Thermodynamic Equations of State

• Thermodynamic equations of state will lead to an

understanding of concepts such as surface tension,
etc.
• Leads to a knowledge of how to predict the
physical property or at least relations between
physical properties.

Fundamentals of Thermodynamics:

• Variables in the lab: P, V, T

• First law: dE = dw + dq
• Energy is state function; any combination of heat
and work possible
• Microscopic scale: energy is sum of rotational,
vibrational, translational and electronic energy
levels.
• Remember w = −PdV; negatvie sign indicates
system energy increases when work done on
system.
• .Assume only PdV work and defining entropy as
dqrev/T ≡ dS
• Leads to first law: dE = −PdV + TdS
• Gibbs Free Energy: G = H −TS
• Helmholtz Energy: F = E − TS

1
 Relationship between E and Volume in
terms of P, V, T
• Take partial of First Law: dE = −PdV + TdS with
respect to V at constant T:
 ∂E   ∂S 
  = −P + T  
 ∂V T  ∂V T
• Equations should be expressed in terms of P, V, T.
• Helmholz free energy: F ≡ E − TS
• Differentiate: dF ≡ dE − TdS − SdT
• Substitute from first law. dF ≡ − PdV + TdS − TdS − SdT
= − PdV − SdT
• Total Differential of F: dF =  ∂F  dV +  ∂F  dT
 ∂V T  ∂T V
 ∂F   ∂ F 
2
• Comparing leads to:   = − P ∧   = − ∂P 
 ∂V T 
 ∂2V∂T   ∂T V
 ∂F   ∂ F 
• And also:   = − S ∧   = − ∂S 
 ∂T V 
 ∂T∂V   ∂V T
 ∂ 2F   ∂ 2F 
• But:  = 
 ∂T∂V   ∂V∂T 
     ∂S   ∂P 
• Substituting from previous two equations:  = 
 ∂V T  ∂T V
 ∂E   ∂P 
• Which is leads to:   = −P + T  
 ∂V T  ∂T V
2
 Pressure Dependence of Enthalpy

• Enthalpy is defined in terms of energy, pressure and

volume: H ≡E + PV.
• Differentiating: dH = dE + PdV + VdP.
• From the first law: dE = − PdV + TdS;
• Substituting: dH = PdV + VdP - PdV + TdS
= VdP + TdS
• Divide by dP and hold T constant:  ∂H  = V + T  ∂S 
 ∂P T  ∂P T
• Use Gibbs Free Energy: G = H − TS or
dG = dH − TdS − SdT
• Substitute for dH: dG=VdP+ΤdS−TdS−SdT=VdP−SdT
• Write total differential for free energy, G(T,P):
 ∂G   ∂G 
dG =   dP +   dT
 ∂P T  ∂T  P
• By inspection:  ∂G  = V ∧  ∂G  = − S
 ∂P T  ∂T  P
 2   2 
• Second derivative: ∂ G  =  ∂V  ∧  ∂ G  = − ∂S 
 ∂P∂T   ∂T   ∂T∂P   ∂P T
  P  
∂V  ∂S 
• Or:  
 = − 
 ∂T P  ∂P T
 ∂H   ∂V
• Substitute for enthalpy equation:  ∂P  = V − T ∂T 
 T  P
3
 Equations of State:Temperature
Dependence
• Recall 3 variables to be used are P, V, T.
• Knowledge of two of the variables allows
determination of the energy state of the system.
• Two polynomial equations of state used here.
– V = f(P) and
– P = f(V)
• V = Vo[1 + ao(T) – a1(T)P + a2(T)P2 + …] where
– coefficients aj are functions of temperature.
– Vo = volume at absolute zero.
• Differentiate with respect to T and neglect higher
terms:  ∂V   ∂ao 
  = Vo  
 ∂T  P  ∂T  P
• When using only the first two terms of the series
expansion, we have: V = Vo[1 + ao(T)].
• Substitute for Vo: Vo = V/[1+ao(T)].
1  ∂V  1  ∂ao 
  =  
V  ∂T  P [1 + a o (T )]  ∂T  P
• When ao << 1, the equations reduces to:
 ∂ao  1  ∂V 
  =   =α
 ∂T P V  ∂T P
where α = volume expansivity, relative change in
volume with temperature; related to temperature
variation of ao. 4
 Equations of State: Pressure Dependence

• Found by taking derivative of equation of state with

respect to pressure:
 ∂V  1  ∂V  V
  = − Voa1 ∨ −   = o a1
 ∂P  T V  ∂P T V
where higher pressure terms are ignored (only first
order considered significant).
• But V = Vo[1+ ao]; so that
1  ∂V  a1
χ=−   = ≈ a1
V  ∂P T 1 + a o
since a1<<a0<<1
§ χ = isothermal compressibility.
§ Pressure as a function of T, V:
2
V − V  Vo − V 
P = Po (T) + P1(T ) o  + P2
( T )   + ....
 Vo   Vo 
§ Pi = material dependent coefficients; determined
experimentally.
§ Po = pressure required to decrease the volume of the
solid at higher temperature to what it would be at 0 K
and no pressure.
§ P0<< P1 or P2

5
 Relationship between Pi and ai

• Recall: V = Vo[1 + ao(T) – a1(T)P + a2(T)P2 + …]

• Solve for Volume: V = 1+ ao (T) − a1( T)P + a2 (T)P2
Vo
V
− 1 = ao (T ) − a1(T )P + a2 (T )P2
Vo
Vo − V
= −ao (T ) + a1( T)P − a2 (T )P2
Vo
• We use this in the earlier equation:
2
V − V  Vo − V 
P = Po (T) + P1(T ) o  + P2
( T )   + ....
 Vo   Vo 
P = Po (T ) + P1 (T )(− ao (T ) + a1P − a2 P2 + ...) +
• To get
P2 (T )(− ao (T ) + a1P − a2 P2 + ...)2 + ....

• Expand the second term

( )
• Neglect squared and higher terms in terms of ao and
Po. P = Po + P − ao + a1P − a2 P 2 + ... +
1

P (− 2ao a1P + ao a2 P + a1 P + ...) + ....

2 2 2 2
2

• This can only be true when the following happens:

Po − P1ao = 0,
P1a1 − 2P2 ao a1 = 1,
6
− P1a2 + 2 P2 ao a2 + P2 a12 = 0
 Relationship between Pi and ai (cont.)

• Solve for ai from Po − P1ao = 0,

P1a1 − 2P2 ao a1 = 1,
− P1a2 + 2 P2 ao a2 + P2 a12 = 0
• Gives: P
ao = o ,
P1
1 1  2P P 
a1 = = 1 + o 2 ,
P1 − 2 P2 ao P1  P12 
P  6P P 
a 2 = 2 1 + o 2 
P13  P12 

• Pi can also be expressed in terms of ai,

• Figure shows that compressibility increases
with atomic number.
• Slopes at high pressures are similar for all.
• Coefficients of expansion nearly constant at
absolute zero (see figure), but increase at
higher temperatures .

7
 Pressure Dependence of Heat Capacity

• Recall the definition of heat capacity: C P =  ∂H 

 ∂T  P

• Take its derivative with respect to P at constant T

 ∂C P  ∂  ∂H   ∂  ∂H  
  =    =   
 ∂P T ∂P  ∂T  P T ∂T  ∂P T  P
 ∂H   ∂V 
• But earlier we showed:   = V − T 
 ∂P T  ∂T  P
 ∂C P  ∂  ∂H   ∂   ∂V  
• Substitute:   =     = V − T   
 ∂P T ∂P  ∂T  P T ∂T   ∂T P  P

 ∂V   ∂T   ∂V   ∂ 2V 
=  −    − T  2 
 ∂T  P  ∂T  P  ∂T P  ∂T  P
 ∂C P   ∂ 2V 
  = −T  2 
 ∂P T  ∂T  P
• We can now use the equation of state to determine
an equation for calculating heat capacity under
various conditions.
• Recall: V = Vo[1 + ao(T) – a1(T)P + a2(T)P2 + …]

[ ]
• Substitute:
 ∂C P   ∂ 2 1 + a o (T ) + a1 (T ) P + a2 (T ) P 2
  = −TVo  
 ∂P T  ∂T 2 P
 ∂C P   ∂ 2 ao (T ) ∂ 2 a1 (T ) ∂ 2
a2 (T ) 2 
 
 = −TVo  + P+ P
 ∂ T 2 2 2 
P  ∂T ∂T ∂T  P
8
 CP Vs P(cont)

• Integration gives the pressure dependence of CP.

 2 2 2 
CP ∂C = −TV P  ∂ ao (T ) + ∂ a1(T ) P + ∂ a2 (T ) P 2 dP
∫ o P o ∫0  
CP
∂T 2 ∂T 2 ∂T 2 
 ∂ 2a (T ) 1 ∂ 2 a (T ) 1 ∂ 2a (T ) 
o
CP = C P − TV  o P+ 1 2
P + 2 P 3
 ∂T 2 2 ∂T 2 3 ∂T 2 
 
• CoP = heat capacity at zero pressure.
• The first second derivative term is dominant at high
temperature and heat capacity is expected to decrease
with increasing pressure in this temperature regime
(see negative sign in equation).
• Recall that alpha is the volume expansitivity: α =  ∂ao 
 ∂T  P

• The first term is the temperature coefficient of thermal

expansion.
• This term nearly linear at high temperatures.

9
 Cv vs P

• Earlier we showed:  ∂E  = − P + T  ∂P 
 ∂V T  ∂T V

• Take derivative of both sides with respect to T:

∂2E ∂2E ∂P ∂T ∂ P ∂ 2P
= =− + +T
∂T ∂V ∂V∂T ∂T ∂T ∂T ∂T 2
 ∂E 
• But: CV =  
 ∂T V
2
• Substitute:  ∂CV  = T ∂ P
 ∂V T 2 ∂T
• Earlier we used the equation of state:
2
V − V   Vo − V 
P = Po (T ) + P1( T ) o  + P2
( T ) V  + ....
 Vo   o 

• Take second derivative:

2
∂2P ∂P22 (T ) Vo − V  ∂P02 (T ) Vo − V 
∂P02 (T )
= + +  + ....
2 2 2  V 2  V
∂T ∂T ∂T  o  ∂T  o 
• Substitute into above equation, 2 P rearrange, and
∂
∫ Vo ∂CV = T ∫V ∂V
integrate: C V
2
CV o
∂T
 ∂P 2 (T ) ∂P 2 (T ) V − V  ∂P 2 (T ) V − V  2 
CV ∂C = T V  0 + 2 o + 0 o + ...dV
∫ o V ∫Vo      
CV
 ∂T 2 ∂T 2  Vo  ∂T 2  Vo  

10
 CV vs P(cont)
 
• But d  Vo − V  = − dV so that
 Vo 
 2
Vo
2 2 2 
CV ∂C = −V T V  ∂ P0 (T ) + ∂P1 (T ) Vo − V  + ∂P2 (T ) Vo − V  + ...d  Vo − V 

∫ o V o ∫Vo        Vo
CV ∂T 2
 ∂T 2  Vo  ∂T 2  Vo   
which becomes:
 ∂P 2 (T ) V − V  1 ∂P 2 (T ) V − V  2 1 ∂P2 (T )  V − V  3 
o
CV = CV − VoT  0 o + 1 o + 2 o + ...
 
 ∂T 2  Vo  2 ∂T 2  Vo      
3 ∂T 2  Vo 
 
• Theoretical calculations using heat capacity can be
done with constant volume;
• Experimental evaluation of heat capacities are usually
at constant pressure.
• A relationship between the two needed.
• The total derivatives for S(T,V) and S(T,P) multiplied by
T are:
∂S ∂S  dV ∧ TdS = T  ∂S  dT + T  ∂S  dP
TdS = T   dT + T      
 ∂T V  ∂V T  ∂T  P  ∂P T
• First term first reaction: CPdT
• First term second reaction: CVdT
• We also note the following Maxwell reactions:
 ∂S  =  ∂P  ∧  ∂S  = − ∂V 
       
 ∂V T  ∂T V  ∂P T  ∂T  P
• Substitute into above equations and subtract from each
other to get:
(CP − CV )dT = T  ∂P  dV − T 
∂V  dP

 ∂T V  ∂T P
11
 CV vs P(cont2)

• At either constant volume or temperature we get:

(C P − CV ) = T  ∂P   ∂V 
 
 ∂T V  ∂T  P
• We now find the two partials using the equations of
state:
 ∂P   ∂Po   ∂P1  Vo − V  V 
  =  +   
  − P1 
d  + ....
 ∂T V  ∂T V  ∂T V  Vo   Vo T
• Assume: V = Vo and third term is zero since it is at
constant volume:  ∂P   ∂ (a / a )  α
  ≈ o 1
=
 ∂T V  ∂T  a1
• Taking the derivative at constant pressure of the other
equation of state to obtain the other partial:
 ∂V 
  = Vo 
(
 ∂ 1 + a (T ) − a (T ) P + a (T ) P 2
o 1 2 )
 ∂T  P ∂T 
 P
 ∂a (T ) ∂a1(T ) ∂a (T ) 2   ∂a (T ) 
= o − P+ 2 P  = o 
 ∂T ∂T ∂T  P  ∂T P =0
= αV0
• Substitute into equation at top of page to get:
o TVoα 2
o
C −C =
P V a1
TVoα 2
=
χ

which allows us to determine one heat capacity for the

other, if molar volume and α is known. 12
 S, E, G vs P

• Pressure’s effect on these variables determined as we

did with heat capacity.
• For Entropy recall that: S = ∫T CV dT
0 T

• Substitute for CV from earlier relationships:

C
S = ∫0T V dT =
T
CVo T  ∂P 2 (T )  V − V  1 ∂P 2 (T )  V − V  2 1 ∂P 2 (T ) V − V

3 
= ∫0
T dT − Vo ∫  0 
o
+
1

o
 +
2

o 
 + ... dT

0  ∂T
2
T  Vo  2 ∂T 2
 Vo  3 ∂T 2
 Vo
 
 ∂ P (T ) V − V  1 ∂P (T ) V − V  2 1 ∂ P (T ) V − V 3 
o
= CV ln T − Vo  0 o + 1 o + 2 o + ... 
 ∂T  Vo  2 ∂T  Vo  
3 ∂T  Vo   
 
• Energy is determined from the relationship we
developed earlier:  ∂E   ∂P 
  = −P + T  
 ∂V T  ∂T V
• We use the equation of state to determine an
expression for this:
 ∂P 
T  − P =
 ∂T V
2
  ∂Po     ∂P1   Vo − V    ∂P2   Vo − V 
T   − P +
o T   − P1  +
  ∂T
T   − P2  + ....
  ∂T V    ∂T V   V o    V   V o 

13
 S, E, G vs P(cont)

• Now we rearrange and integrate:

E
∫ Eo dE = E − Eo =
  ∂P    ∂P1   Vo − V    ∂P2   Vo − V 
2   V − V 
− Vo ∫  T   − + − + − + d  
o o
 Po  
T  P1   
T  P2   ...
   ∂T V    ∂T V   Vo    ∂T V   Vo    Vo 
2
  ∂P   V − V  1   ∂P1   V − V  1   ∂P2  V − V 
E = Eoo − Vo T  o  − Po   o  + T   − P1   o  + T   − P2   o 
  ∂T V   Vo  2   ∂T V   Vo  3   ∂T V   Vo 

• Free Energy, G = f(P,V, T): dG = −SdT + VdP.

[ ]
• Replace each term
G T (
T )
P 2
∫Goo dG = − ∫0 So + ∫0 Cv od ln T dT + ∫0 Vo 1 + ao + a1P + a2 P dP

G = Eoo − ∫0T (∫0T Cv o d ln T )dT + PVo 1 + ao + a1P + a2 P 2 

 1 1 
 2 3 
• Equations of state used with standard thermodynamic
relationships to determine values of thermodynamic
quantities from a set of data.
:

14