36

Chapter 2

First Law of Thermodynamics

Now that we have established that the internal energy is a state function, we
want to be sure that we know how many variables have to be specified to describe the state of the system. If the system involves only PV work, the internal
energy of a mass of a pure substance can be described by a mathematical function of T, V, and n or T, P, and n ; these functions are represented by U (T, V, n )
and U (T, P, n ). We will give the precise form of these functions only for ideal
gases because the functions for real substances are very complicated. The internal energy of a homogeneous binary mixture can be specified by a function
U (T, V, n1 , n2 ), U (T, P, n1 , n2 ), or U (T, P, x1 , nt ), where x1 is the mole fraction of
substance 1 and nt is the total amount of material in the system. Thus the description of the extensive state of a homogeneous mixture of N species requires N 2
variables, one of which must be extensive. The intensive state of a pure substance
is determined by two intensive variables (T and P ), and the intensive state of
a homogeneous binary mixture is determined by three intensive variables (T, P,
and x1 ). Thus the intensive state of a homogeneous mixture of N species is specified by N 1 independent intensive variables. In Section 5.4 we will discuss the
change in this rule when chemical reactions are involved and are at equilibrium.

2.3 EXACT AND INEXACT DIFFERENTIALS

The internal energy U is a state function, like V, because it depends only on the
state of the system. The integral of the differential of a state function along any
arbitrary path is simply the difference between values of the function at two limits.
For example, if a system goes from state a to state b , we can write

dU  Ub

Ua  U

(2 .11)

Since the integral is path independent, the differential of a state function is called
an exact differential. The quantities q and w are not state functions. The integrals
of their differentials in going from state a to state b depend on the path chosen.
Therefore, their differentials are called inexact differentials. We will use d instead
of d to indicate inexact differentials. In going from state a to state b the work w
done is represented by

dw  w

(2 .12)

Note that the result of the integration is not written wb wa , because the amount
of work done depends on the particular path that is followed between state a
and state b. For example, when a gas is allowed to expand, the amount of work
obtained may vary from zero (if the gas is allowed to expand into a vacuum) to
a maximum value that is obtained if the expansion is carried out reversibly, as
described in Section 2 .4.
If an infinitesimal quantity of heat dq is absorbed by a system, and an infinitesimal amount of work dw is done on the system, the infinitesimal change in
the internal energy is given by
dU  dq

dw

(2 .13)

2 .3 Exact and Inexact Differentials

where the d is used with U since dU is an exact differential and d is used with q
and w because they are inexact differentials. In other words, U is a function of
the state of the system, and q and w for a process depend on the path.
It is interesting to note that the sum of two inexact differentials can be an
exact differential. To illustrate this point further, we consider the path from
a to b in Fig. 2 .5. We may define the path by a curve y  y (x ) connecting
a and b .
The differential dz  y dx is not an exact differential,

dz  z 

y dx  area I

(2 .14)

because this area depends on the path between a and b , as may be seen from
Fig. 2 .5.
The differential dz  y dx x dy is an exact differential. Since dz  d(xy ),

d z  z

d(xy )  xb yb

(2 .15)

xa ya

x dy is an exact differential may be seen from

The reason dz  y dx
Fig. 2 .5. The integral of dz from state a to state b may be written

dz  z 

y dx

x dy  area I

area II

(2 .16)

The sum of these areas is independent of the shape of the curve (path) between a and b . If  dz does not depend on the path taken between the points,
then dz is said to be an exact differential. Thermodynamic quantities like U,
H, S, and G (all of which will soon be introduced) form exact differentials ,
since their values are dependent on the state variables and not on the path by
which the system got there. There is a simple test to see whether a differential
is exact.
For a system with just two independent degrees of freedom, the total differential dz of a quantity z may be determined by the differentials dx and dy in two
other quantities x and y . In general,
dz  M (x, y ) dx

N (x, y ) dy

(2 .17)

where M and N are functions of the independent variables x and y .

To show the test for exactness we now consider a function z that has an exact
differential. If z has a definite value at each point in the xy plane, then it must be
a function of x and y . If z  f (x, y ), then
dz 

!x 
!z

dx

!y 
!z

dy

(2 .18)

37
b

yb
II

y
ya

a
I

xa

Figure 2 .5 Path of a system in

going from state a to state b .

xb

38

Chapter 2

First Law of Thermodynamics

Comparing equations 2 .17 and 2 .18, we find

M (x, y ) 

 x

(2 .19)

 y

(2 .20)

N (x, y ) 

Since the mixed partial derivatives are equal,

     

(2 .21)

 y   x 

(2 .22)

z
x

y x

z
y

x y

then
M

This equation must be satisfied if dz is an exact differential. It is Eulers criterion

for exactness. This relation is also very useful for obtaining relations between the
derivatives of thermodynamic functions.
To illustrate the use of equation 2 .22 let us reconsider the differential dz 
y dx . Since M  y and N  0, ( M / y )x  1 and ( N / x )y  0, so that equation 2 .22 is not satisfied. Therefore, dz  y dx is not an exact differential. On the
other hand, dz  y dx x dy is an exact differential: M  y , N  x so that
( M / y )x  1, ( N / x )y  1, satisfying equation 2 .22.

Example 2 .1

An inexact differential and an exact differential

Suppose
dz  xy 3 dx

3x 2 y 2 dy

Can z be a function of the state of a system (i.e., a function of x and y )? The partial derivatives of z are

 x
z

 xy 3 ,

 y
z

 3x 2 y 2

The mixed partial derivatives of z are

2z

x y

 3xy 2 ,

2z

y x

 6xy 2

Thus dz is not an exact differential, and so z cannot be a function of the state of the system.
However, consider the total differential of z !:
dz !  2xy 3 dx

3x 2 y 2 dy

Can z ! be a function of the state of a system? The partial derivatives of z ! are

 !
z
x

 2xy 3 ,

 !
z
y

 3x 2 y 2

2 .4 Work of Compression and Expansion of a Gas at Constant Temperature

The mixed partial derivatives of z ! are
2z

2z

!  6xy 2 ,

x y

!  6xy 2

y x

Since the mixed partial derivatives are equal, dz ! is an exact differential, and so z ! can be
a function of the state of the system. In fact, z !  x 2 y 3 const.

When the differential of a physical quantity is inexact, it may be possible to

use it to define another physical quantity that has an exact differential by multiplying by an integrating factor. For example, if the differential of the physical
quantity f (x, y ) is given by
df (x, y )  y (xy

1) dx " x dy

(2 .23)

 2xy

(2 .24)

df (x, y ) is an inexact differential because

[ y (xy
y

1)]

(" x )
x

 "1

(2 .25)

However, multiplying equation 2.23 by the integrating factor 1/y 2 yields

df !

df
 x
y2

1
x
dx " 2 dy
y
y

(2 .26)

The mixed partial derivatives are

(x

1/y )
y

"

1
y2

(2 .27)

"

1
y2

(2 .28)

("x /y 2 )
x

The function f ! is given by

f !(x, y ) 

x2
2

x
y

const.

(2 .29)

Integrating factors are useful for obtaining exact differentials from inexact differentials and in solving first-order differential equations.

2.4 WORK OF COMPRESSION AND EXPANSION

OF A GAS AT CONSTANT TEMPERATURE
Since work done in compressing a gas is positive, we start by considering the compression of a gas at constant temperature using the idealized apparatus shown in
Fig. 2 .6. The gas is contained in a rigid cylinder by a frictionless and weightless

39