THERMODYNAMIC PROCESSES

Uf

 dU  U
Regardless
Exact differentials: U  f U0 of path!
U0

Another, equivalent criterion of exactness of dz :

 dz  0
As we said, and

So, and are not exact differentials.

EULER CRITERION:
Based on the Euler
If dM  A( x, y )dx  B( x, y)dy Criterion are Maxwell
Relations, a “family”
 M   M  of important identities
  dx    dy in thermodynamics.
 x  y  y  x
is an exact differential, i.e.,
 dM  0
Then and    M      M  
only then:         
 y  x  y  x  x  y  x  y
 A   B  Also, the Euler Criterion
Meaning that: 
 y    x  is essential for introducing
 x   y the notion of entropy!
Another important formula, very often used in thermal
physics, is the so-called “Cyclic Chain Rule”:

Suppose that : M ( x, y ) const.

 M   M 
Then dM  0  0  dx    dy
 x  y  y  x
By rearranging, we get:
 M 
 
 x   y  x
It is not the most elegant
proof of this theorem – if
you want a more “orthodox”   
proof, it can be found in math
 y  M  M 
books (and a more general
 
 x  y
theory is the theory of “Jacobi
Determinants”, a.k.a.
“Jacobians”
Examples: Path independence – a simple exercise:

An ideal gas is initially at (p0 , T0 ) and then compressed and

heated to (pf , Tf ). What is the change ΔV in the gas volume?

First, we solve the

problem by “brute force”: pV  kNT (ideal gas
equation)

T0 Tf
V0  kN ; V f  kN ;
p0 pf
 T f T0 
V  V f  V0  kN  
p p 
 f 0 
Exercise, cont.: Let’s try to get the same by integration

 V   V 
V  V (T , p) and dV    dT    dp
 T  p  p T

kNT  V  kN  V  kNT
V so    and     2
p  T  p p  p T p

It can be readily checked that the Euler Criterion is satisfied!

So, we have:
kN T
dV  dT  kN 2 dp
p p
 Let’s now integrate.
First, along Path 1:
from p0 to pf with T = const. = T0
then
From T0 to Tf with p = const. = pf

pf Tf
dp kN
V    kNT0 2   dT
p0
p T0 p f
pf
 1 
 kNT0   2  
kN
T f  T0 
 p  p0 p f
 T0 T0 T f T0   T f T0  Same as
 kN      kN    by “brute
p p p p  p p  force” – OK!
 f 0 f f   f 0 
Try the other path: from T0 to Tf with p = p0 = const.,
then from p0 to pf with T= Tf = const.:
Tf pf

p  kNTf  p 2
kN dp
V   dT 
T0
p0 0

 T f T0 T f T f   T f T0 
 kN  
p
    kN 
 p
 
 OK!!! ☺
 0 p 0 p 0 p f   f p 0 

Another important comment: there are some “standard”

coefficients, or “response functions” characterizing
materials. For the most often used materials, the values
of those coefficients are given in many books.
We have already discussed the heat capacities Cv and Cp
that are such “response functions”. Let’s introduce more:
 1  V  Constant pressure (isobaric) volume
p    expansitivity (a.k.a. “volume thermal
V  T  p expansion coefficient”).

1  V 
 T     Isothermal compressibility
V  p T

The volume differential dV we have used may be expressed

in terms of these coefficients:

dV  V   p dT  V   T dp
Next example: “Free expansion of gas into vacuum” – a
Good illustration of the use of the “cyclic chain rule”

The gas surges into the formerly evacuated space, and

eventually comes to equilibrium, now occupying the entire
container. The question: does the gas temperature
change in such a process?
Try the First Law: U  Q  W
But Q=0 because the walls are thermally insulated, and
W=0 because the gas did not do any work! So, ΔU=0. It
does not tell us very much…
Let’s consider the temperature as a function of the
Internal energy U and volume V: T=T(U,V). Then:
 T   T 
dT    dU    dV
 U V  V U
But dU=0, so
 T 
dT    dV
 V U
We don’t know the value of this derivative, but here the
“cyclic chain rule” offers much help:
 U  One of these
  derivatives we
 T   V T
   already know!
 V U  U  Could you tell
 
 T V which one?
Yes! You are right, it’s the constant volume heat capacity!

 U 
   CV
 T V
 U 
So, we only need to know the other derivative:  
 V T
For ideal 3 (you have to
monoatomic U  kNT trust me!)
gas: 2

 U 
It means that ideal gas does not
So,    0 !!! change its temperature in the
 V T free expansion proces!!!
Can you explain, why?
A more realistic gas model is the well-known
Van der Waals gas with a state equation:

 N 
2
pV  kNT   p  a 2 V  Nb  kNT
 V 
Constants to be determined from
experiments on a given gas

The internal energy of van der Waals gas can be obtained

From calculations that tare not trivial (so we will skip them):

2
N a
U van der Waals  CV T  U0
V Undetermined integration
constant
Van der Waals gas vacuum expansion, cont.:
From the energy equation, we get:

 U 
2
N
   a 
 V T V 
Inserting into the formula we got on Slide 10:
 U 
2
N
  a 
 T   V T 2
   
V aN
  
 V U  U  CV CV  V 2
 
 T V

aN 2 It is negative – the temperature

So: dT   dV
CV V 2
decreases!
We want to calculate the change of T in the process –
but we cannot integrate dT without knowing how Cv depends
on temperature.
Again, Euler’s Criterion will help us to answer that question:

 U   U 
2
N
U  U (T ,V )  dU    dT    dV  C dT  a  dV
 T V  V T
V
V 

Because dU is for sure an exact differential (how do we

know that?), we can apply the Euler Criterion to get:
 CV    N 
2 The right side is obviously zero,
    a   meaning that CV is not a function of V.
 V T  T  V   So, the integration is straightforward:

dV aN  1 1 
Tf 2 Vf 2
aN
T   dT   V V 2  CV  V f  V0 
T0
CV 0  