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Section 2D. State Functions and Exact Differentials

This document discusses state functions and exact differentials in thermodynamics. It provides examples to show: 1) State functions have exact differentials, while path functions do not. Heat (dq) for a reversible expansion of a perfect gas is an inexact differential and path dependent. 2) Entropy (dS) is shown to be an exact differential, making entropy a state function. 3) The heat (q) for a monoatomic gas undergoing two different paths between two states is path dependent, with q1 not equal to q2, demonstrating heat is a path function.

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223 views4 pages

Section 2D. State Functions and Exact Differentials

This document discusses state functions and exact differentials in thermodynamics. It provides examples to show: 1) State functions have exact differentials, while path functions do not. Heat (dq) for a reversible expansion of a perfect gas is an inexact differential and path dependent. 2) Entropy (dS) is shown to be an exact differential, making entropy a state function. 3) The heat (q) for a monoatomic gas undergoing two different paths between two states is path dependent, with q1 not equal to q2, demonstrating heat is a path function.

Uploaded by

Akib Imtihan
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Section 2D. State Functions and Exact Differentials


Can use the mathematical properties of state functions to draw conclusions about relationships
between physical properties - including ones that may be totally unexpected. Practically, we can
combine measurements of different properties to determine the value of a property we require.

2D.1 Exact and Inexact Differentials


Recall:
State Function: a property that only depends on the current state of the system and is independent
of its history, e.g., internal energy U and enthalpy H
Path function: physical quantities that depend on the path between two states, e.g., work w and
heat q

We now need to have a mathematical aside to introduce some useful information about functions
of more than one variable (multivariable calculus).

MB.2 Multivariable calculus


MB2.1 Partial derivatives
Consider a function that depends on the variable x and y, i.e., f(x,y). We can write the differential
as

( ∂x ) ( ∂y )
∂f ∂f
df = dx + dy
y x

( ∂x )
∂f
where, for example, the partial derivative involves taking the derivative of the function
y
with respect to x, while taking y to be a constant.
Example: Write the different df for f (x, y) = A x 3 + Bx 2 y + Cx y 2 + D y 2 + E.

( ∂x )
∂f
= 3A x 2 + 2Bx y + C y 2 = g(x, y)
y

( ∂y )
∂f
= Bx 2 + 2Cx y + 2D y = h(x, y)
x

MB.2.2 Exact Differentials


Euler criterion: df , where

( ∂x ) ( ∂y )
∂f ∂f
d f = g(x, y)d x + h(x, y)d y, and g(x, y) = and h(x, y) = ,
y x
is an exact differential if and only if, the following condition is satisfied:

( ∂y ) ( ∂x ) ( ∂y∂x ) ( ∂x∂y )
∂g ∂h ∂2 f ∂2 f
= i.e., =
x y
The satisfaction of this criterion implies that the order of application of differentiation is not
important for functions with exact differential. An exact differential is an infinitesimal quantity
that, when integrated, gives a result independent of the path. State functions have exact
differentials. Path functions do not have exact differentials, and thus upon integration gives a
result that depends on the path.
25

Is our previous example, an exact differential?

( ∂y )
∂g
= 0 + 2Bx + 2C y
x

( ∂x )
∂h
= 2Bx + 2C y + 0
y
These are equivalent, so df for the example function is an exact differential.

Thermodynamic state functions depend on more than one state variable, e.g., U(T,P), U(p,V), or
U(T,V), etc... Suppose we take U = U(T,V). The change in internal energy U when temperature T
and volume V are changing is:

( ∂T ) ( ∂V )
∂U ∂U
dU = dT + dV = CV dT + πT dV
V T
The differential dU depends on the constant volume heat capacity, and we have introduced a new
quantity: the internal pressure πT. Note that for a perfect gas πT = 0, as the internal energy
depends only in the temperature, and, hence, there will be no change in the internal energy for
changing volume at constant temperature.

Let us consider another thermodynamic example Is dV an exact differential? Since V is a state


function, we expect dV to be an exact differential, but how do we show this mathematically?
n RT
For the perfect gas, we have V(T, p) = where we have written V(T,p) to clearly show that
p
the volume is a function of two variables T and p. Hence, the differential can be written as

( ∂T ) ( ∂p )
∂V ∂V
dV = dT + dT
p T

( p2 )
nR −n RT
= dT + dp
p
To show that dV is an exact differential, we must show

( ∂p ( ∂T )p) ( ∂T ( ∂p )T)
∂ ∂V ∂ ∂V
=
T p
From the results above, we have

∂( p ) ( )
−nRT
nR ∂
p2 −n R −n R
= ⟹ = 

∂p ∂T p2 p2
T
p
Therefore, we conclude that indeed dV is an exact differential.

What about inexact differentials? Let us consider as an example the heat for the reversible
expansion of a perfect gas due to heating.
26

( ∂T )
∂U n RT n RT
d q = dU + pdV = dT + dV = CV dT + dV
V
V V
For a perfect gas, the constant volume heat capacity does not depend on volume, i.e,

( ∂V )
∂CV
=0
T
However,
∂( V )
nRT
nR
=
∂T V
V
These are clearly not equal, so dq is an inexact differential, and therefore, is a path function.

However, what if we consider a change in entropy dS (we will discuss much more on entropy in
Section 3: The 2nd and 3rd Laws), where
dq CV nR
dS = = dT + dV
T T V
Now, we have

( )
∂(CV /T )
=0
∂V T
and
∂( V )
nR

=0
∂T
V
Hence, dS is an exact differential and S is a state function.

In order to more clearly see how the value of an integral between specific end points (states of
the system) depends on the pathway, let’s consider the heat for a very specific change of state for
1 mole of a monoatomic perfect gas:
T1,V1 T2,V2

n RT 3 RT
For this process, d q = nCV,m dT + dV = RdT + dV where we have used
V 2 V
3
CV,m = R for a monoatomic gas and the fact we are considering 1 mole.
2
Among the many possible pathways to get from State 1 to State 2, two are the following
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
27

To find the heat, we must integrate over the paths, i.e.,

( V1 ) 2
T2V2 V2 T2
RT1 3 V2 3
∫T V ∫V ∫T 2
Path 1: q1 = dq = dV + RdT = RT1 ln + R(T2 − T1)
1 1 1
V 1

( V1 )
T2V2 T2 V2
3 RT2 3 V2
∫T V ∫T ∫V V
Path 2: q2 = dq = RdT + dV = R(T2 − T1) + RT2 ln
1 1 1
2 1
2

These are clearly not equal, q1 ≠ q2, and therefore the value depends on the path.

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