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Thermodynamics

State variables depend on the state only

Cannot be defined during irreversible processes

Changes can be calculated using ANY path

Partial derivatives: change in X due to change in Y with Z

constant

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 1 / 24

Equivalent processes - to calculate state variables

Calculate the final temperature when cold ice is dropped into hot water.
Proceed by assuming a series of processes in which the energy goes into
some unspecified storage reservoir
The water cools to 0◦ .
The ice warms to 0◦ .
The ice melts.
Finally, the sum of these energies is put back into the system to warm the
water back up from 0◦ to its final temperature, or refreeze some ice.
This is an example of using an equivalent process to make a
thermodynamic problem mathematically tractible.
It is legitimate because temperature and internal energy are state variables.

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 2 / 24

What is Heat

Newton: 1690
The rate of heat loss of a body is proportional to the tem-
perature difference between the body and its surroundings.

Lavoisier: 1790
Heat consists of a self-repellent fluid, caloric, that flows
from hotter bodies to colder bodies.

Joule and Thomson: 1851

Heat is not a substance, but a dynamical form of
mechanical effect

Google: 2018...

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 3 / 24

What is heat? (something to do with reversible processes)

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 4 / 24

What is heat?

Lavoisier’s Elements 1789

Arsenic. Molybdena. Tungstein. Manganese. Nickel. Cobalt. Bismuth.

Antimony. Zinc. Iron. Tin. Lead. Copper. Mercury. Silver. Platina. Gold.
“Metals”

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 5 / 24

Father of Chemistry

Lavoisier’s Elements 1789

“Earths”
Lime, Magnesia, Barytes, Alumine, Silice
“Radicals”
Sulphur, Phosphore, Carbon, fluorique, boracique, muriatique (Chlorine),

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 6 / 24

What is heat?

and Caloric? Lavoisier’s Elements 1789

“Gases”
nitrogen, oxygen hydrogen Heat Light

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 7 / 24

What is heat?

Lavoisier classified heat as an element because.

1 You could mix it with other things, and change them.
2 It wasn’t made of other elements.
3 There’s a finite amount in any fuel.
4 Diffuses and flows to equilibrium concentration
5 but then came the boring problem.
Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 8 / 24
Boring

Yellow pages, (pre-1996).

Elon Musk’s hyperloop, (2017)

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 9 / 24
Boring Cannons

“An inexhaustible source of caloric”

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 10 / 24

Boring
Observation attributed to Sir Benjamin Thompson ( Reichsgraf von
Rumford).
“ ...we must not forget to consider that most remarkable circumstance,
that the source of the Heat generated by Friction, in these Experiments,
appeared evidently to be inexhaustible. It is hardly necessary to add, that
anything which any insulated body, or system of bodies, can continue to
furnish without limitation, cannot possibly be a material substance: and it
appears to me to be extremely difficult, if not quite impossible, to form
any distinct idea of any thing, capable of being excited and
communicated, in the manner the heat was excited and communicated in
these Experiments, except it be MOTION. “

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 11 / 24

Rumford 2 Lavoisier 0

Rumford: Colonel and Loyalist in US Revolution, Bavarian Army Minister,

founded Englischer Garten in Munich and Royal Institution of London
married Marie-Anne Lavoisier.

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 12 / 24

Lavoisier (50) Guillotined for selling dodgy fags.
Lavoisier, scientific genius and member of the Ferme Generale (privatised
Royal tax collectors) accused by rival scientist and revolutionary Marat
{Lavoisier, guillotined at 50 via
{Jean-Paul Marat, murdered at 50 by
{Charlotte Corday, guillotined at 25 by
{ by Charles Sanson, executioner dynasty for 150 years
}}}

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 13 / 24

INTERNAL ENERGY - ANOTHER STATE FUNCTION

Joule used falling weights to turn paddles to heat water.

The same work (mgh) always produce the same rise

in temperature.

The mechanical equivalent of heat: 4.2 × 103 J kg−1 K−1 .

The same value as using electric heating with a mechanical dynamo.
Joule had proved that heat could be produced by work alone.

If a thermally ISOLATED system is brought from one equilibrium state to

another, the work necessary is independent of the process used.

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 14 / 24

Internal Energy

If a THERMALLY ISOLATED system is brought from one equilibrium state

to another, the work necessary is independent of the process used.

Joule’s observation “independent of the process used” requires

there is a state function U, which we call the internal energy.

∆U = U2 − U1 = Wadiabatic

1 Work done adiabatically equals the change in U.

2 Does not define absolute value (U=0)
3 This is a restricted form of the First Law of Thermodynamics.
4 It applied to the thermally isolated system, not the whole Universe.

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 15 / 24

First Law of Thermodynamics

Conservation of Energy

Clausius: In all cases in which work is produced by the agency of heat, a

quantity of heat is consumed which is proportional to the work done; and
conversely, by the expenditure of an equal quantity of work an equal quantity
of heat is produced.
Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 16 / 24
Heat, Work and Internal Energy

What about the thermally isolated constraint?

If system is not thermally isolated, W 6= U2 − U1

Can include heat U2 − U1 = W + Q,
where Q is the energy transfer which cannot be accounted for as work,
Define Q as positive for heat going INTO the system:

Heat is the exchange of energy between the system and the surroundings
that cannot be identified as work (eg mechanical work).

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 17 / 24

Illustration of the difference between W and Q

Same experiment, different definition of the system.

system


9
e e e e e e e  I e e e e e e e  I

gas gas

 e e e e e e e  e e e e e e eKAA
i
PPP 
1
P  A
system
heating coil

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 18 / 24

First Law of Thermodynamics

This leads to the general statement of the First Law of Thermodynamics,

for infinitesimal changes:

dU = d¯W + d¯Q,

where both d¯W and d¯Q are path-dependent. For work done mechanically
on a compressible fluid, First Law for infinitesimal reversible processes is:

dU = −PdV + d¯Q
Work: electrical, magnetic, gravitational etc.
Internal energy: kinetic and potential energy.
Potential energy includes chemical, nuclear, mass, gravitational.
The first law has time-reversal symmetry.

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 19 / 24

THE HEAT CAPACITY (C) OF A SYSTEM

“Heat needed to raise the temperature by 1 degree”

 
Q dQ
C = lim =
∆T →0 ∆T dT
Specific heat capacity is c = C /m, where m is the mass.
Molar heat capacity is c = C /n, where n is the number of moles.
(confusingly denoted by the same symbol)
Also, specify what is held constant. Using dQ = dU + PdV
     
∂ QV ∂U ∂U
CV = = =
∂T V ∂T V ∂T V
   
d QP dU + PdV ∂H
CP = = =
dT dT P ∂T P
Introducing enthalpy, H = U + PV a state function useful when the
pressure is known.
Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 20 / 24
Derive difference between heat capacities Cp − CV


    
∂H ∂U ∂V
CP = = +P (1)
∂T P ∂T P ∂T P
   
∂U ∂U
dU = dT + dV
∂T V ∂V T
           
∂U ∂U ∂U ∂V ∂U ∂V
⇒ = + = Cv +
∂T P ∂T V ∂V T ∂T P ∂V T ∂T P
Substituting this in the equation for Cp ,
    
∂U ∂V
CP − CV = P + ,
∂V T ∂T P
∂U
= 0 and so (CP − CV ) = P ∂V



For Ideal gas ∂V T ∂T P = nR.

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 21 / 24

Slow Ideal Gas Processes - Isothermal

Reversible Isothermal Expansion of an Ideal gas ∆T = 0

For isotherms, it is convenient to write the equation of state P(V,T):
Isotherms are hyperbolae
P = nRT /V ∝ 1/V
T is constant, P depends only on V .
Reversible means work done on system is equal
and opposite to work done on surroundings

Z Z
V2
PdVT = nRT dV /V = nRT ln( )
V1
.

Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 22 / 24

Fast Ideal Gas Process - Adiabats
Reversible Adiabatic Expansion (No heat transfer: ∆U =work )
First Law: d¯Q = dU + PdV = Cv dT + PdV .
R R
Adiabatic (d¯Q = 0), so PdV = − Cv dT = −Cv ∆T
Substitute for P = nRT /V , replace nR by Cp − Cv and put
d¯Q = 0 (adiabatic).
Cv dT nRdV
− =
T V
−cv ln(T ) = (cp − cv )ln(V ) + ln(A)
T −cv = AV cp −cv
A−1/cv = TV (cp −cv )/cv Define: γ = CP /CV = cP /cv

TV γ−1 = a constant, A
γ
Equivalently: PV = a different constant
(γ−1)/γ
And also: TP = yet another constant
Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 23 / 24
Irreversible Free Expansion and Joule Coefficient
Rigid adiabatic contained, partitioned into equal volumes: gas & vacuum

System: All gas inside the container. partition

Irreversible Process: Partition breaks.

On system: V 

V
no work, no heat, so Ui = Uf gas vacuum
So we can write T = T (U, V ),
break

∂T
 
∂T
 partition
dT = dV + dU ? ?
∂V U ∂U V

∂T
 2V
= dV gas everywhere
∂V U
= µJ dV ;
This defines the “Joule coefficient” µJ
(For Ideal gas, U = U(T ) so Tf = Ti , so µJ = 0)
Graeme Ackland Lecture 3: FIRST LAW OF THERMODYNAMICS September 21, 2018 24 / 24