Thermodynamics EPS

Basics
Zeroth law: If two objects are in thermal equilibrium with a third, then they must be in ther-
mal equilibrium with each other.

First law: The change in the internal energy of a system equals the heat supplied to the
system plus the work done on the system.

dU = d̄Q + d̄W.

Second law: Heat flows from hot to cold, or entropy can never decrease in an isolated system,
or heat cannot be completely converted to work.

Third law: It is impossible to reach absolute zero.

Open system: Can exchange energy and matter with its surroundings.

Closed system: Can exchange energy but not matter with its surroundings.

Isolated system: Cannot exchange energy or matter with its surroundings.

State variable: Describes the equilibrium state of a system regardless of the way that the
system acquired that state.

Process variable: A variable that is path dependent through any process.

Temperature: Intensive property and state variable. Heat always flows from higher tempera-
ture to lower temperature.

Heat: The energy transferred due to thermal contact. Process variable.

Internal energy: The total energy contained in a system. Extensive property and state variable.

Quasistatic process: A process through which the system always remains in equilibrium.

Reversible process: The system can be restored to its original state without change to its
surroundings. Quasistatic without friction.

Irreversible process: Not reversible.

Entropy: Extensive state variable defined by the equation:

Z f
d̄QR
d̄QR = T dS =⇒ ∆S = .
i T

where the heat is supplied through a reversible process.

Processes
Isobaric: Constant pressure.

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Isothermal: Constant temperature.

Adiabatic: No heat exchange. For an ideal gas,

nD + 2 CP
T V γ−1 = constant, P V γ = constant, γ= = ,
nD CV
where nD is the number of degrees of freedom.

Isochoric: Constant volume.

Heat capacity: Extensive property defined by

d̄Q
C≡ .
dT
Constant volume heat capacity: Heat capacity at constant volume,
 
∂U
CV = .
∂T V

Constant pressure heat capacity: Heat capacity at constant pressure,

        
∂U ∂V ∂V ∂U
CP = +P = CV + +P .
∂T P ∂T P ∂T P ∂V T

Cycles
Work done: The work done by the system is

W = Qin − Qout .

Efficiency (heat engine): Is the work done per heat added

W Qout
η≡ =1−
Qin Qin

Coefficient of performance (fridge): Is the heat removed from the cold reservoir per work
supplied
QC QC
ωF ≡ = .
W QH − QC
Coefficient of performance (heat pump): Is the heat added to the hot reservoir per work
done,
QH QH
ωP ≡ = .
W QH − QC

Second Law
Kelvin statement: No process is possible in which the sole effect is the absorption of heat from
a reservoir and its complete conversion into work. So the efficiency must always be less than one.

Clausius statement: No process is possible in which the sole effect is the transfer of heat
from a colder reservoir to a hotter reservoir.

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Clausius inequality: For any process from state A to B,
I Z B
d̄Q d̄Q
≤ 0 =⇒ S(B) − S(A) ≥ .
T A T
For both, the equality only holds for reversible processes.

Carnot’s theorem: Of all cycles operating between two reservoirs, a reversible cycle is the
most efficient. All reversible cycles therefore have the same efficiency, given by
TC
η =1− .
TH

Thermodynamic Potentials
Internal energy: Total energy in the system U = U (S, V ). Useful for isentropic (adiabatic)
and isochoric processes.
dU = T dS − P dV.
Helmholtz function: F = F (T, V ), useful for isothermal and isochoric processes.

F = U − T S =⇒ dF = −SdT − P dV.

The amount of work that can be extracted from a system with an isothermal process is less than
or equal to the change in the Helmholtz function (hint: use Clausius inequality):

∆W ≤ −∆F.

Gibbs function: G = G(T, P ) is useful for isothermal and isobaric processes.

G = U − T S + P V =⇒ dG = −SdT + V dP.

In an isothermal and isobaric process, the Gibbs function is minimized (hint: use Clausius
inequality):
∆G ≤ 0.
Enthalpy: H = H(S, P ), useful for isentropic (adiabatic) and isobaric processes.

H = U + P V =⇒ dH = T dS + V dP.

The constant pressure heat capacity is

   
∂H ∂S
CP = =T
∂T P ∂T P

Maxwell relations: These all follow from the potentials, easy to derive - no need to memorize.
               
∂T ∂P ∂T ∂V ∂S ∂P ∂S ∂V
=− , = , = , =− .
∂V S ∂S V ∂P S ∂S P ∂V T ∂T V ∂P T ∂T P

Adiabatic Expansions
Reversible expansion: The process is isentropic, dS = 0. We are interested in ( ∂T /∂V )S .
The gas always cools.    
∂T T ∂P
=− .
∂V S CV ∂T V

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Free expansion (Joule): Internal energy is constant, dU = 0. The gas usually cools. The
Joule coefficient η = dT /dV is
       
∂T 1 ∂U 1 ∂P
η= =− =− T −P .
∂V U CV ∂V T CV ∂T V

Throttling (Joule-Kelvin): The process is isenthalpic. We are interested in the Joule-

Thompson coefficient µ = dT /dP . The gas may cool or heat.
   
∂T V 1 ∂V
µ= = [βT − 1], β = .
∂P H CP V ∂T P

where β is the thermal expansivity.

Inversion temperature: The temperature above which the gas always cools under throttling.

Chemical Potential
Chemical potential: Is the change in the internal energy per particle added under constant
entropy and volume. Intensive state variable.
 
∂U
µ= , =⇒ dU = T dS − P dV + µdN.
∂N S,V

Other definitions: Equivalently,

 
∂S
µ = −T .
∂N U,V

In terms of the Helmholtz and Gibbs potentials,

   
∂F ∂G
µ= = .
∂N T,V ∂N T,P

The chemical potential can be thought of as the Gibbs free energy per particle. (Very subtle
point, see Tong’s statistical physics.)

Phase Transitions
Phase of matter: Is any distinct volume where the chemical and physical properties of the
material within are uniform.

State of matter: The usual definition - more general than phase.

Phase transitions: They are isothermal processes. Entropy always changes.

Latent heat of fusion: Heat required to fully transition from a solid to a liquid phase. Ex-
tensive variable.

Specific latent heat of fusion: Is the latent heat of fusion per unit mass (or amount).
Intensive variable.
∆Qmelting
LF = .
m

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Specific entropy of fusion: Entropy released per unit mass during melting:
LF
sF = .
T
Latent heat of condensation: Heat required to fully transition from a gas to a liquid phase.
Extensive variable. Can define specific latent heat of condensation and vaporisation similarly.

Phase diagrams: See below.

First order phase changes: Specific volume and entropy of the two phases are different.
The specific Gibbs functions are the same.

Clausius-Clapeyron equation: Describes the slope of a PT diagram along a phase boundary.

dP ∆s L
= = ,
dT ∆v T ∆v
where L is the specific latent heat, s is specific entropy and v is specific volume.

How to derive: Write ds with s = s(T, v). Note that during phase changes, dT = dP = 0.

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Third Law
Basic macroscopic statement: It is impossible to reach absolute zero in a finite number of
steps.

Basic microscopic statement: The entropy of a perfect crystal at absolute zero is zero.

Planck statement: The entropy tends to zero as the temperature tends to zero.

Nernst statement: The entropy change in a process between two equilibrium states associated
with a change in external parameters tends to zero as the temperature approaches absolute zero.

Heat capacities: Tend to zero as temperature approaches absolute zero.

Thermal expansivity: Tends to zero.

   
∂S ∂V
0= =− .
∂P T ∂T P

Maths: Exact Differentials

RB
Let dz be an exactRdifferential, meaning A dz is path independent. Hence, there exists a func-
tion z = z(x, y) = dz. Then, the following hold.

Reciprocal rule:
  "  #−1
∂z ∂x
= .
∂x y ∂z y

Cyclic rule:      
∂x ∂y ∂z
= −1.
∂y z ∂z x ∂x y

Exact differential: If z = z(x, y), then

   
∂z ∂z
dz = dx + dy.
∂x y ∂y x