8: Thermodynamics - Physics LibreTexts

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Mathematical introduction
If there exists a relation f(x,y,z)=0 between 3 variables, one can
write: x=x(y,z), y=y(x,z) and z=z(x,y). The total differential dz of z is
than given by:

dz=(∂z∂x)ydx+(∂z∂y)xdy(8.1)

By writing this also for dx and dy it can be shown that

(∂x∂y)z⋅(∂y∂z)x⋅(∂z∂x)y=−1(8.2)

Because dz is a total differential ∮dz=0.

A homogeneous function of degree m obeys: εmF(x,y,z)=F(εx,εy,εz). For

such a function Euler’s theorem applies:

mF(x,y,z)=x∂F∂x+y∂F∂y+z∂F∂z(8.3)

Definitions
 The isochoric pressure coefficient: βV=1p(∂p∂T)V
 The isothermal compressibility: κT=−1V(∂V∂p)T
 The isobaric volume coefficient: γp=1V(∂V∂T)p
 The adiabatic compressibility: κS=−1V(∂V∂p)S
A process without transfer of heat to or from a system, so that Q = 0, is called
adiabatic, and such a system is said to be adiabatically isolated.[5][6] The
simplifying assumption frequently made is that a process is adiabatic. For
example, the compression of a gas within a cylinder of an engine is assumed to
occur so rapidly that on the time scale of the compression process, little of the
system's energy can be transferred out as heat to the surroundings. Even though
the cylinders are not insulated and are quite conductive, that process is idealized
to be adiabatic. The same can be said to be true for the expansion process of
such a system.

For an ideal gas it follows that: γp=1/T, κT=1/p and βV=−1/V.

Thermal heat capacity
 The specific heat at constant X is: CX=T(∂S∂T)X
 The specific heat at constant pressure: Cp=(∂H∂T)p
 The specific heat at constant volume: CV=(∂U∂T)V

For an ideal gas : Cmp−CmV=R. Further, if the temperature is high enough

to thermalize all internal rotational and vibrational degrees of
freedom: CV=12sR. Hence Cp=12(s+2)R. From their ratio it now follows
that γ=(2+s)/s. For a lower T one needs only to consider the thermalized
degrees of freedom. For a Van der Waals gas: CmV=12sR+ap/RT2.

In general:

Cp−CV=T(∂p∂T)V⋅(∂V∂T)p=−T(∂V∂T)2p(∂p∂V)T≥0(8.4)

Because (∂p/∂V)T is always <0, the following is always valid: Cp≥CV. If the
coefficient of expansion is 0, Cp=CV, and this is true also at T=0K.

The laws of thermodynamics

The zeroth law states that heat flows from higher to lower temperatures. The
first law is the conservation of energy. For a closed system: Q=ΔU+W,
where Q is the total added heat, W the work done and ΔU the difference in
the internal energy. Notice that the work is taken as the work done by the
system on the surroundings. In differential form this
becomes: dQ=dU+dW, where d means that the it is not a differential of a
state function. For a quasi-static process: dW=pdV. So for a reversible
process: dQ=dU+pdV.

For an open (flowing) system the first law is: Q=ΔH+Wi+ΔEkin+ΔEpot. One
can extract an amount of work Wt from the system or add Wt=−Wi to the
system. In chemistry, one uses the opposite convention, that positive work is
work done on the system.

The second law states: for a closed system there exists an additive
quantity S, called the entropy, the differential of which has the following
property:

dS≥dQT(8.5)
If the only processes occurring are reversible: dS=dQrev/T. So, the entropy
difference after a reversible process is:

S2−S1=∫12dQrevT(8.6)

For a reversible cycle: ∮dQrevT=0.

For an irreversible cycle: ∮dQirrT<0.

The third law of thermodynamics is (Nernst's law):

limT→0(∂S∂X)T=0(8.7)

From this it can be concluded that the thermal heat capacity →0 if T→0, so
absolute zero temperature cannot be reached by cooling through a finite
number of steps.

State functions and Maxwell relations

The state functions and their differentials are:

dU=TdS−pd
Internal energy: U
V
H=U+p dH=TdS+Vd
Enthalpy:
V p
F=U−T dF=−SdT−p
Free energy:
S dV
Gibbs free G=H−T dG=−SdT+V
energy: S dp

From this one can derive Maxwell’s relations:

(∂T∂V)S=−(∂p∂S)V , (∂T∂p)S=(∂V∂S)p , (∂p∂T)V=(∂S∂V)T ,

(∂V∂T)p=−(∂S∂p)T(8.8)

From the total differential and the definitions of CV and Cp it can be derived
that:

TdS=CVdT+T(∂p∂T)VdV and TdS=CpdT−T(∂V∂T)pdp(8.9)

For an ideal gas:

 Sm=CVln(TT0)+Rln(VV0)+Sm0 and Sm=Cpln(TT0)−Rln(pp0)+S
′m0(8.10)

Helmholtz’ equations are:

(∂U∂V)T=T(∂p∂T)V−p , (∂H∂p)T=V−T(∂V∂T)p(8.11)

For a macroscopic surface: dWrev=−γdA, with γ the surface tension. From

this follows:

γ=(∂U∂A)S=(∂F∂A)T(8.12)

Processes
The efficiency η of a process is given by: η=Work doneHeat added

The cold factor ξ of a cooling down process is given by: ξ=Cold

deliveredWork added

Reversible adiabatic processes

For adiabatic processes: W=U1−U2. For reversible adiabatic processes

using Poisson’s equation with γ=Cp/CV one gets that pVγ=constant.
Also: TVγ−1=constant. Also Tγp1−γ=constant. Adiabats are steeper on a p-
V diagram than isotherms because γ>1.

Isobaric processes

Here: H2−H1=∫21CpdT. For a reversible isobaric process: H2−H1=Qrev.

Throttle processes

This is also called the Joule-Kelvin effect and is the result of an adiabatic
expansion of a gas through a porous material or a small opening. Here H is a
conserved quantity, and dS>0. In general this is accompanied with a
change in temperature. The quantity which is important here is the throttle
coefficient:

αH=(∂T∂p)H=1Cp[T(∂V∂T)p−V](8.13)

The inversion temperature is the temperature where an adiabatically

expanding gas maintains the same temperature. If T>Ti the gas heats up,
if T<Ti the gas cools down. Ti=2TB, with for TB: [∂(pV)/∂p]T=0. The
throttle process is, for example, used in refrigerators.

The Carnot Cycle

The system undergoes a reversible cycle consisting of two isotherms and two
adiabats

1. Isothermal expansion at T1. The system absorbs an amount of

heat Q1 from the reservoir.
2. Adiabatic expansion with a temperature drop to T2
3. Isothermal compression at T2 removing an amount of heat Q2 from the
system.
4. Adiabatic compression with the temperature increasing to T1

The efficiency for a Carnot cycle is:

η=1−|Q2||Q1|=1−T2T1:=ηC(8.14)

The Carnot efficiency ηC is the maximal efficiency at which a heat engine

can operate. If the process is applied in reverse order and the system
performs a work −W the cold factor is given by:

ξ=|Q2|W=|Q2||Q1|−|Q2|=T2T1−T2(8.15)

The Stirling cycle

The Stirling cycle consists of 2 isotherms and 2 isochoric processes. The

efficiency in the ideal case is the same as for a Carnot cycle.

Maximum work
Consider a system that changes from state 1 into state 2, with the
temperature and pressure of the surroundings given by T0 and p0. The
maximum work which can be obtained from this change is, when all
processes are reversible:

1. Closed system: Wmax=(U1−U2)−T0(S1−S2)+p0(V1−V2).

2. Open system: Wmax=(H1−H2)−T0(S1−S2)−ΔEkin−ΔEpot.

The minimum work needed to attain a certain state is: Wmin=−Wmax.

Phase transitions
Phase transitions are isothermal and isobaric, so dG=0. When the phases
are indicated by α, β and γ: Gαm=Gβm and

ΔSm=Sαm−Sβm=rβαT0(8.16)

where rβα is the heat of transition from β to phase α and T0 is the transition
temperature. The following holds: rβα=rαβ and rβα=rγα−rγβ. Further

Sm=(∂Gm∂T)p(8.17)

so G has a kink in the transition point and the derivative is discontinuous. In

a two phase system Clapeyron’s equation is valid:

dpdT=Sαm−SβmVαm−Vβm=rβα(Vαm−Vβm)T(8.18)

For an ideal gas one finds for the vapor line at some distance from the
critical point:

p=p0e−rβα/RT(8.19)

There also exist also phase transitions with rβα=0. For those there will only
be a discontinuity in the second derivatives of Gm. These second-order
transitions appear as organization phenomena.

A phase-change of the 3rd order, with e.g. [∂3Gm/∂T3]p non continuous

arises e.g. when ferromagnetic iron changes to the paramagnetic state.

Thermodynamic potential
When the number of particles within a system changes this number becomes
a third state function. Because addition of matter usually takes place at
constant p and T, G is the relevant quantity. If a system has many
components this becomes:

dG=−SdT+Vdp+∑iμidni(8.20)
where μ=(∂G∂ni)p,T,nj

is called the thermodynamic potential. This is a partial quantity. For V:

V=∑i=1cni(∂V∂ni)nj,p,T:=∑i=1cniVi(8.21)
where Vi is the partial volume of component i. The following holds:

Vm0==∑ixiVi∑ixidVi

where xi=ni/n is the molar fraction of component i. The molar volume of a

mixture of two components can be a concave line in a V-x2 diagram: the
mixing leads to a contraction of the volume

The thermodynamic potentials are not independent in a multiple-phase

system. It can be derived that ∑inidμi=−SdT+Vdp, this gives at
constant p and T: ∑ixidμi=0 (Gibbs-Duhmen).

Each component has as many μ’s as there are phases. The number of free
parameters in a system with c components and p different phases is given
by f=c+2−p which is called the Gibbs phase rule.

Ideal mixtures
For a mixture of n components (the index 0 is the value for the pure
component):

Umixture=∑iniU0i , Hmixture=∑iniH0i , Smixture=n∑ixiS0i+ΔSmix(8.22)

where for ideal gases: ΔSmix=−nR∑ixiln(xi).

For the thermodynamic potentials: μi=μ0i+RTln(xi)<μ0i. A mixture of two

liquids is rarely ideal: this is usually only the case for chemically related
components or isotopes. In spite of this Raoult’s law holds for the vapour
pressure for many binary mixtures: pi=xip0i=yip. Here xi is the fraction of
the ith component in liquid phase and yi the fraction of the ith component in
gas phase.

boiling point ΔTk and a decrease of the freezing point ΔTs. For x2≪1:
A solution for one component in a second gives rise to an increase in the

ΔTk=RT2krβαx2 , ΔTs=−RT2srγβx2(8.23)

with rβα the heat of evaporation and rγβ<0 the melting heat. For the osmotic
pressure Π of a solution: ΠV0m1=x2RT.

These are called collegative properties

Conditions for equilibrium
When a system evolves towards equilibrium the only changes that are
possible are those for
which: (dS)U,V≥0 or (dU)S,V≤0 or (dH)S,p≤0 or (dF)T,V≤0 or (dG)T,p≤0.
In equilibrium for each component: μαi=μβi=μγi.

Statistical basis for thermodynamics

The number of possibilities P to distribute N particles on n possible energy
levels, each with a g-fold degeneracy is called the thermodynamic
probability and is given by:

P=N!∏igniini!(8.24)

The most probable distribution, that with the maximum value for P, is
the equilibrium state. When Stirling’s equation, ln(n!)≈nln(n)−n is used,
one finds the Maxwell-Boltzmann distribution for a discrete system . The
occupation numbers in equilibrium are then given by:

ni=NZgiexp(−WikT)(8.25)

The state sum Z is a normalization constant, given

by: Z=∑igiexp(−Wi/kT). For an ideal gas:

Z=V(2πmkT)3/2h3(8.26)

The entropy can then be defined as: S=kln(P). For a system in

thermodynamic equilibrium this becomes:

S=UT+kNln(ZN)+kN≈UT+kln(ZNN!)(8.27)

For an ideal gas, with U=32kT then: S=kN+kNln(V(2πmkT)3/2Nh3)

Application to other systems

Thermodynamics can be applied to other systems than gases and liquids. To
do this the term dW=pdV has to be replaced with the correct work term, for
example dWrev=−Fdl for the stretching of a wire, dWrev=−γdA for the
expansion of a soap bubble or dWrev=−BdM for a magnetic system.
A rotating, non-charged black hole has a temperature T=ℏc/8πkm. It has
an entropy S=Akc3/4ℏκ with A the area of its event horizon. For
a Schwarzschild black hole A is given by A=16πm2. Hawkings area theorem
states that dA/dt≥0.

Hence, the lifetime of a black hole ∼m3.