NOTE

P H Y S I C S

THERMODYNAMICS
MOLAR HEAT CAPACITY

What you already know What you will learn

• Standard thermodynamic process • Molar heat capacity for a mixture of

• Adiabatic process gases

• Cyclic process • Gas ratio 𝛾 for a mixture of gases

• Work done in general/polytropic process • Specific

From the firstheat capacity
law of of solids
thermodynamics,
• Molar heat capacity • Mean free path
dQ
= dU + dW
• Bulk modulus and speed of sound
⇒ nCn dT = nCV dT + PdV
• Efficiency of a cycle
P dV
⇒ C n = CV +
n dT
Example Given,
An ideal gas undergoes a process where T = T0e𝛼V. Find
T = out
T0 eαthe
V molar specific heat capacity for this
process if the molar specific heat capacity at a constant volume is CV .
d  dV 
⇒ (T ) = T0 eαV  α 
dT  dT 
Solution
dV
⇒1= Tα
From the first law of thermodynamics, dT
dQ
= dU + dW dV 1
⇒ =
dT  PV 
⇒ nCn dT = nCV dT + PdV  nR  α
 
P dV
⇒ C n = CV + P dV R
n dT ⇒ =
n dT α V
Given,
Hence, molar heat capacity for the process is,
αV
T = T0 e
R
C=
n CV +
d  dV  αV
⇒ (T ) =
T0 eαV  α 
dT  dT 
dV
Tα
⇒1=
dT
dV 1
⇒ =
dT  PV 
 nR  α
 
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P dV R
 02

Molar Heat Capacity for a Mixture of Gases

Consider a mixture of m number of non-reacting

gases of quantities n1, n2,..., nm, respectively. The
molar heat capacities at a constant volume of the
gases are CV1 , CV2 , ..., CVm , respectively.

Let us assume that the total number of moles of

gas in the mixture (hydrogen, oxygen, nitrogen,
etc., shown in different colours) is nmix, and the
equivalent molar heat capacity at a constant
volume is CVmix . Since the mixture is at the same
temperature (say T), the internal energy Umix is
given by,
Umix = U1 + U2 + ... + Um
⇒ nmix CVmix=
T n1CV1 T + n2CV2T + ... + nmCVm T
n1CV + n2CV2 + ... + nmCVm
⇒ CVmix =1
nmix
n1CV + n2CV2 + ... + nmCVm
⇒ CVmix =1
n1 + n2 + ... + nm

Similarly, the molar heat capacity of the gas mixture at constant pressure is given by,
n1C P1 + n2C P2 + ... + nmC Pm
C Pmix =
n1 + n2 + ... + nm

The gas ratio γ of the mixture is given by,

C Pmix
γ mix =
CVmix
n1C P + n2C P2 + ... + nmC Pm
⇒ γ mix =1
n1CV1 + n2CV2 + ... + nmCVm

Specific Heat Capacity of Solids

The atoms in solids cannot translate but are free to vibrate about their equilibrium positions (lattice
vibrations) in three-dimensional (3D) space. In general, there are six ways a molecule in a solid
can possess vibrational energy, and it can be considered as a substance having six degrees of
freedom. According to the equipartition of energy, all the degrees of freedom are associated with
1
the same energy, i.e., kT.
2
1
⇒ The energy of each atom = 6 × kT = 3kT
2
⇒ The energy of one mole of solid atoms ≈ 3kT × NA = 3RT
⇒ The specific heat capacity of a solid per mole of atoms ≈ 3R ≈ 25 J mol–1K–1

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 03

Specific Heat Capacity of Water

Unlike many liquids, water molecules can form hydrogen H H

bonds with each other. These H-bonds are not as strong as O O
the intramolecular polar covalent bonds. They can still store
H H H H
a significant amount of potential energy explaining the higher
boiling and melting points of water. Because of the shown O
network of hydrogen bonds, the density of water does not vary
as much with pressure and has exceptionally high molar heat H H H H
capacity among liquids. In this context, we can treat water like a O O
partially ordered system.
In water, all molecular vibrations, rotations, and translations contribute to the heat capacity. In a
water molecule at 25 °C, there are two hydrogen atoms and one oxygen atom, and there are six
degrees of freedom (three translational + two rotational + one vibrational) per atom. Therefore, the
total degrees of freedom of a water molecule are 18.
Translation
Rotation

y z
Vibration

x
y

6 9 18

Number of degrees of freedom

6 DOF
1
The energy of a water molecule = 18 × kT =
9kT
2 O

The energy of one mole of water molecules = 9kT × N A =

9RT

9RT H H
The energy corresponds to each atom in the water molecule = = 3RT
3 6 DOF 6 DOF

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 04

Therefore, the specific heat capacity of water per mole of atoms at 25 °C comes out as 3R, which
is very close to its experimental value of 3.02R. Since it has three atoms and a molecular weight of
3.02 × 3 × 8.31
18 g mol −1, the specific heat capacity of water per gram is = 4.18 J g −1K −1 , which
18
matches the experimental value (1 cal) known to us.

• The experimental heat capacities of the substances containing complicated molecules

are generally slightly greater than those containing simple molecules.
• We cannot derive the molar heat capacities of other liquids in the same way we did
of water. For example, the molar heat capacity of metallic liquids only contains the
vibrational and translational parts, and it comes out as 4.5R per mole of atoms.
• We have always considered heat capacities to be temperature-independent. However,
this is not the case for most substances. The experimental heat capacities generally
increase with an increase in temperature.

Mean Free Path

The average distance travelled by a gas molecule between two successive collisions is known as
its mean free path.
Mathematically, the mean free path is given as,
1
λ=
2nπ d 2
Where,
n = Number of particles per volume or number density
d = Diameter of the particles
In a general sense, the mean free path decreases with an increase in the number density and/or
the size of the particles.

Revisiting Bulk Modulus and Speed of Sound

The bulk modulus of a substance is given by,

dP
β = −V
dV
The speed of sound under the isothermal assumptions (Newton’s formula) is given by,
P
v=
ρ
The speed of sound under the adiabatic assumptions (Laplace’s correction) is given by,
γP 1.40×1.013×105
=v = ≈ 332 ms −1
ρ 1.29

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 05

Example

A cylinder filled with a monatomic gas at temperature T0, pressure P0, and
P0 , V0 , T0
volume V0 is separated by a diathermic wall as shown in the figure. Find the
V
final pressure if the volume is decreased to 0 ,
2
(a) Suddenly
(b) Slowly V0
P0 , ,T
Assume the surroundings at temperature T0. 2 0

Solution

(a) If the gas is compressed suddenly, then the diathermic wall does not have enough time to
release the heat to the surroundings. During the process, the heat of the system (here, gas)
remains constant, making it an adiabatic process.
Therefore,
γ γ
PV
i i = Pf V f
5
 3
V   5
⇒ Pf = P0 ×  0   Since the gas is monatomic , γ = 3 
 V0   
 2 
5
⇒ Pf = 23 P0

(b) If the gas is compressed slowly, then at each stage of the process, the diathermic wall releases
excess heat to keep the system at the same temperature as the surroundings, i.e., T0. Hence,
this process matches the description of being isothermal, and according to Boyle’s law,
PV
i i = Pf V f

V0
⇒ Pf = P0 ×
V0
2
⇒ Pf =
2P0

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 06

Example

P0 , V0 , T0 P0 , V0 , T0

A cylinder is filled with H2 and He in two equal chambers separated by an

adiabatic movable piston. The H2 chamber is slowly heated with a heater. H2 He
1
The final volume of the He chamber is th of the initial volume. Find the
8
heat given to the system. Assume the heat loss to the surroundings to be V0
zero. 8

H2 He

Solution MAIN

Let us assume that the initial pressure, volume, and temperature of both chambers are P0, V0, and
T0, respectively. The heat is provided in the H2 chamber, and as a result, the piston moves towards
V
the He chamber. It is given that the final volume of the He chamber is 0 .
8
V0 15V0
Therefore, the final volume of the H2 chamber is, 2V0 − =
8 8
Since the gases are separated by an adiabatic piston, the He gas does not receive or lose any heat
throughout the process. Hence, the compression of He can be considered as adiabatic.
For the He chamber,
γ γ
PV
i i = Pf V f
5
 3
V   5 
⇒ Pf = P0 ×  0   γ = 3 for He since it is monatomic 
 V0   
 8 
5
⇒ Pf =
8 P0 3

⇒ Pf =
32P0
The process is carried slowly; therefore, the pressure in each chamber will be the same at each
stage. Hence, the final pressure of both chambers is 32P0.

The heat given to the H2 chamber can be found by using the first law of thermodynamics as the
sum of the change in internal energy and the work done on the piston.
(i) The change in the internal energy,
f 
∆U H2 =  nR ∆T 
2  H2
f 
⇒
= ∆U H2  ( Pf V f − PV
i i )
2  H2
5  15V0 
⇒= ∆U H2   32P0 × − P0V0  
2 
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8 
5
 f 
07 ∆U H2 =  nR ∆T 
2  H2
f 
⇒
= ∆U H2  ( Pf V f − PV
i i )
2  H2
5  15V0 
⇒
= ∆U H2   32P0 × − P0V0  
2  8 
5 
⇒ ∆U H2 =  (59P0V0 ) 
2 
295
⇒ ∆U H2 = P0V0
2

(ii) The resultant of the work done by both the gases is zero since the initial and final kinetic
energies of the piston are the same, i.e., zero.
⇒ WH2 + WHe =
0
⇒ WH2 =
− WHe
 PV
i i − Pf V f 
⇒ WH2 =
− 
 γ − 1  He
 V0 
 P0V0 − 32P0 × 8 
⇒ WH2 =
− 
 5 
−1
 3 
 
 −3P0V0 
⇒ WH2 =
− 
 2 
 3 
9
⇒ WH2 = P0V0
2

Hence, the heat supplied to the H2 chamber (or the system) is given by,
∆Q =∆U + W
295 9
⇒ ∆Q = P0V0 + P0V0
2 2
⇒ ∆Q =152P0V0

Alternatively, we can also apply the first law of thermodynamics to the system of both gases. In that
f  f 
case, the change in internal energy will be the resultant of both the gases  nR∆T  +  nR∆T  .
2  H2  2 He
The work done on the system would be zero as its total volume will remain constant, i.e., 2V0.

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 08

Example

P
B C
2P0

n moles of a monatomic gas undergoes a cyclic process

as shown in the P-V graph. It consists of four processes,
namely A-B, B-C, C-D, and D-A. Find ∆U, W, and ∆Q for each P0
process. A D

V0 2V0 V

Solution

Processes A-B and C-D are isochoric, and processes B-C and D-A are isobaric. We know the following
about ∆U, W, and ∆Q:
f
∆U
=
2
( Pf V f − PVi i )
W = Area under the P-V curve
∆Q = ∆U + W

∆U, W, and ∆Q for the processes are calculated in the following table:

Process ∆U W ∆Q

3 3
A-B (2P0V0 − P0V0 ) = P0V0 0 1.5P0V0
2 2

3
B-C (2P0 × 2V0 − 2P0V0 ) =
3P0V0 2P0V0 5P0V0
2

3
C-D ( P0 × 2V0 − 2P0 × 2V0 ) =
− 3P0V0 0 –3P0V0
2

3 3
D-A ( P0V0 − 2P0V0 ) =
− P0V0 –P0V0 –2.5P0V0
2 2

A-B-C-D-A 0 P0V0 P0V0

In the given process, we are supplying 1.5P0V0 + 5P0V0 = 6.5P0V0 amount of heat into the cycle. From
which, P0V0 amount of heat gets converted into the work done and rest (5.5P0V0) gets rejected by
the cycle.

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 09

Efficiency of a Cycle

In cyclic processes, the heat supplied does not entirely get converted into work. A fraction of
it is rejected into the surroundings and is irrecoverable. The efficiency of a cycle denoted by 𝜂 is
expressed as follows:
Work done
η =
Heat supplied
Recall the previous problem in which we supplied 6.5P0V0 of heat during processes A-B and B-C. The
net work done by the cycle came out to be P0V0, and 5.5P0V0 of heat was lost to the surroundings.
Therefore, the efficiency of the cycle is given by,
P0V0
=η = 0.15
6.5P0V0
⇒ % 𝜂 = 15
Let us consider a cycle receiving Q1 amount of heat from a
reservoir at a higher temperature. During one cycle, it does W Reservoir
amount of work and releases Q2 amount of heat to the sink. Q1

According to the conservation of energy,

Q1 = W + Q2
⇒ W = Q1 – Q2 Cycle

W
Hence, the efficiency of the cycle is given by, Q2
W Q − Q2
η = 1
=
Q1 Q1 Sink
Q2
⇒ η =1 −
Q1
 Q2 
⇒ %η =1 −  × 100
 Q1 

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