HEAT CAPACITY

When heat flows into a system, provided no phase change occurs, its temperature will
increase. The increment dT by which T increases is proportional to the amount of heat flow
dq.
dq
is called the heat capacity [Units J/K].
dT

The ratio

Definition: The heat capacity (denoted by C) is the increment in heat dq required to

increase the temperature by an amount dT.
C is an extensive quantity but molar heat capacity Cm = C/n is an intensive quantity
(property). Usually subscript m is omitted. The quoted units then define whether C or Cm is
intended. The term specific heat capacity, i.e. heat capacity per gram, is also used.
The value of the heat capacity however depends on the circumstances under which the
system is heated. So in order to have a defined heat capacity one must specify the
condition.
1). Isochoric (constant volume), heat capacity is abbreviated as CV. If heat is supplied at
constant volume (dV = 0), the system can do no PV work (assuming the system does no
other kind of work). Then, from first law of thermodynamics

dq V

dU
q

By definition CV

CV

From an ideal gas

dU
dT

dU
dU CV dT
dT

2). Isobaric (constant pressure) heat capacity is abbreviated as Cp. If the heat is supplied
at constant pressure, usually the sample expands doing work against the external
pressure. Thus in addition to raising the temperature some extra heat is required for the
expansion work. Hence, more heat will be required to raise the system temperature
under constant pressure condition than under constant volume condition. Thus CP > CV
From 1st law of thermodynamics dU = dq + dw and dw= -PdV, then

dU dq P dV
dq dU P dV
CP

U P dV
H

dT
T
P T P

dqp

For an ideal gas:

H

CP

dH
dT

dH
dH C P dT
dT

In order to obtain U when an ideal gas is heated from temperature T1 to T2 at constant

volume, the integrated form of dU CV dT is to be used.
T2

U CV dT

where CV is the heat capacity at constant volume.

T1

Similarly the enthalpy change H when an ideal gas is heated from temperature T1 to T2 at
T2

constant pressure is given by H C P dT .

T1

where CP is the heat capacity at constant pressure.

Note if CV and Cp are given as molar heat capacities then;
T2

T2

T1

T1

U nCV dT and H nC P dT .
For an ideal gas it can be shown that Cp Cv = R

HEAT CAPACITIES OF GASES

The heat capacity of a gas at constant pressure Cp exceeds the heat capacity of that gas at
constant volume, Cv, because the gas performs work on its surroundings as it expands at
constant pressure. If the volume is held constant such expansion work by the gas is
impossible.

From the kinetic molecular theory of gases, the energy, U, of one mol of ideal monatomic
gas as a function of temperature is given as:

U 32 RT

U
32 R
Therefore Cv
T v

and Cp = Cv, + R =

5
2

R since, the enthalpy of an ideal gas is greater than its internal energy

by PV (= RT). So that H =

3
2

RT + RT =

5
2

RT

H
C p
5 R
T p 2

The heat capacity of a perfect gas is independent of temperature.

Predicting Heat Capacities of gases: The equipartition theorem

We can predict the heat capacities of monoatomic, diatomic or polyatomic gases based on
equipartition theorem, simply by counting the degrees of freedom. The mean energy per
1
2

degree of freedom per mol of monatomic ideal gas is

RT. Note however that the

classical equipartition theorem holds in the high-temperature limit.

The internal energy of 1 mol of monatomic ideal gas is

possess, on average,

3
2 kBT

3
2

RT. This means that each particle

units of energy. Monatomic particles have only three

translational degrees of freedom, corresponding to their motion in three dimensions. They

possess no internal rotational or vibrational degrees of freedom. Thus, the mean energy per
degree of freedom per mol of monatomic ideal gas is

1
2

RT.

For rigid (non-vibrating) linear molecules and rigid diatomic molecules, the internal energy
U=

3
2

RT + RT =

5
2

RT; where RT is the contribution of rotational degrees of freedom

(rotational energy).
U
5 R for rigid diatomic molecules.
Therefore giving Cv
T v 2

P = linear momentum = mv

J = angular momentum = I

I = moment of Inertia = miri2

= angular velocity

Real Gases: Temperature Dependence of Heat Capacities:

In figure 1 the dependence of constant pressure molar heat capacity, Cp, on temperature is
shown for a number of gases. In general the more complex the molecule, the greater is its
molar heat capacity and the greater is the increase of heat capacity with rising temperature.
It has been customary to express the molar heat capacity of a gas empirically as a power
series in the temperature, either as:
C P T T 2 ...

or C P a bT cT 2 ...

The value of constant volume molar heat capacity, Cv, can then be found from Cp at any
temperature by using the relation: Cp = Cv + R.

C2H6

110

CP,mean / J mol-1 K-1

90

C2H4
SO3

70

C2H2
SO2

50

H2S
Cl2

NH3

HCl

30
300

500

700

900

1100

1300

1500

T/K

Fig. 1: Variation of molar heat capacities with temperature for some gases.

Example
1. One mol of methane gas originally at 298 K and 1 atm is heated at constant pressure
until the volume is doubled. Assuming the gas behaves ideally, calculate U and H for
the process. The molar heat capacity of methane at constant pressure is Cp = 22.34 +
48.1 x 10-3T J mol-1 K-1.
Answers:

10587 and 13065 J.