28

In the previous lecture, we had considered the heat for a very specific change of state for 1 mole
of a monoatomic perfect gas:
T1,V1 T2,V2

We had considered the following two pathways

Constant T expansion Constant V heating
Path 1: T1,V1 T1,V2 T2,V2

Path 2: Constant V heating Constant T expansion

T1,V1 T2,V1 T2,V2

and shown q1 ≠ q2.

What about the change in entropy over these two paths?

CV nR 3R nR
dS = dT + dV = dT + dV
T V 2 T V

( V1 ) 2 ( T1 )
T2V2 V2 T2
R 3R V2 3 T2
∫T V ∫V ∫T 2 T
Path 1: S1 = dS = dV + dT = R ln + R ln
1 1 1
V 1

( T1 ) ( V1 )
T2V2 T2 V2
3R R 3 T2 V2
∫T V ∫T ∫V V
Path 2: S2 = dS = dT + dV = R ln + R ln
1 1 1
2 T 1
2

The results are the same for both pathways. S is a state function.

2E. Adiabatic Changes

Recall that an Adiabatic System: a system in which transfer of work between system and
surroundings is possible, but no transfer of heat or matter between them can occur.

2E.1 The change in temperature

When a gas expands adiabatically (q=0), the temperature goes down. Work is done so internal
energy decreases but no heat enters the system, so the internal energy decreases, and thus T
decreases.

Let’s think about the change in internal energy for this process involving an expansion (increase
in volume) accompanied by a decrease in temperature; to do so, we will consider two steps: (i) a
constant temperature expansion and (ii) a constant volume cooling, see Figure below. Since
internal energy is a state function, the choice of pathway does not matter!
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For step (i): ΔU = 0

For step (ii): ΔU = CV ΔT (if heat capacity is temperature independent); therefore, if we think
of an infinitessimal change, dU = CV dT

Since q = 0 (as the process is adiabatic), dU = d w

Considering expansion work, CV dT = − pdV

If we now consider the reversible, adiabatic expansion for a perfect gas, we can write
n RT
CV dT = − dV
V
Rearranging:
CV,m 1
dT = − dV (now using the molar heat capacity)
RT V
Integrating:
Tf CV,m Vf
1
∫T RT ∫V
dT = − dV
i i
V

CV,m Tf Vf
( Ti ) ( Vi )
ln = − ln
R
Using the properties of logarithms, we can write
1
c
Tf
( Ti ) ( Vf )
Vi
= where c = CV,m /R

Equivalently, we can write: ViTic = Vf Tfc

 30

Consider the following reversible, adiabatic expansion of a non-linear polyatomic perfect gas (or,
e.g., the reversible adiabatic expansion of cyclopentane, where we assume that this can be treated
as a perfect gas since on an exam, this the heat capacity is not for this compound is not on the
data sheet). Find the final temperature and pressure, the change in internal energy, and the work
done.

1 mol perfect gas

1 mol perfect gas

27.4 dm3
66.5 dm3

450.0K, 1.37 bar ?? K, ?? bar

1
c

( Vf )
Vi
To find Tf, Tf = Ti

c = CV,m /R = 3R /R = 3, where we have used the expression for the heat capacity of a perfect
gas. Therefore,
1
3

( 66.5 d m 3 )
3
27.4 d m
Tf = 450.0 K = 335 K