Lecture 10

...
Thermodynamics
Only two independent variables = Maxwell and other Relations
Equation of state as a 2D surface in a non-Euclidean space
Second Law in terms of properties of the system: Potentials U,H,F,G
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 1 / 20
Two questions
dV

Evaluate dP s ?
(dV/dP)s = ???
Compressibility of a particular
substance?
Half a Maxwell relation?
Adiabatic change in volume as
pressure increases?
Something to do with Power and
Voltage?
Dependent and Independent Variables
In thermodynamic derivations, it is
not obvious what to choose as the
dependent variable.
This is the physics of the question.
The rest is just maths.
Ewe chews
Example: The difference in heat capacities, CP CV
What is the general relation between CP and CV ?

CP CV = nR is valid only for an Ideal gas
Constant volume = no work. dU = TdS PdV = TdS

U S
CV = dQV /dT = =T
T V T V
This suggests working with the entropy : S = S(T , V )

S S
dS = dT + dV
T V V T
To relate to Cp = (H/T )p = T (S/T )p , differentiate the equation

wrt T at constant P.

S S T S V
CP = T =T +T
T P T V T V V T T P
Identify terms which are materials properties

S S V
CP = T +T
T V V T T P
Introducing heat capacity

S
CV = T
T V
and isobaric thermal expansivity:

V 1
=
T P V

S
CP CV = TV
V T
Eliminate the unmeasurable

S
CP CV = TV
V T
Recall S is not readily measurable, so use Maxwell to eliminate S.

S P P V
= =
V T T V V T T P
and introduce the isothermal bulk modulus and thermal expansivity (again)

P 1 V 1
= V = KV = K
V T V T P V
P
and = V1 V

K = V V T T P
CP CV = TV 2 K = TV 2 /
where = 1/K is the isothermal compressibility.

Deconstruct CP CV = TV 2 K = TV 2 /
CP CV V = extensive quantity.
K is positive for all known substances.
2 is positive.
CP > CV , even for negative thermal
expansion.
CV = CP at the density maximum in water.
is small except for gases. CP CV : for
solids and liquids often lazily just give
heat capacity
Difference is NOT due to work done
expanding the material.
Variations in CV and CP

CV
What is V ?
T

CV S S
= T =T
V T V T V T T V T V
2P

P
= T =T
T T V V T 2 V
using a Maxwell relation. An analogous analysis for CP yields

2
CP V
= T
P T T 2 P
We can calculate
these directly from equation of state.
CP
e.g. P is Zero for Ideal Gas V=RT/P.
T
formally, infinite for a phase transition (volume changes at constant T,P.).
Aside: Latent heats and the Lambda Function
HeatRcapacity of liquid He becomes infinite at a phase transition.

T +t
L = T t cv dT
The energy equation. Why demonstrations dont work.
Relate the volume and pressure derivatives of the internal energy to

material properties and gradients of equation of state.
Differentiate dU = TdS PdV , wrt dV and eliminate S using a Maxwell
relation:

U S P T
=T P =T P = P
V T V T T V
U

Is force the derivative of energy? Compare F = U, P = V S
Increasing energy under pressure
Similarly, differentiate dU = TdS PdV , wrt dP and eliminate S using a

Maxwell relation:

U V V
= T P = TV + PV T
P T T P P T
The ratio of heat capacities CP /CV
It can be shown using Maxwell relations that

CP T
=
CV S
where T and S are, respectively, the isothermal and adiabatic
compressibilities:

1 V 1 V
T = and S =
V P T V P S
This provides another useful link between thermal and mechanical

properties of materials.
The entropy of an ideal gas, again
For entropy per mole s = s(T , V ), we can always write

s s dT
ds = dT + dV = cV + KdV
T V v T T
This equation applies to any fluid. is thermal expansivity, K bulk

modulus.
For an Ideal gas K = R/v and cv is a constant. Integration then gives
s = cv ln T + R ln v + s0
Similarly s = cP ln T R ln P + s0 .
Again, we relate changes in entropy to measurable quantities via the
equation of state.
Availability
1904 Prince Piero Ginori Conti. generating electric energy from geothermal steam
How much work can be extracted from a system?

Depends on surroundings, but how?
Availability - non Infinite reservoirs
Second-law for system with surrounding reservoir at T0 , P0
S + Ssurr 0
Q
S 0
T0
Q is heat transferred from the reservoir into the system.
First law for system gives Q = U + P0 V :
U + P0 V T0 S 0
Define a new function called the Availability, A,
A = U T0 S + P0 V
Availability A = U T0 S + P0 V
Availability is not Gibbs free energy.

Depends on both the system and surroundings. A(S, V , P0 , T0 ),
Spontaneous changes in availability are always negative
A = U T0 S + P0 V 0
At equilibrium, nothing more can change: Availability is minimised
dA = dU T0 dS + P0 dV = 0
Availability incorporates all potentials
At equilibrium (T = T0 , P = P0 ), dA = 0
If T = T0 & P = P0 A = U TS + PV G is minimum
If T = T0 & V = const A = U TS + const F is minimum
If S is const. & V = const A = U + const U is minimum
If S is const. & P = P0 A = U const + PV H is minimum
If U is const. & V = const A = const T0 S S is maximum
Minimising Availability maximises entropy of the Universe.

Availability is minimised when system is in equilibrium with
surroundings.
Availability tells us how far from equilibrium we are
Useful Work
We assumed the only work done by the system was in expanding against
the environment P0 V , but heat transfer could produce other useful work.
In that case the First Law becomes
U = Q W = Q W useful P0 V (1)
where Q is the heat transported from the surroundings to the system,
U + P0 V T0 S + W useful = W useful A 0
Maximum useful work is Wmax = A. (iff all changes are reversible).

This is also clearly seen if we look at a small differential change of A:
dWuseful dA = dU + T0 dS P0 dV
= (T0 T )dS + (P P0 )dV
Available for work
dWuseful (T0 T )dS + (P P0 )dV

Useful work could come from
moving entropy (heat) from hot body (T ) to cold body (T0 ).
pushing a piston against a pressure (P0 )
Once the availability is used up - no more work.
n.b. the system T changes as it equilibrates
Idealised engines had two infinite T-reservoirs, hot and cold.
Real engines need continual supply of energy to maintain the temperatures.

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...

Only two independent variables = Maxwell and other Relations

Equation of state as a 2D surface in a non-Euclidean space

Second Law in terms of properties of the system: Potentials U,H,F,G

What is the general relation between CP and CV ?

To relate to Cp = (H/T )p = T (S/T )p , differentiate the equation

and isobaric thermal expansivity:

where = 1/K is the isothermal compressibility.

using a Maxwell relation. An analogous analysis for CP yields

HeatRcapacity of liquid He becomes infinite at a phase transition.

Relate the volume and pressure derivatives of the internal energy to

Similarly, differentiate dU = TdS PdV , wrt dP and eliminate S using a

It can be shown using Maxwell relations that

This provides another useful link between thermal and mechanical

For entropy per mole s = s(T , V ), we can always write

This equation applies to any fluid. is thermal expansivity, K bulk

For an Ideal gas K = R/v and cv is a constant. Integration then gives

How much work can be extracted from a system?

Second-law for system with surrounding reservoir at T0 , P0

Define a new function called the Availability, A,

Availability is not Gibbs free energy.

Minimising Availability maximises entropy of the Universe.

where Q is the heat transported from the surroundings to the system,

Maximum useful work is Wmax = A. (iff all changes are reversible).

dWuseful (T0 T )dS + (P P0 )dV

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