“Please make Cthulhu Owl the course mascot”

R’lyeh is a city characterized by architecture of non-Euclidean geometry.

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 1 / 19
 ...Thermodynamics

Analytic Relations in Thermodynamics.

Maxwell and Cyclic Relations.
Equation of state, can relate thermodynamic measurables.
Heat capacity, thermal expansion, compressibility/bulk modulus.
Specify what is held constant: Cp and Cv ; Ks and KT
Force may not be the derivative of energy.
Availability: work from equilibration.

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 2 / 19
Fukushima Disaster I

Gibbs Free Energy

G=U - TS + PV

Favours high entropy at high

temperature

2H2 O → 2H2 + O2

Entropy is counting things...

The earthquake and tsunami killed
2>3 over 15,000 people.
There were no casualties caused by
Hydrogen explosion. radiation exposure.

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 3 / 19
 Free Expansion and Joule Coefficient

Reanalyse Irreversible Free Expansion (see lecture 4)

Surroundings “rigid adiabatic” partition
means dS0 = 0; dV0 = 0.

 V
Choose thermodynamic potential U:
gas vacuum

dU = dQ + dW = 0 + 0 = 0 break
partition
? ?
System: How does change in V
affect T? 2V
gas everywhere
∂T


Want ∂V U

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 4 / 19
The Joule coefficient for a free expansion
∂T ∂T
dV + ∂T




Want ∂V U
, so use dT = ∂V U ∂U V dU
Consider an equivalent reversible process e.g. choosing U =constant; dU = 0
Z Vf   Z Vf
∂T
∆T = dV = µJ dV
Vi ∂V U Vi

Eliminate “unmeasureable” U, S
Use cyclical rule, central equation, & Maxwell relation
       
∂T ∂T ∂U 1 ∂U
µJ = =− =− ×
∂V U ∂U V ∂V T CV ∂V T
   
∂U ∂S
=T −P
∂V T ∂V T
   
1 ∂P
µJ = P −T
CV ∂T V
Thus µJ can be calculated fom the Equation of State.

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 5 / 19
 1 ∂P



Examples: µJ = CV P −T ∂T V
Ideal gas : µJ = 0 (as before)

The van der Waals equation: for one mole (P + va2 )(v − b) = RT ,
can be written as a virial expansion: Equation of state in powers of density.

   2 !
 a  1 1
Pv = RT 1+ b− + b2 + ...
RT v v
= RT 1 + B2 /v + B3 /v 2 + ...

B2 , B3 ... are temperature dependent (B1 = 1 gives ideal gas limit).

To estimate ∆T , need (µJ ) for that gas and the increase ∆v in volume.
Estimate µJ using the first virial coefficient:
1 RT 2 dB2
µJ = − × 2 ×
cv v dT
For argon, dB2 /dT = 0.25 cm3 mol−1 K−1 . Doubling its volume gives
∆T ≈ - 0.6 K.
Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 6 / 19
Fukushima disaster II

”The name of our corporate

character, because of the way it’s
written, has been regarded as
inappropriate, or has been
misunderstood among
English-speaking people”
Fridge manufacturer Fukushima
Industries

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 7 / 19
The Joule-Kelvin coefficient for a throttling process
Real refrigeration requires cycling of the working fluid, i.e. flow.
Joule-Kelvin Expansion is a forced expansion (throttling process) e.g.
gas forced adiabatically through porous plug: work done, no heat transfer.

porous plug

gas 

gas
- -
Pi , Ti Pf , Tf

Pi + dP gas Pf − dP Pi gas Pf
sample sample
- Pi , Vi , Ti - Pf , Vf , Tf

before after
Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 8 / 19
Joule-Kelvin Expansion and Coefficient

For a Joule-Kelvin expansion the surroundings,

have no entropy change ∆S = 0
exert constant external pressure. ∆P = 0 (both sides)
Relevant thermodynamic potential for the system is enthalpy.
consider a reversible isenthalpic process.
Rest of cycle: Pressure difference is maintained by pump (work), hot
reservoir is a heat exchanger to the atmosphere.

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 9 / 19
Joule-Kelvin Expansion and Coefficient

The most appropriate indicator diagram shows TP.

The states visited (Pi , Ti ), (Pf 1 , Tf 1 ), (Pf 2 , Tf 2 ),

etc. forms an isenthalp.

Isenthalps typically have a maximum temperature.

The curve through the maxima of the isenthalps is

called the inversion curve.

Cooling: (∂T /∂P)H > 0

Warming: (∂T /∂P)H < 0.

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 10 / 19
Analytics

Change P, conserve H, so consider T = T (P, H)

      Z Pf
∂T ∂T ∂T
dT = dP + dH = dP = µJK dP
∂P H ∂H P ∂P H Pi

Relate µJK = (∂T /∂P)H to measurable material properties. Eliminate

“unmeasurable” H, S using triple product and Maxwell.
       
∂T ∂T ∂H 1 ∂H
µJK = =− =− ×
∂P H ∂H P ∂P T CP ∂P T

Using dH = TdS + VdP ⇒ ∂H ∂S

∂P T = T ∂P T + V we get...
   
1 ∂V
µJK = T −V
CP ∂T P

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 11 / 19
using a Maxwell relation in the final step to eliminate the unmeasurable S,
leaving a differential of the equation of state.
Approximately, ∆T = µJK ∆P,
T ∂V



1 ideal gas:
∂T P = V , so µJK = 0 .
2 For a real gas ∆T may be negative or positive depending on
conditions.
3 Inversion temperature is obtained from the condition µJK = 0
4 Maximum inversion temperature by then setting P = 0.

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 12 / 19
Table of values of maximum inversion temperature, Tinmax ,
for various gases

max inversion temp

gas (Tinmax )
argon 723 K = 450◦ C
nitrogen 621 K = 348◦ C
hydrogen 205 K = -68◦ C
helium 51 K = -222◦ C

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 13 / 19
Thomas Midgley

Most unlucky scientist ever

Dichlorodiuoromethane (Freon-12)
and other CFCs discovered and
promoted by Thomas Midgley (1889
- 1944).
CFCs destroyed the ozone layer and
are about 10,000 times better
greenhouse gas than CO2 .
Invented tetraethyllead additive to
petrol “antiknocking” as well.
Crippled by polio, died in 1944
strangled by a device he invented to
turn him over in bed.

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 14 / 19
Vapour compression cycle

A massive ∂V


∂T P occurs on boiling.
Exploit this to get an efficient fridge.
Dichlorodifluoromethane (Freon-12) ideal working fluid
Boiling point (1atm) : −29.8o C

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 15 / 19
Vapour compression cycle

A massive ∂V


∂T P occurs on boiling.
Exploit this to get an efficient fridge.
Dichlorodifluoromethane (Freon-12) ideal working fluid
Boiling point (1atm) : −29.8o C
Banned in 1996
(ozone layer, supergreenhouse gas)

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 16 / 19
Liquifying gases: Air and helium

Joule-Kelvin expansion used

because fewer moving parts
Pre-cooling is needed to give
Ti < the maximum inversion
temperature (e.g. 51K in He)
Pre-cooling by controlled
adiabatic expansions above
vapour-to-liquid phase
transition.
High pressure, gas throttled -
some liquefies
the rest helps pre-cool incoming
gas, via a heat exchanger.

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 17 / 19
Additional thermodynamic coordinates for other systems

So far we assumed material properties are restricted to P, V, T and S. But

there are other possibilities which can be treated similarly. The table
shows different co-ordinates, distinguishing between intensive variables
(like pressure P) and extensive variables (like volume V ).
system intensive extensive infinitesimal
variable variable work ON system

gas or fluid P V −PdV

wire or rod F (tension) L (length) FdL
(electric) cell E (“emf”) Z (charge) E dZ
magnetic material B0 (induction) M (mag.moment) B0 dM
dielectric material E (electric field) P (polarisation) EdP

Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 18 / 19
The rubber band or “wire”
Extend first law to include work done ON the band, FdL
Ignore −PdV  FdL:

dU =d¯Q − PdV + FdL → dU =d¯Q + FdL

re-use results replacing V with L and P with −F.
           
∂S ∂P ∂S ∂(−F) ∂S ∂F
= → = → =−
∂V T ∂T V ∂L T ∂T L ∂L T ∂T L
For an isothermal stretch, the chain-like molecules become less tangled, (
more ordered - lower entropy)
Using the Maxwell relation and product rule
     
∂S ∂F ∂L
<0→ <0
∂L T ∂L T ∂T F
∂F


∂L T is positive, so rubber is expected to have a negative coefficient of
linear expansion L1 ∂T
∂L


F
.
Similarly, a rubber band stretched at constant force will cool.
Graeme Ackland Lecture 1: Systems and state variables October 21, 2016 19 / 19