Lecture 5

First Law (Contd.)

5.0.1 P − V Work

For free expansion, i.e., expansion aganist Pext = 0, w = 0. Thus, there is no work to be
done for gas to expand in a vacuum.
Expansion against a constant pressure P = Pext :
Z 2
w = − Pext dV = − Pext (V2 − V1 ) (5.1)
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Now we will consider any reversible change occurring from State 1 to State 2. Re-
versible change means a change that can be reversed by infinitesimal modification of
a variable. Let us consider a state where the external pressure is the same as that of
the pressure of the gas inside a cylinder. That is, Pext = P. Now, if we change Pext to
Pext − δP, gas expands reversibly. When we change Pext to Pext + δP, gas compresses
reversibly. Along the reversible expansion or compression, the volume of the gas will
become equilibrated to the external pressure (i.e., Pext , which is changed during the
process).
Let us now consider an experiment where the gas is compressed suddenly at a con-
stant temperature. The initial pressure is P1 , and the final pressure is P2 . The initial
volume is V1 , and the final volume is V2 . Due to the sudden change in pressure, work
done can be computed here is

w = − P2 (V2 − V1 )

and is denoted by the shaded area in yellow color, in Figure 5.1a. But we can do the

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 P2 P2 P2 P2

P1 P1 P1 P1

P1, V1, T P2, V2, T V2 V1 V2 V1 V2 V1 V2 V1

(a) (b) (c) (d)

P1 P1 P1 P1

P2 P2 P2 P2

P1, V1, T P2, V2, T V1 V2 V1 V2 V1 V2 V1 V2

(e) (f) (g) (h)

Figure 5.1: P-V work for compression of gas (a-d) and expansion of gas (e-h) done in single
and multiple steps. Here (d) and (h) show compression/expansion done in infinite
steps.

same process in multiple steps. E.g., first the gas was compressed to (V1 + V2 )/2 and
then from (V1 + V2 )/2 to V1 . The work lost to the surroundings is shaded in Figure
5.1b. The work done in this case is less than when the compression was done in one
step. Similarly, when one adds more steps in compressing the gas, the total work done
becomes lesser and lesser. If one compresses the gas in an infinite number of steps
where the volume changes are infinitesimally small, that provides the least amount of
work lost to the surroundings; see Figure 5.1c. In that case
Z Z V2
w= d̄ w = − dV P
V1

Here P is the internal pressure of the gas and is always in equilibrium with the external
pressure. Thus, we can use here the P, as defined by the equations of the state of the
gas.
Now consider an expansion work done, where the volume is changed from V1 to V2 ,
and pressure is changed from P1 to P2 . Work done is

w = − P2 (V2 − V1 )

. Here, the work done by the gas on the surrounding during the expansion is the lowest

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if done in one step; see Figure 5.1. If done in more steps, more work can be extracted
from the gas expansion.
The expansion or compression done in infinitesimally small steps, as discussed
above, is a reversible process. In such a case, the work for expansion and compression
is of the same magnitude and in opposite directions. During the reversible process,
the internal and the external pressures balance each other. If these conditions are not
obeyed during a process, then the process is irreversible process. For such a cyclic
process:
Z V2 Z V1
wcycle = − dV P − dV P = 0 (5.2)
V1 V2

In reality, all real processes are irreversible. However, we will study reversible pro-
cesses as the limiting cases for the work. It is also easier to use reversible conditions for
theoretical calculations because equations of state can be used directly.
If an ideal gas is allowed to expand reversibly at a constant temperature, then the
external pressure is always the same as P = nRT/V during the expansion process.
Thus,
Z V2
wrev = − dV P (5.3)
V1
Z V2
nRT V
= − dV = −nRT ln 2 . (5.4)
V1 V V1

If the gas is compressed, then V2 < V1 , and thus wrev is positive (i.e., work done on
the gas). For expansion, wrev is negative (i.e., work done by the gas). For an ideal gas,
P1 V1 = P2 V2 . Thus,

P2
wrev = nRT ln . (5.5)
P1

Do it yourself: for van der Waals equation of state, show that

an2
Z V2  
nRT
wrev = − dV − 2
V1 V − nb V
V2 − nb
 
2 1 1
= −nRT ln + an − (5.6)
V1 − nb V1 V2

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5.1 Various Kinds of Work

There are many other forms of work (other than PV work). E.g., stretching of a rubber
band (d̄ w = f dL), the motion of a charge in a potential (d̄ w = ϕ dq, where ϕ is the
potential, and dq is the charge) etc. Interestingly enough, the variables that are involved
in the work contain conjugate pairs of intensive and extensive variables:
P (intensive) and V (extensive);
f (intensive) and L (extensive);
ϕ (intensive) and q (extensive).
If a system is doing the above-mentioned works, then

dU = d̄ q − Pext dV + f dL + ϕdq . (5.7)

5.2 Change in State at Constant Volume

We will first look at the change in internal energy at constant volume. Since U is a state
function, we can write:
   
∂U ∂U
dU = dT + dV (5.8)
∂T V ∂V T

If only pressure-volume work, then

dU = d̄ q − Pext dV (5.9)

By equating the two equations, we get

     
∂U ∂U
d̄ q = dT + Pext + dV (5.10)
∂T V ∂V T

Let us now consider a process occurring at constant volume. Then,

 
∂U
d̄ q = dT + 0 (5.11)
∂T V

We define the heat capacity CV at constant volume as,

 
d̄ q ∂U
CV = =
dT ∂T V

Units of CV is J K−1 and CV is J K−1 mol−1 .

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 Now,
Z T2
∆UV = dT CV (const. V) (5.12)
T1
= CV ( T2 − T1 ) = CV ∆T ≡ qV (if CV is not temperature dependent) (5.13)

Note that CV of a gas is actually temperature dependent. It can be considered constant

only for a small range of temperature changes.

5.3 Change in State at Constant Pressure

At constant P, w = − P∆V. Then,

∆UP = q P − P∆V (5.14)

U2 − U1 = q P − P(V2 − V1 ) (5.15)

⇒ q P = (U2 + PV2 ) − (U1 + PV1 ) (5.16)

= H2 − H1 ≡ ∆H (5.17)

where we define a new state function, called enthalpy, as

H = U + PV . (5.18)

From q P = ∆H, we can write

d̄ q P = dH (5.19)

H is an extensive quantity.