# 1

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.
system energy increases when work done on
system.
• Assume only PdV work and defining entropy as
dq
rev
/T ≡ dS
• Leads to first law: dE = −PdV + TdS
• Gibbs Free Energy: G = H −TS
• Helmholtz Energy: F = E − TS
2
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:
• Equations should be expressed in terms of P, V, T.
• Helmholz free energy:
• Differentiate:
• Substitute from first law.
• Total Differential of F:
• And also:
• But:
• Substituting from previous two equations:
SdT PdV
SdT TdS TdS PdV dF
− − ·
− − + − ≡
T T
V
S
T P
V
E

,
`

.
|

+ − ·

,
`

.
|

TS E F − ≡
SdT TdS dE dF − − ≡
dT
T
F
dV
V
F
dF
V T

,
`

.
|

+

,
`

.
|

·
V T
T
P
T V
F
P
V
F

,
`

.
|

− ·

,
`

.
|
∂ ∂

∧ − ·

,
`

.
|

2
T V
V
S
V T
F
S
T
F

,
`

.
|

− ·

,
`

.
|
∂ ∂

∧ − ·

,
`

.
|

2

,
`

.
|
∂ ∂

·

,
`

.
|
∂ ∂

T V
F
V T
F
2 2
V T
T
P
V
S

,
`

.
|

·

,
`

.
|

V T
T
P
T P
V
E

,
`

.
|

+ − ·

,
`

.
|

3
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:
• Divide by dP and hold T constant:
• Use Gibbs Free Energy: G = H − TS or
dG = dH − TdS − SdT
• Substitute for dH: dG=VdP+ΤdS−TdS−SdT=VdP−SdT
• By inspection:
• Second derivative:
• Or:
• Substitute for enthalpy equation:
TdS VdP
TdS PdV - VdP PdV dH
+ ·
+ + ·
T T
P
S
P
H

,
`

.
|

+ ·

,
`

.
|

T V
dT
T
G
dP
P
G
dG
P T

,
`

.
|

+

,
`

.
|

·
S
T
G
V
P
G
P T
− ·

,
`

.
|

∧ ·

,
`

.
|

T P
P
S
P T
G
T
V
T P
G

,
`

.
|

− ·

,
`

.
|
∂ ∂

,
`

.
|

·

,
`

.
|
∂ ∂

2 2
T P
P
S
T
V

,
`

.
|

− ·

,
`

.
|

P T
T
V
P
H

,
`

.
|

− ·

,
`

.
|

T V
4
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 = V
o
[1 + a
o
(T) – a
1
(T)P + a
2
(T)P
2
+ …] where
– coefficients a
j
are functions of temperature.
– V
o
= volume at absolute zero.
• Differentiate with respect to T and neglect higher
terms:
• When using only the first two terms of the series
expansion, we have: V = V
o
[1 + a
o
(T)].
• Substitute for V
o
: V
o
= V/[1+a
o
(T)].
• When ao << 1, the equations reduces to:
where α = volume expansivity, relative change in
volume with temperature; related to temperature
variation of a
o
.
P
o
P
T
a
T
V

,
`

.
|

·

,
`

.
|

o
V
P
o
P
T
a
T a T
V
V
o

,
`

.
|

+
·

,
`

.
|

)] ( 1 [
1 1
α ·

,
`

.
|

·

,
`

.
|

P P
o
T
V
V T
a 1
5
Equations of State: Pressure Dependence
• Found by taking derivative of equation of state with
respect to pressure:
where higher pressure terms are ignored (only first
order considered significant).
• But V = V
o
[1+ a
o
]; so that
since a
1
<<a
0
<<1
§ χ = isothermal compressibility.
§ Pressure as a function of T, V:
§ P
i
= material dependent coefficients; determined
experimentally.
§ P
o
= pressure required to decrease the volume of the
solid at higher temperature to what it would be at 0 K
and no pressure.
§ P
0
<< P
1
or P
2
1
o
T
1 o
T
a
V
V
P
V
V
1
a V
P
V
·

,
`

.
|

− ∨ − ·

,
`

.
|

1
o
1
T
a
a 1
a
P
V
V
1

+
·

,
`

.
|

− · χ
....
V
V V
) T ( P
V
V V
) T ( P ) T ( P P
2
o
o
2
o
o
1
o
+
]
]
]

+
]
]
]

+ ·
6
Relationship between P
i
and a
i
• Recall: V = V
o
[1 + a
o
(T) – a
1
(T)P + a
2
(T)P
2
+ …]
• Solve for Volume:
• We use this in the earlier equation:
• To get
• Expand the second term
• Neglect squared and higher terms in terms of a
o
and
P
o
.
• This can only be true when the following happens:
( )
( ) .... ... 2
...
2
2 2
1
2
2 1
2
2 1
2
1
+ + + + −
+ + − + − + ·
P a P a a P a a P
P a P a a P P P
o o
o o
2
2 1 o
o
o
2
2 1 o
o
2
2 1 o
o
P ) T ( a P ) T ( a ) T ( a
V
V V
P ) T ( a P ) T ( a ) T ( a 1
V
V
P ) T ( a P ) T ( a ) T ( a 1
V
V
− + − ·

+ − · −
+ − + ·
....
V
V V
) T ( P
V
V V
) T ( P ) T ( P P
2
o
o
2
o
o
1
o
+
]
]
]

+
]
]
]

+ ·
( )
( ) .... ... ) ( ) (
... ) ( ) ( ) (
2
2 2 1
2 2 1
2
1
+ + − + −
+ + − + − + ·
P a P a T a T P
P a P a T a T P T P P
o
o o
0 2
, 1 2
, 0
2
1 2 2 2 2 1
1 2 1 1
1
· + + −
· −
· −
a P a a P a P
a a P a P
a P P
o
o
o o
7
Relationship between P
i
and a
i
(cont.)
• Solve for a
i
from
• Gives:
• P
i
can also be expressed in terms of a
i
,
• 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 .
0 2
, 1 2
, 0
2
1 2 2 2 2 1
1 2 1 1
1
· + + −
· −
· −
a P a a P a P
a a P a P
a P P
o
o
o o

,
`

.
|
+ ·

,
`

.
|
+ ·

·
·
2
1
2
3
1
2
2
2
1
2
1 2 1
1
1
6
1
,
2
1
1
2
1
,
P
P P
P
P
a
P
P P
P a P P
a
P
P
a
o
o
o
o
o
8
Pressure Dependence of Heat Capacity
• Recall the definition of heat capacity:
• Take its derivative with respect to P at constant T
• But earlier we showed:
• Substitute:
• We can now use the equation of state to determine
an equation for calculating heat capacity under
various conditions.
• Recall: V = V
o
[1 + a
o
(T) – a
1
(T)P + a
2
(T)P
2
+ …]
• Substitute:
P
P
T
H
C

,
`

.
|

·
P
T
T
P T
P
P
H
T T
H
P P
C
]
]
]

,
`

.
|

·
]
]
]

,
`

.
|

·

,
`

.
|

P T
T
V
P
H

,
`

.
|

− ·

,
`

.
|

T V
P
T
P
P
P P P
P
P
T
P T
P
T
V
T
P
C
T
V
T
T
V
T
T
T
V
T
V
T V
T T
H
P P
C

,
`

.
|

− ·

,
`

.
|

,
`

.
|

,
`

.
|

,
`

.
|

,
`

.
|

·
]
]
]

,
`

.
|

·
]
]
]

,
`

.
|

·

,
`

.
|

2
2
2
2
[ ]
P
o
o
T
P
P
o
o
T
P
P
T
T a
P
T
T a
T
T a
TV
P
C
T
P T a P T a T a
TV
P
C

,
`

.
|

+

+

− ·

,
`

.
|

,
`

.
|

+ + + ∂
− ·

,
`

.
|

2
2
2
2
2
1
2
2
2
2
2
2 1
2
) ( ) ( ) (
) ( ) ( ) ( 1
9
C
P
Vs P(cont)
• Integration gives the pressure dependence of C
P
.
• C
o
P
= 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
• Recall that alpha is the volume expansitivity:
• The first term is the temperature coefficient of thermal
expansion.
• This term nearly linear at high temperatures.

,
`

.
|

+

+

− ·

,
`

.
|

+

+

− ·

3
2
2
2
2
2
1
2
2
2
0
2
2
2
2
2
1
2
2
2
) (
3
1 ) (
2
1 ) (
) ( ) ( ) (
P
T
T a
P
T
T a
P
T
T a
TV C C
dP P
T
T a
P
T
T a
T
T a
TV C
o
o
P P
P o
o
C
C
P
P
o
P
P
o
T
a

,
`

.
|

· α
10
C
v
vs P
• Earlier we showed:
• Take derivative of both sides with respect to T:
• But:
• Substitute:
• Earlier we used the equation of state:
• Take second derivative:
• Substitute into above equation, rearrange, and
integrate:
V T
T
P
T P
V
E

,
`

.
|

+ − ·

,
`

.
|

2
2 2 2
T
P
T
T
P
T
T
T
P
T V
E
V T
E

+

+

− ·
∂ ∂

·
∂ ∂

V
V
T
E
C

,
`

.
|

·
2
2
T
P
T
V
C
T
V

·

,
`

.
|

....
V
V V
) T ( P
V
V V
) T ( P ) T ( P P
2
o
o
2
o
o
1
o
+
]
]
]

+
]
]
]

+ ·
....
) ( ) ( ) (
2
2
2
0
2
2
2
2
2
0
2
2
+
]
]
]

+
]
]
]

+

·

o
o
o
o
V
V V
T
T P
V
V V
T
T P
T
T P
T
P

·

V
V
C
C
V
o
V
o
V
V
T
P
T C
2
2

,
`

.
|
+
]
]
]

+
]
]
]

+

·

V
V
o
o
o
o C
C
V
o
V
o
V
dV
V
V V
T
T P
V
V V
T
T P
T
T P
T C ...
) ( ) ( ) (
2
2
2
0
2
2
2
2
2
0
11
C
V
vs P(cont)
• But so that
which becomes:
• 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:
• First term first reaction: C
P
dT
• First term second reaction: C
V
dT
• We also note the following Maxwell reactions:
• Substitute into above equations and subtract from each
other to get:
o o
o
V
dV
V
V V
d − ·

,
`

.
| −

,
`

.
| −

,
`

.
|
+
]
]
]

+
]
]
]

+

− ·

V
V
o
o
o
o
o
o
o
C
C
V
o
V
o
V
V
V V
d
V
V V
T
T P
V
V V
T
T P
T
T P
T V C ...
) ( ) ( ) (
2
2
2
2
2
2
1
2
2
0

,
`

.
|
+
]
]
]

+
]
]
]

+
]
]
]

− · ...
) (
3
1 ) (
2
1 ) (
3
2
2
2
2
2
2
1
2
2
0
o
o
o
o
o
o
o
o
V V
V
V V
T
T P
V
V V
T
T P
V
V V
T
T P
T V C C
dP
P
S
T dT
T
S
T TdS dV
V
S
T dT
T
S
T TdS
T P T V

,
`

.
|

+

,
`

.
|

· ∧

,
`

.
|

+

,
`

.
|

·
P T V T
T
V
P
S
T
P
V
S

,
`

.
|

− ·

,
`

.
|

,
`

.
|

·

,
`

.
|

( ) dP
T
V
T dV
T
P
T dT C C
P V
V P

,
`

.
|

,
`

.
|

· −
12
C
V
vs P(cont2)
• At either constant volume or temperature we get:
• We now find the two partials using the equations of
state:
• Assume: V = V
o
and third term is zero since it is at
constant volume:
• Taking the derivative at constant pressure of the other
equation of state to obtain the other partial:
• Substitute into equation at top of page to get:
which allows us to determine one heat capacity for the
other, if molar volume and α is known.
( )
P V
V P
T
V
T
P
T C C

,
`

.
|

,
`

.
|

· −
....
1
1
+

,
`

.
|

]
]
]

,
`

.
|

+

,
`

.
|

·

,
`

.
|

T
o o
o
V
V
o
V
V
V
d P
V
V V
T
P
T
P
T
P
( )
1
1
/
a T
a a
T
P
o
V
α
·

,
`

.
|

,
`

.
|

( )
0
0
2
2 1
2
2 1
) ( ) ( ) ( ) (
) ( ) ( ) ( 1
V
T
T a
P
T
T a
P
T
T a
T
T a
T
P T a P T a T a
V
T
V
P
o
P
o
P
o
o
P
α ·

,
`

.
|

·

,
`

.
|

+

·

,
`

.
|

+ − + ∂
·

,
`

.
|

·
χ
α
α
2
1
2
o
o
o o
TV
a
TV
C C
V P
·
· −
13
S, E, G vs P
• Pressure’s effect on these variables determined as we
did with heat capacity.
• For Entropy recall that:
• Substitute for C
V
from earlier relationships:
• Energy is determined from the relationship we
developed earlier:
• We use the equation of state to determine an
expression for this:

·
T V
dT
T
C
S
0

,
`

.
|
+
]
]
]

+
]
]
]

+
]
]
]

− ·

,
`

.
|
+
]
]
]

+
]
]
]

+
]
]
]

·
·

·
...
) (
3
1
) (
2
1
) (
ln
...
) (
3
1 ) (
2
1 ) (
3
2
2
1 0
0
3
2
2
2
2
2
2
1
2
2
0
0
0
o
o
o
o
o
o
o
o
V
T
o
o
o
o
o
o
o
T
o
V
T V
V
V V
T
T P
V
V V
T
T P
V
V V
T
T P
V T C
dT
V
V V
T
T P
V
V V
T
T P
V
V V
T
T P
V dT
T
C
dT
T
C
S
V T
T
P
T P
V
E

,
`

.
|

+ − ·

,
`

.
|

....
2
2
2
1
1
+
]
]
]

]
]
]

,
`

.
|

+
]
]
]

]
]
]

,
`

.
|

+
]
]
]

,
`

.
|

· −

,
`

.
|

o
o
V o
o
V
o
V
o
V
V
V V
P
T
P
T
V
V V
P
T
P
T P
T
P
T
P
T
P
T
14
S, E, G vs P(cont)
• Now we rearrange and integrate:
• Free Energy, G = f(P,V, T): dG = −SdT + VdP.
• Replace each term
• Equations of state used with standard thermodynamic
relationships to determine values of thermodynamic
quantities from a set of data.
:
2
2
2
1
1
2
2
2
1
1
3
1
2
1
...
]
]
]

]
]
]

,
`

.
|

+
]
]
]

]
]
]

,
`

.
|

+
]
]
]

]
]
]

,
`

.
|

− ·

,
`

.
| −
¹
¹
¹
'
¹
¹
¹
¹
'
¹
+
]
]
]

]
]
]

,
`

.
|

+
]
]
]

]
]
]

,
`

.
|

+
]
]
]

,
`

.
|

· − ·

o
o
V o
o
V o
o
o
V
o
o oo
o
o
o
o
V o
o
V
o
V
o
o
o
E
E
V
V V
P
T
P
T
V
V V
P
T
P
T
V
V V
P
T
P
T V E E
V
V V
d
V
V V
P
T
P
T
V
V V
P
T
P
T P
T
P
T V
E E dE
o
( ) [ ]
( )
]
]
]

+ + + +
∫ ∫
− ·

+ + + +
∫ ∫
+ − ·

2
2 1
0 0
0
2
2 1
0 0
3
1
2
1
1 ln
1 ln
P a P a a PV dT T d C E G
dP P a P a a V dT T d C S dG
o o
T T
o
v oo
P
o o
T T
o
v o
G
G
oo

T. 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. dF ≡ − PdV + TdS − TdS − SdT = − PdV − SdT Total Differential of F: dF =  ∂F  dV +  ∂F  dT      ∂V T  ∂T  2  V  ∂ F  ∂F   = − ∂P  Comparing leads to:   = −P ∧     ∂V∂T  ∂V T   ∂T V 2  And also: But:  ∂ 2F   ∂ 2F   =   ∂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  ∂ F   ∂F   = − ∂S    = −S ∧     ∂T∂V   ∂T V  ∂V T   . V.Relationship between E and Volume in terms of P. Helmholz free energy: F ≡ E − TS Differentiate: dF ≡ dE − TdS − SdT Substitute from first law.

Differentiating: dH = dE + PdV + VdP. dH = PdV + VdP .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      ∂V Or:    ∂T   P     Substitute for enthalpy equation:  ∂P  = V − T ∂T   T  P  ∂P∂T   ∂T  P    ∂S  = −   ∂P T  ∂T∂P     ∂P T ∂H ∂V 3 . pressure and volume: H ≡E + PV.Pressure Dependence of Enthalpy • • • • • • • • Enthalpy is defined in terms of energy. G(T. From the first law: dE = − PdV + TdS.PdV + TdS Substituting: = 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.

Two polynomial equations of state used here. 1  ∂V  V  ∂T 1   ∂ao   =    P [1 + a o (T )]  ∂T  P • When ao << 1. the equations reduces to: 1  ∂V   ∂ao    =   =α ∂T  P V  ∂T  P  where α = volume expansivity. related to temperature variation of ao. Substitute for Vo: Vo = V/[1+ao(T)]. – 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. relative change in volume with temperature. we have: V = Vo[1 + ao(T)]. – Vo = volume at absolute zero. V. T.Equations of State:Temperature Dependence • • • Recall 3 variables to be used are P. 4 . Knowledge of two of the variables allows determination of the energy state of the system. 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.

 Vo   Vo  2 § § § Pi = material dependent coefficients. so that χ=− 1  ∂V  a1 ≈ a1   = V  ∂P T 1 + a o • § § since a1<<a0<<1 χ = isothermal compressibility. V: V − V V − V  P = Po (T) + P1(T ) o + P2 (T ) o   + .. P0<< P1 or P2 5 .. But V = Vo[1+ ao].Equations of State: Pressure Dependence • Found by taking derivative of equation of state with respect to pressure: 1  ∂V  V  ∂V    = − Voa1 ∨ −   = o a1 V  ∂P T V  ∂P  T where higher pressure terms are ignored (only first order considered significant). Po = pressure required to decrease the volume of the solid at higher temperature to what it would be at 0 K and no pressure.. determined experimentally. Pressure as a function of T.

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 2 • We use this in the earlier equation: • V − V V − V  P = Po (T) + P1(T ) o + P2 (T ) o   + ..) + ..)2 + .. • • Expand the second term Neglect squared and higher terms in terms of ao and Po...... 1 2 − P a2 + 2 P2 ao a2 + P2 a1 = 0 1 6 . 1 P a1 − 2P2 ao a1 = 1..  Vo   Vo  P = Po (T ) + P1 (T )(− ao (T ) + a1P − a2 P2 + . + ) 2 2 2 2 P (− 2ao a1P + ao a2 P + a1 P + ....... P = Po + P − ao + a1P − a2 P 2 + ..) + To get P2 (T )(− ao (T ) + a1P − a2 P2 + .. 1 2 ( • This can only be true when the following happens: Po − P ao = 0.

Slopes at high pressures are similar for all. Figure shows that compressibility increases with atomic number.) • Solve for ai from Po − P ao = 0. P 1 a1 = 1 1  2P P  = 1 + o 2 . 7 . 1 P a1 − 2P2 ao a1 = 1.Relationship between Pi and ai (cont. Coefficients of expansion nearly constant at absolute zero (see figure). P − 2 P2 ao P  1 1 P2  1  P  6P P  a 2 = 2 1 + o 2  P3  P2  1  1  • • • • Pi can also be expressed in terms of ai. but increase at higher temperatures . 1 2 − P a2 + 2 P2 ao a2 + P2 a1 = 0 1 • Gives: P ao = o .

Recall: V = Vo[1 + ao(T) – a1(T)P + a2(T)P2 + …] Substitute:  ∂ 2 1 + a o (T ) + a1 (T ) P + a2 (T ) P 2  ∂C P    = −TVo    ∂P T ∂T 2   ∂ 2V   ∂C P    = −T  2   ∂T   ∂P T   P [ ]  P 8  ∂ 2 ao (T ) ∂ 2 a1 (T ) ∂ 2 a2 (T ) 2   ∂C P  + P+ P    = −TVo  2 2  ∂T 2   ∂P T ∂T ∂T   P .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 ∂  ∂H   ∂  ∂H    ∂C P  = =          ∂P T ∂P  ∂T  P T ∂T  ∂P T  P  ∂H   ∂V    = V − T   ∂P T  ∂T  P • • But earlier we showed: Substitute:  ∂  ∂H   ∂   ∂C P   ∂V V −T  =    =    ∂P T ∂P  ∂T  P T ∂T   ∂T  ∂V =  ∂T   ∂T   ∂V  −    P  ∂T  P  ∂T     P  P  ∂ 2V    −T 2   ∂T  P  P • • • We can now use the equation of state to determine an equation for calculating heat capacity under various conditions.

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 . 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). 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 a1(T ) 2 1 ∂ 2a2 (T ) 3  o o CP = C P − TV  P+ P + P  2 2  ∂T 2  2 ∂T 3 ∂T   • • • • • CoP = heat capacity at zero pressure.CP Vs P(cont) • Integration gives the pressure dependence of CP.

..dV CV ∂T 2 ∂T 2  Vo  ∂T 2  Vo  Substitute into above equation. and 2 CV ∂C = T V ∂ P ∂V integrate: ∫ o V ∫V 2   10 ... rearrange..  Vo   Vo  2 • Take second derivative: ∂2P 2 ∂P0 (T ) 2 2 ∂P2 (T ) Vo − V  ∂P0 (T ) Vo − V  = + +  + ..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  CV =    ∂T V • • • But: 2 Substitute:  ∂CV  = T ∂ P   2  ∂V T ∂T Earlier we used the equation of state: V − V  V − V P = Po (T ) + P1( T ) o + P2 ( T ) o   + ... 2 2 2  V 2  V ∂T ∂T ∂T  o  ∂T  o  2 • o CV ∂T  ∂P 2 (T ) ∂P 2 (T ) V − V  ∂P 2 (T ) V − V  2   CV ∂C = T V  0 2 o 0 o + ∫ o V ∫Vo   +   + .

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

 +   =  1 V   ∂T V  ∂T V  ∂T V  Vo   o T   • Assume: V = Vo and third term is zero since it is at constant volume:  ∂P   ∂ (a / a )  α   ≈  ∂T V  ∂T o 1 =  a1 • Taking the derivative at constant pressure of the other equation of state to obtain the other partial:  ∂ 1 + a (T ) − a (T ) P + a (T ) P 2  ∂V  o 1 2   = Vo   ∂T  ∂T  P  ( )  P • Substitute into equation at top of page to get: TVoα 2 C −C = P V a1 o o ∂a (T ) 2   ∂a (T ) ∂a1(T )  ∂a (T )  = o − P+ 2 P  = o  ∂T ∂T  ∂T  P  ∂T P =0 = αV0 TVoα 2 = χ which allows us to determine one heat capacity for the other.. 12 . if molar volume and α is known..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:  ∂P1  Vo − V  V   ∂P   ∂Po    − P d   + ..

For Entropy recall that: S = ∫T CV dT 0 T Substitute for CV from earlier relationships: TC S = ∫0 V dT = T 2 o 2 2 2 T T CV dT − V  ∂P0 (T )  Vo − V  + 1 ∂P (T )  Vo − V  + 1 ∂P2 (T ) Vo − V 1 = ∫0 o ∫     2  V T 3 ∂ T 2  Vo  o  2 ∂T 2  Vo  0  ∂T 3     + . G vs P • • • Pressure’s effect on these variables determined as we did with heat capacity........   ∂T  Vo  2 ∂T  Vo  3 ∂T  o        • 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   ∂Po     ∂P   V − V    ∂P2   V − V  T + T   − Po  + T  1  − P   o  − P2   o  1   + .  ∂T V  ∂T V  Vo    ∂T V  Vo       2 13 . dT    ∂ P (T ) V − V  1 ∂P (T ) V − V  2 1 ∂ P (T ) V − V 3  o  0  o o o 1 2 = CV ln T − Vo + +  V  + .S. E.

S. • 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 ) [ ] 1 1   T T G = Eoo − ∫0 (∫0 Cv o d ln T ) + PVo 1 + ao + a1P + a2 P 2  dT 2 3   ( • Equations of state used with standard thermodynamic relationships to determine values of thermodynamic quantities from a set of data.. T): dG = −SdT + VdP.d  o    1       ∂T V   Vo    ∂T V   Vo     ∂T V   Vo     ∂P   V − V  1   ∂P   Vo − V  1   ∂P2    Vo − V  1 E = Eoo − Vo T  o  − Po   o 1  + 2 T  ∂T  − P   V  + 3 T  ∂T  − P2   V  V V    o     o    ∂T V   Vo  • Free Energy. G vs P(cont) • Now we rearrange and integrate:     2 E ∫ Eo dE = E − Eo = 2   ∂P   V −V    ∂P   Vo − V    ∂P2   Vo − V    o  1 − Vo ∫  T  − Po  + T  − P  + T  − P2   + .V. : 14 . E. G = f(P..