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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
dq V
dU
q
By definition CV
CV
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
CP
dH
dT
dH
dH C P dT
dT
U CV dT
T1
Similarly the enthalpy change H when an ideal gas is heated from temperature T1 to T2 at
T2
T2
T1
T1
U nCV dT and H nC P dT .
For an ideal gas it can be shown that Cp Cv = R
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
3
2 kBT
3
2
1
2
RT.
For rigid (non-vibrating) linear molecules and rigid diatomic molecules, the internal energy
U=
3
2
RT + RT =
5
2
(rotational energy).
U
5 R for rigid diatomic molecules.
Therefore giving Cv
T v 2
P = linear momentum = mv
J = angular momentum = I
= angular velocity
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
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: