  U  ( pV )  U  ( p2V2  p1V1 )

To calculate change in internal energy,

p1V1 p2V2

T1 T2
 10 1 5  4

300 T2
T2  600K

q  CT  50(600  300)  15kJ

w   pext V  1(4  1)  3L.atm  0.3kJ
U  q  w
U  15 0.3
U  14.7kJ
 
H  14.7  (5  4  10 1)100103 kJ  15.7kJ
Q. For the reaction, A  B; H  25kJ / mol

For the reaction, B  C ; H  18kJ / mol

The decreasing order of enthalpy of A,B,C follows
the order
(a) A, B, C (b) B, C, A
(c) B, A, C (d) C, A, B

Soln. From the first Rx, enthalpy of B > A.

x  25  x 
From the second Rx, enthalpy of B > C.
x  25 x  7 
Q. The enthalpy change accompanying the
formation of NH3(g) from its elements at 298 K is
-46.1 kJ. Estimate the change in internal energy.

Soln. H  U   ( pV )

N 2 ( g )  3H 2 ( g ) 
 2 NH 3 ( g )
ng  2  (1  3)  2
H  U  ng (RT )
U  H  ng ( RT )  46.1  ( 2  8.314  103  298)
U  41.1kJ
Q. Water is heated to boiling under a pressure of
1.0 atm. When an electric current of 0.50 A from a
12 V supply is passed for 300 s through a
resistance in thermal contact with it, it is found
that 0.798 g of water is vaporized. Calculate the
molar internal energy and enthalpy changes at the
boiling point (373.15 K).
Soln. ΔH = qp = (0.50 A)(300 s)(12 V) = ( 1800) J
1800J 1
H m   41kJmol
0.798 / 18mol
In the process H2O(l) → H2O(g) the change in the
amount of gas molecules is Δng = +1 mol, so
ΔUm = ΔHm − RT = +38 kJ mol−1
 FIRST LAW OF THERMODYNAMICS
Energy can neither be created nor destroyed,
although it can be transformed from one form
to another.

Another way to say it is that the change in

internal energy of a system is equal to the sum of
the work done on/by it and the amount of heat
energy transferred to/removed from it.

dU = dq + dw Or U = q + w.

The internal energy of an isolated system is

always constant.
 FLOT: dU = dq + dw Or U = q + w.

IUPAC SIGN CONVENTIONS

If the energy of the system is increased, it will
be +ve & if energy of the system is decreased, it
will be regarded as –ve.
q is assigned a positive value if heat is absorbed,
but a negative value if heat is lost by the system.

w is assigned a positive value if work is done on,

but a negative value if work is done by the system.

For processes that do not involve phase changes,

positive ΔE results in temperature increase.
The internal energy is a state function of the
system. Work and heat are not state functions
and do not correspond to exact differentials but
heat exchanged under isochoric or isobaric
conditions is a state function and work involved
in an adiabatic process is a state function.
Q. If an electric motor produced 15 kJ of energy
each second as mechanical work and lost 2 kJ as
heat to the surroundings, then the change in the
internal energy of the motor each second is

Soln. ΔU = −2 kJ − 15 kJ = −17 kJ
Q. Suppose that, when a spring was wound, 100 J
of work was done on it but 15 J escaped to the
surroundings as heat. What is the value of ΔU .

Soln. The change in internal energy of the

spring is ΔU = +100 kJ − 15 kJ = +85 kJ
Q. In a system where ΔU = - 52 kJ, a piston
expanded against a pext of 1.5 atm, giving a
change in volume of 30 L. What is the change in
heat of this system? Take 1 L.atm = 100 J.

(a) -36 kJ (b) -13 kJ

(c) -47.5 kJ (d) 24 kJ
Soln.
pV  1.5  30  45L.atm  45  100  4500J
pV  4.5kJ w   pV  4.5kJ
q  U  w  52  4.5  47.5kJ

The problems based on FLOT involve work done,

heat involved , ΔU & ΔH calculations.

Let us see these (work done, heat involved , ΔU

& ΔH) calculations in various processes.
WORK INVOLVED IN VOLUME CHANGES
OF AN IDEAL GAS
The work done by the gas in
expansion is given as
dw =  Fextdl
Fext
dw   dl. A   Pext dV
A
dwexp =  (pgas dp) dV
dwexp =  pgas . dV =  pdV
dp.dV is the product of two
infinitesimal quantities and
hence neglected.
 The work done by the gas in
compression is given as dw =  Fextdl
Fext
dw   dl. A   Pext dV
A
dw =  (pgas+ dp) dV dp.dV is the product of 2
infinitesimal quantities &
dw =  pgas . dV =  pdV
hence neglected.
Isothermal reversible expansion

The total amount of work done

during the isothermal reversible
expansion of the gas from volume
V1 to V2 is given by
dwexp   pdV
If we perform the integration from V1 to V2
(or Vi to Vf)
V2 V2
nRT
dwexp    PdV    dV
V1 V1
V
 V2 
wexp  nRT (lnV ) |V  nRT ln 
V
2

 V1 
1
  V2   p1 
wexp   nRT ln    nRT ln 
 V1   p2 
 V2   p1 
qexp   wexp  nRT ln   nRT ln 
 V1   p2 
U  0,
H  0

Isothermal reversible compression

If the gas is compressed reversibly from V2 to V1 ,

V1 V1
nRT
dwcomp    PdV    dV
V2 V2
V
 V1   V2 
wcomp  nRT (lnV ) |V  nRT ln   nRT ln 
V 1

 V2   V1 
2
  V2
  p1 
wcomp  nRT ln  nRT ln 
 V1
  p2 
 V2   p1 
qcomp   wcomp  nRT ln   nRT ln 
 V1   p2 
U  0, H  0
Total work done when the gas is expands from
V1 to V2 and then compressed from V2 to V1 ,

( wTotal )rev  wexp  wcomp

 V2   V2 
( wTotal ) rev  nRT ln   nRT ln   0
 V1   V1 
Q. Calculate the work which could be obtained
from an isothermal reversible expansion of 1 mol
of Cl2 from 1 dm3 to 50 dm3 at 273 K using ideal
gas behaviour.

(-8.88kJ/mol)

Q. One dm3 of an ideal gas at a pressure of 10 atm

expands reversibly and isothermally from its
volume to 10 dm3 . How much of heat is absorbed
and how much of work is done in expansion?

(2.33kJ, -2.33kJ)
 Isothermal irreversible expansion

The total amount of work done

during the isothermal
F irreversible
dw   F .dl   dl. A   Pext dV
expansion of the A gas from volume
V1 to V2 (or Vi to Vf) is given by
Since external/ opposing pressure remain constant
in irreversible expansion, so
V2

dwexp   Pext dV   P2  dV wexp   P2 (V2  V1 )

V1
qexp  wexp  p2 (V2  V1 )

U  0, H  0
 Isothermal irreversible compression

The total amount of work done during

the isothermal irreversible
F
compression of the
dw   F .dl   dl. Agas
  Pfrom
ext dV volume
A
V2 to V1 (or Vf to Vi) is given by
Since external/ opposing pressure remain constant
in irreversible compression, so
V1

dwcomp   Pext dV   Pext  dV wcomp   P1 (V1  V2 )

V2

wcomp  P1 (V2  V1 )
qcomp  wcomp   p1 (V2  V1 )

U  0, H  0
Total work done when the gas is expands from
V1 to V2 and then compressed from V2 to V1 ,

( wTotal )irrev  wexp  wcomp

( wTotal )irrev  wexp  wcomp   P2 (V2  V1 )  P1 (V2  V1 )

( wTotal )irrev  (V2  V1 )( p1  p2 )

p1 ,V1 p1,V2
Since V2 > V1 and p1 > p2 , then
P
( wTotal )irrev  ve

p2 ,V1 p2 ,V2
V
Comparison of Work Done Comparison of Heat Exch

1.( wcomp )irrev1  ( wcomp )irrev2  ( wcomp )rev 1. ( qcomp )rev  ( qexp )rev
2.( wexp )irrev1  ( wexp )irrev2  ( wexp )rev 2. (qcomp )rev  (qexp )irrev

3. ( wcomp )irrev  ( wexp )rev 3. ( qcomp )irrev  ( qexp )rev

4. ( wcomp )rev  ( wexp )irrev 4.( qexp )irrev1  (qexp )irrev2  (qexp )rev

5. ( wcomp )rev  ( wexp )rev 5. (qcomp )irrev1  (qcomp )irrev2  (qcomp )rev
 Free expansion of an ideal gas

Free expansion occurs when the external pressure

is zero, i.e. there is no opposing force. When an ideal
gas is allowed to expand freely i.e against vacuum,
then the gas does not do any work as pext is zero.
dw   pext dV
dw  0
As no work is done by the gas in free expansion,
there is no change in internal energy of the gas.
dU  0 & dH  0
 dq  dU  dw  0  0  0
Comparision of magnitude of work involved in
reversible expansion of an ideal gas with that
in irreversible expansion.
V2   V2 
wrev  nRT ln wrev  nRT ln 1    1
V1   V1 
 V2 
x    1
 V1 
x 2 x3
ln(1  x)  x    ......
2 3
 V2   nRT
wrev  nRT   1  higherterms.  (V2  V1 )  higherterms
 V1   V1

wrev  p1 (V2  V1 )  higherterms wirrev  pext (V2  V1 )  p2 (V2  V1 )

wrev  wirrev  p1 V2  V1   higherterms  p2 V2  V1 

 wrev  wirrev  p1 V2  V1   p2 V2  V1   V2  V1  p1  p2 

During expansion of an ideal gas V2  V1 & p1  p2

wrev  wirrev  ve

Therefore, work involved in reversible expansion

of an ideal gas is more than that involved in
irreversible expansion.

Remember that, work involved in irreversible

compression of an ideal gas is more than that
involved in reversible compression.
Q. Calculate the work done when 28 g of iron
reacts with hydrochloric acid in: (a) a closed
vessel; (b) an open beaker at 27oC.
Soln. (0 & -1.23 kJ)
Fe( s )  2 HCl (aq) 
 FeCl2 (aq)  H 2 ( g )
nH 2 RT
( a ) V  0, w  0 (b)V  VH 2  VSo ln  VH 2 
p
wexp   p(V )  0.5  0.082  300  0.1  1.23kJ
Q.The internal energy change when 1.0 mole CaCO3
in the form of calcite converts to aragonite is 0.21
kJ. Calculate the difference between the enthalpy
change and the change in internal energy when the
pressure is 1.0 bar given that the densities of the
solids are 2.71 g cm−3 and 2.93 g cm−3, respectively.
Soln. ΔH = H(aragonite)-H(calcite)
ΔH = {U(a)+pV(a)}−{U(c)+pV(c)}

ΔH = ΔU + p{V(a) − V(c)} = ΔU + pΔV

The volume of 1.0 mol CaCO3 (100 g) as aragonite

is 34 cm3, and that of 1.0 mol calcite is 37 cm3.

pΔV = (1.0 × 105 Pa) × (34 − 37) × 10−6 m3 = −0.3 J

Q. Calculate the difference between ΔH and ΔU

when 1.0 mol Sn(s, grey) of density 5.75 g cm−3
changes to Sn(s, white) of density 7.31 g cm−3 at
10.0 bar. At 298 K, ΔH = +2.1 kJ.
[ΔH − ΔU = −4.4 J]
Q. Two moles of zinc is dissolved in HCl at 25oC.
The work done in an open vessel is
(a) -2.477 kJ (b) -4.955 kJ
(c) 0.0489 kJ (b) None
Q. A given mass of gas expands from the state A
to state B by three paths 1, 2 and 3 as shown in the
figure. If w1, w2 and w3 respectively be the
magnitude of work done by the gas along three
paths then
(a) w1 > w2 > w3 (b) w1 < w2 < w3
(c) w1 = w2 = w3 (d) w2 < w3 < w1
Q. Heat absorbed by a system in going through a
cyclic process shown in figure is

(a )107 J (b)106 J

(c)102 J (d )104 J

Q. In a cyclic process shown in P-V diagram, the

magnitude of work done is
 V2 V1 
2
 p2  p1 
2

(a)   (b)  
 2   2 

(c)  p2  p1 V2  V1  (d ) V2  V1 
2
4
 HEAT EXCHANGED
It is the transfer of energy that takes place due to
difference of temp between system & surroundings.
HEAT CAPACITY
It is the quantity of heat required to raise the
temperature of the given amount of substance
by 1 degree or 1 Kelvin.
dq
C Its unit is J K1 or J /°C.
dT
where C = Heat capacity, dq = Amount of heat
absorbed by the system and dT = Rise in temp.
Heat capacity is an extensive quantity.
SPECIFIC HEAT CAPACITY

The amount of heat required to raise the temp

of 1 gm of a substance by 1 degree is called
specific heat or specific heat capacity.

Specific heat capacity =

Heat absorbed
Rise in temperatur e  mass (in gm )

Heat capacity C dq
s s 
mass (in gm) m mdT
dq  msdT
Its unit is J K1 g-1 or J /g.°C.

Specific Heat capacity is an intensive quantity.

MOLAR HEAT CAPACITY

The amount of heat required to raise the temp

of 1 mole of a substance by 1 degree is called s
molar heat capacity.
Heat absorbed
Molar heat capacity =
Rise in temperature  no.ofmoles
Heat capacity C dq
Cm  Cm  
no.ofmoles n ndT
dq  nCm dT
Its unit is J K1 mol-1 or J /mol.°C.

Molar Heat capacity is an intensive quantity.

 dq dq
Cm   M  sM
m
dT mdT
M
Molarheatcapacity  Specificheatcapacity Molarmass

SHC & MHC are process dependent for gases.

Specific heat capacity at constant volume (sv) &

Specific heat capacity at constant pressure (sp).

Molar heat capacity at constant volume (Cv) &

Molar heat capacity at constant pressure (Cp).
 RELATION BETWEEN Cp & Cv
FOR AN IDEAL GAS

H = U + pV , For an ideal gas H = U + nRT

Changes in enthalpy for an infinitisimal change

in temperature,

dH = dU + nRdT

nCpdT= nCvdT + nRdT

Cp = Cv + R Cp - Cv = R

spM - svM = R, sp - sv = R/M

 dU = dq + dw
At constant volume, dw = -pext dV= 0
dU= (dq)v

Cm v  dqv dU

ndT ndT
dU  nCm v dT

At constant pressure, (dq)p = dU + pdV = dH

dqp
Cm p  
dH
dH  nCm p dT
ndT ndT
For any substance heat capacity is temp
dependent & given as

C = a + bT + cT2 + …….
If the temp dependence is not given and gases are
ideal, then the heat capacity can be calculated
using degree of freedom.
DEGREE OF FREEDOM
It is the number of independent variables needed
to specify the position & configuration of a system
completely.
Kinetic energy of molecule at a given temp T for
each DOF = ½ kT
1 1
U kT  N A  f  RTf
2 2
Differentiate U wrt T gives dU fR

dT 2
 fR fR
dU  dT dU  nCv dT   nCv  Cv ( asn  1)
2 2
fR R ( f  2)
Cv  & C p  Cv  R 
2 2
R( f  2)
Cp f 2 2
  2   1
Cv fR f f
2
For monoatomic gas, f=3;For diatomic gas, f=5;
For Linear polyatomic gas, f=5;For non- linear
polyatomic gas, f=6.
n1Cv  n2Cv n1 f1  n2 f 2
Cv mix  1 2 f mix 
n1  n2 n1  n2
(C p ) mix
C p mix  Cv mix  R  mix 
(Cv ) mix
 mix  1
2
f mix
At moderate Temps. Linear Non-Linear
Monoatomic Diatomic Polyatomic Polyatomic
gas gas gas gas
3R 5R 5R
Cv 3R
2 2 2
5R 7R 7R
Cp 4R
2 2 2
Cp 5 7 7 4
  1 .6  1 .4  1 .4  1.33
Cv 3 5 5 3
Hg,Ne, N2,O2, CO2 , NO2,H2O,
He,Ar H2,Cl2 C2H2 SO2,NH3
Q. A vessel contains 1 mol of He and 1 mol of N2.
Calculate the atomicity of mixture.
 At higher temperatures, vibrational modes also
become active. In all vibrational systems, the
energy has both kinetic & potential components.

According to classical principle of equi partition of

energy, each form of energy manifested by a
molecule contribute 1/2 R to heat capacity of a gas.

Thus a contribution of 2*1/2 R i.e R to heat capacity

of a gas for each mode of vibration.

To specify the location in space of n separate atoms

require 3n cordinates.
When atoms combine to form a molecule, the atoms
no longer behave independently & their locations are
determined by translational, rotational & vibrational
motion which the molecule undergoes.
For a linear molecule, there are 5 kinds of motion
due to translation & rotation, the molecule must
then have (3n-5) modes of vibration.
For a non-linear molecule, there are 6 kinds of
motion due to translation & rotation, the molecule
must then have (3n-6) modes of vibration.
The maximum heat capacity at constant volume
for a linear molecule thus consist of 3/2R for
translational, 2/2R for rotation & (3n-5)R for
vibration, making a total of (3n-5/2)R.
The maximum heat capacity at constant volume for
a non-linear(bent) molecule thus consist of 3/2R
for translational, 3/2R for rotation & (3n-6)R for
vibration, making a total of (3n-3)R.
These maximum heat capacity at constant volume
for a linear & non-linear(bent) molecule are
approached at sufficiently high temperatures.
Q. Calculate the maximum high temperature heat
capacity at constant volume to be expected for (i)
acetylene & (ii) ammonia.
Soln: The maximum high temperature heat capacity
at constant volume for acetylene= (3*4-
5/2)R=19/2R =19 cal K-1 mol-1 & for ammonia =
(3*4-3)R = 18 cal K-1 mol-1 .
Q. Which has maximum internal energy at 290 K?

(a) Neon gas (b) Nitrogen gas

(c) Ozone gas (d) Equal

Q. A system containing 5 moles of an ideal gas was heated

from temperature T1 = 300 K to temperature T2 = 400 K.
The internal energy of the gas increased by ΔU = 800 J.
how did the enthalpy of the system change.

Soln: ΔH = ΔU + Δ(PV) Δ(PV) = p2V2-p1V1

For an Ideal gas, Δ(PV) = Δ(nRT)

ΔH = ΔU + nRΔT = 800 + [5*8.314(400-300)]

ΔH = 4957 J
 THERMODYNAMIC CHANGES IN ADIABATIC
CHANGE IN VOLUME OF AN IDEAL GAS

In adiabatic expansion or compression, dq=0.

So, Acc to FLOT, dU = dw or ΔU = w.
If there is an expansion, dw will be –ve & dU will
also be –ve i.e there occurs a decrease in internal
energy of the system. Hence, temp falls & cooling
is observed.
If there is a compression, dw will be +ve & dU will
also be +ve i.e there occurs an increase in internal
energy of the system. Hence, temp rises &
heating is observed.
  U   U 
dU    dT    dV
 T V  V T
 U 
For an ideal gas   0
 V T
 U 
dU    dT  nCv dT
 T V
For a finite change, U  U 2  U1  nCv T2  T1 

w  U  nCv T2  T1 
andH  U  pV   U   pV   U  nRT
H  nCv T2  T1   nRT2  T1   nCv  R T2  T1 
H  nCp T2  T1 
H C p
or  
U Cv
 U  nCv T2  T1 

H  nCp T2  T1 

The expressions are applicable to any type of

adiabatic process, reversible or irreversible but
the final temperature would be different in each
case. Thus, value of ΔU & ΔH are different.

Reversible Expansion
or Compression process
dw  ( pgas  dp)dV   pgas dV   pdV

 dw   pdV
The integration can not be performed directly
because p is a function of V & T both as they
are changing in adiabatic process.

If the final temp is available then ΔU & ΔH can

be calculated using following expressions.

U  nCv T2  T1 
H  nCp T2  T1 

If final temperature is not available and final

pressure or volume is given then, we first
calculate final temperature.
 nRT RT
dU  dw nCv dT   pdV   dV Cv dT   dV
V V
T2 dT V2 dV
For a finite change, Cv T1  R
T V1 V

Assuming Cv to be independent of temperature, then

Cv R
T V  T2   V2 
Cv ln 2   R ln 2 ln   ln 
T1 V1  T1   V1 
Cv R
 T2   V1 
     T2  v V2   T1  v V1 
C R C R

 T1   V2 
R

T  v V   Constant TV  Constant  TV  1 …….(1)

C R Cv

R R
Cv  RT 
T     Constant T  R
 Constant  Tp
Cp Cp
p
 p 
1

Tp 
 Constant …….(2)
 C
 pV 
v

  V  Constant pCvV p  Constant

R C

 R 
pV   Constant …….(1)

Irreversible Expansion or Compression process

dU  dw U  w
U  nCv T  nCv T2  T1  H  nCp T  nCp T2  T1 

nCv T   popp (V2  V1 )

If popp,p1, p2,T1 are given, then we first calculate the

final temperature after expansion or compression.
nCv T2  T1    popp (V2  V1 )  popp (V1  V2 )
 nRT1 nRT2   RT1 RT2 
nCv T2  T1   popp    Cv T2  T1   popp   
 p1 p2   p1 p2 
 In a special case when popp=p2, then
 RT1 RT2  RT1 p2
Cv T2  T1   p2      RT2
 p1 p2  p1
RT1 p2  Rp2 
CvT2  RT2   CvT1 C pT2  T1   Cv 
p1  p1 
 Rp 2 
T1   Cv 
T2   p1 
Cp

Q. 2 moles of an ideal diatomic gas at 300 K & 5

atm are expanded adiabatically to a final pressure
of 2 atm against a constant pressure of 1 atm.
Calculate the final temp, q, w, ΔU & ΔH .
T2  270K , q  0, U  w  1247J , H  1746J
 Q. During an adiabatic reversible process, the
pressure of a gas is found to be proportional to
the cube of its absolute temperature. The ratio
of Cp/Cv for the gas is
(a) 3/2 (b) 5/3
(c) 7/2 (d) 4/3
Soln. pT 3
1

Tp 
 Constant  k

 k
pT 1
k p 
 kT 1

T 1


pT  1  3   3 / 2
 1
Q. A sample of argon at 1.0 atm pressure and 25oC
expands reversibly and adiabatically from 0.50 L
to 1.00 L. Calculate its final temperature, the work
done during the expansion, and the change in
internal energy. The molar heat capacity of argon
at constant volume is 12.48 JK-1 mol-1.
 Comparision between reversible isothermal &
reversible adiabatic expansion of an ideal gas
Let a gas from initial state p1 & V1 undergoes
reversible isothermal & reversible adiabatic
expansion such that the final volume(Vf) is same.
Let piso & padi be the final pressures in the two
processes respectively.
For isothermal expansion, p1V1  pisoV f
Vf p1
 …….(1)
V1 piso
For adiabatic expansion, p1V1  padiV f

Vf  p
   1 …….(2)
 V1  padi
 Since for an expansion, Vf > V1 and  > 1, thus

Vf  Vf
   So that p1

p1
 V1  V1 padi piso
 piso  padi
In adiabatic expansion, temp. falls
whereas in the isothermal
expansion, temp. remain same.
Since final volumes are same, acc to Gay Lussac’s
law pressure is proportional to temp. at constant
volume for a fixed mass of a gas. piso would be > padi.
The magnitude of work involved in reversible
isothermal expansion is greater than that involved
in adiabatic process.
The physical reason for difference is that, in an
isothermal expansion, energy flows into the
system as heat and maintains the temp; as a
result, the press. does not fall as much as in an
adiabatic expansion.
Slope of an reversible isothermal expansion curve
of an ideal gas
k k  pV p
pV  k p
V
Slopeiso 
dp
 2  2

dV V V V

Slope of an reversible adiabatic expansion curve

of an ideal gas
dp  k  pV   p
pV   k
k
p  Slopeadia    1   1
   
V dV V V  V 
 Slopeadia   Slopeiso

The slope of a reversible adiabatic expansion is

more steeper than that of a reversible isothermal
expansion. Therefore, adiabatic curve lie below
the isothermal curve.
Q. When a sample of argon (for which γ = 5/3 ) at
100 kPa expands reversibly and adiabatically to
twice its initial volume, what will be the final
pressure?

 V1 
Soln: p2    p1
 V2 
5/3
1
p2     100kPa 
2
p2  32kPa

For an isothermal doubling of volume, the final

pressure would be 50 kPa.
 P-V Diagrams/ Indicator Diagram

Isobar

Isochor

wisobaric  wisothermal  wadiabatic  wisochoric

 THERMODYNAMIC CHANGES IN ISOBARIC
CHANGE IN VOLUME OF AN IDEAL GAS
In such a process, n and p are same. i.e dp = 0 but
volume & temp changes.
 nRT2 nRT1 
V2

dw   Pext dV   Pext  dV w   Pext (V2  V1 )   Pext   

V1  p p 

If pext = p, then w  nRT1  nRT2   nR(T1  T2 )

In expansion, T2 > T1 , so wexp = -ve and in

compression, T2 < T1 , so wcomp = +ve
U  nCv (T2  T1 )

(q) p  U  w  nCv (T2  T1 )   nR(T2  T1 )  nCp(T2  T1 )  H

P P

V T

V For isobaric process there

is no distinction between
reversible and irreversible
process.
T
THERMODYNAMIC CHANGES IN ISOCHORIC
CHANGE IN PRESSURE OF AN IDEAL GAS
In such a process, n and V are same. i.e dV = 0
but pressure & temp changes.
dw   Pext dV  0 w0
U  nCv (T2  T1 )

(q)V  U  nCv (T2  T1 )


H  nCp (T2  T1 ) 
At constant volume, the heat entering the system
will increase the internal energy while heat leaving
the system will lower the internal energy.
P P

V T

For isochoric process

V

there is no distinction
between reversible and
irreversible process.
T
 ANALYSIS OF POLYTROPIC PROCESS

pV x  cons tan t
dqgp
For a general process, C gp 
ndT
dU  dq  dw dq  dU  dw

dU  dw dU dw dU   pdV  dU pdV
C gp    Cgp    
ndT ndT ndT ndT  ndT  ndT ndT

nCv dT pdV p  dV 
Cgp    Cv   
ndT ndT n  dT 
For any general process, the molar heat capacity
can be calculated if volume as a function of
temperature is known.
 pV x  cons tan t
nRT x
V  k  nRTV x 1
V
k
T
nRV x 1
Differentiate T with respect to volume,V.
dT  ( x  1)k k (1  x )
 x

dV nRV nRV x
dT pV x (1  x) p(1  x)
 x

dV nRV nR
dV nR
  C gp  Cv 
p nR
dT p (1  x) n p(1  x)
R
 C gp  Cv 
(1  x)
(a) For Isothermal process, x = 1, Cgp = infinity
H 2O( s) 
T
H 2O(l )
dT= 0 for Isothermal process, thus molar heat
capacity of H2O in equilibrium with its vapors is
infinity.
(b) For Adiabatic process, x =  , Cgp = 0
R
C gp  Cv 
(1   )
R R R R
 1   Cv   Cv  
Cv  1  1 1 

Cgp  Cv  Cv  0