Equilibrium Thermodynamics

Thermodynamics describes Equilibrium systems.

Large numbers of atoms where each part has the same properties.
No net internal flows of heat or material
TWO variables describe state of a fluid (e.g. P and T)
Division between system and surroundings (reservoir)
Processes can be reversible or irreversible

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First Law

Status - always true, by definition

Key point - Energy is conserved

Equation
dU = dW + dQ,
where both dW and dQ are
path-dependent.

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State variables

Quantities that belong to the system alone, T, P, V

Not necessarily measurable, or well-defined zero U, S, G, F
Not those due to interplay with surroundings (Q, W)
Only well defined at equilibrium

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Equation of state

P(V,T)
TWO variables describe state of a fluid (e.g. P and T)
All properties can be deduced from EoS via derivatives etc.
e.g.


P+

PV = nRT

a
(V nb) = nRT
(V /n)2

Big table of measured numbers

for real material.
Discontinuity at phase transition

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The efficiency of a heat engine

Heat engines.
Two reservoirs, out of equilibrium. + system
Heat flows from hot to cold.
Work done.

Heat Engine
hot body
T1
Q1

W-

= W /Q1 = 1 Q2 /Q1
Leads to Kelvin statement of 2nd law
(also Heat pumps and refrigerators)

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Q2

T2
cold body

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Carnot cycle

Most efficient engine

Reversible
Adds heat at highest T
Remove heat at lowest T
adiabats+isotherms
=1

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T2
Q2
=1
Q1
T1

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Clausius inequality form system round a cycle

I

dq
0,
T

Clausius inequality

Zero for reversible processes.

Must exist a state variable: Entropy
dqR
T
Increasing entropy
for
irreversible
processes
H
For system: system dSsystem = 0
H
For surroundings: system dSsurrounds > 0
dS =

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Equivalent statements of Second Law

Status : Statistical. Relies on Avogadro Number  1.

1

Heat cannot flow from a cooler to a hotter reservoir.

Heat cannot be 100% converted to Work

Reversible cycles are the most efficient engines possible

Entropy cannot decrease

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Entropy is

The quantity which defines the arrow of time.

Z
dS =

dQ
T

S = k ln W the number of microstates in a macrostate

P
S = i pi ln pi the statistical uncertainty

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Foundation of mathematics in thermodynamics

The Equation of state is a (fairly) well-behaved function.

Differential: If I change X, how does Y change
Does not fully specify the process
Partial Differential + while holding Z constant
Strictly, cannot integrate along an irreversible path.
BUT, can use equivalent reversible path for changes in state variables
Generally deal with changes in state variables, not absolute values

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Central Equation

Combine the first and second laws.

dU = dQ + dW

dU = TdS - PdV

This equation involves only state variables.

Can be integrated independent of the path
Integration can be applied to irreversible processes.

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Potentials
U(V,S), H(P,S), F(V,T), G(P,T)
Contain new information beyond P, T and EoS
Useful for analytic work with natural coordinates
Actual value (Energy = 0) poorly defined
First differentials are state variables, e.g.

dG = SdT + VdP = S =

dG
dT


;V =
P

dG
dP


T

Second derivatives are material properties, e.g. compressibility





1 dV
1 d 2G
=
s =
V dP s
V dP 2 s

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Maxwell Relations

Second derivative of potentials

V
T
=
P S
S P ,




T
P
V S = S V ,




P
S
T V = V T ,




V
S
T P = P T ,

similarly for other thermodynamic coordinates, e.g. magnetic, electric.

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Electromagnetic Thermodynamics
Can use thermodynamics to deduce...

Planck distribution
Stefans Law
Magnetic cooling (types of entropy)

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Phases

coexisting phases have equal

Gibbs free energy
dG = VdP SdT
constant pressure boundary coexistence line
constant volume boundary coexistence region

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Clausius Clapeyron and Ehrenfest

Slope of a phase boundary on a phase diagram.


dP
L
l
=
=
dT pt
T (v2 v1 )
T (V2 V1 )
Special case - vapourisation: V2 >> V1 , ideal gas
ln P =

l
+ constant
RT

Ehrenfest : Second order Clausius Clapeyron



cP,1 cP,2
CP,1 CP,2
dP
=
=
dT pt
Tv (1 2 )
TV (1 2 )
dP
2 1
=
dT
2 1
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Third Law

Status: empirical,
requires quantum
mechanics, broken
symmetry.
dS(T = 0) = 0
S(T = 0) = 0

At T=0, there is only one arrangement of atoms.

Quantum ground state
Superfluid He - all atoms in single, entangled quantum state.
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The Chemical Potential is ...

The extra energy from adding a particle dU = TdS PdV + dN

The specific Gibbs = g for a pure substance.
The quantity which drives particle flow.
The quantity which defines chemical equilibrium

All of the above!

Exists (and equilibrates) for each species P
independently i .
Total Gibbs Free Energy minimised G = i Ni i .

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Fourth Law

Status: Non-existent
Describes how systems get to equilibrium.
Self organisation of steady states

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Summary

Einstein:
Thermodynamics is the only physical theory of universal content which I
am convinced, within the areas of applicability of its basic concepts, will
never be overthrown.

Planck:
I had no alternative but to tackle the problem again ... from the side of
thermodynamics... the fundamental connection lies in the dependence of
entropy with the energy

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