Equilibrium Thermodynamics I:

Introduction [tsc1]

Thermodynamic system and thermodynamic state:

All matter consists of particles. Particles are always in motion of one kind
or another. Thermodynamic systems, which contain a macroscopic number
of particles, are vibrant under all circumstances.
Thermodynamic systems at equilibrium are in thermodynamic states which
are specified by a set of time-independent state variables. The time-dependence
associated with particle motion is averaged out in this description.
Equilibrium thermodynamics identifies functional relations between state
variables. Such relations are named equations of state. They must satisfy
stability criteria associated with thermodynamic equilibrium.
A thermodynamic state is also called macrostate. It represents a macroscopic
number of microstates, each of which describes the state of all particles in
the thermodynamic system.

State variables:
In homogeneous systems, it is useful to distinguish between extensive and
intensive state variables. Extensive variables are proportional to the size of
the system, whereas intensive variables are independent of system size.
The first group of state variables are named thermodynamic functions. They
come in (thermodynamically conjugate) pairs here listed side by side. The
variables on the left (right) are extensive (intensive). The product of each
pair has units of energy.

V : volume p: pressure
S: entropy T: temperature
M : magnetization H: magnetic field
N : number of particles µ: chemical potential
n: number of moles µ̄: chemical potential
X: generic extensive variable Y: generic intensive variable

Ratios of extensive variables, e.g. N/V (particle density), are intensive.

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The second group of state variables are named thermodynamic potentials
or free energies. They are all extensive, but can be rendered intensive by
scaling, e.g. U/N (per particlee) or U/V (per unit volume).

U: internal energy
E: enthalpy
A: Helmholtz free energy
G: Gibbs free energy
Ω: grand potential

The third group of state variables are named response functions. Some defi-
nitions make them extensive, other definitions make them intensive.

CV : isochoric heat capacity cV : isochoric specific heat

Cp : isobaric heat capacity cp : isobaric specific heat
χT : isothermal susceptibility
χS : adiabatic susceptibility
κT : isothermal compressibility
κS : adiabatic compressibility
αp : thermal expansivity

Symbols vary between sources, especially for thermodynamic potentials.

In inhomogeneous systems, most intensive state variables become functions
of position, whereas all extensive variables become integrals over position.

Equations of state:
The empirical specification of a thermodynamic system is traditionally ex-
pressed in the form of two kinds of equations of state.

B Thermodynamic equation of state:

Functional relation between thermodynamic variables.
For example: pV = nRT (classical ideal gas).
B Caloric equation of state:
Temperature dependence of internal energy or heat capacity.
For example: U = CV T with CV = const (classical ideal gas).

The complete thermodynamic information about a system is encoded in this

dual specification. In more complex systems, the thermodynamic equation
of state consists of multiple relations.

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Thermodynamic equation of state for a classical gas:
Classical ideal gas: pV = nRT ,

n = N/NA (number of moles),

NA = 6.022 × 1023 (Avogadro’s number),
R = NA kB = 8.314J mol−1 K−1 (gas constant),
kB = 1.381 × 10−23 J K −1 (Boltzmann constant).

an2
 


Van der Waals gas: p + 2 V − nb = nRT .
V

Ad-hoc generalization of ideal gas. Pressure reduction, −an2 /V 2 , ac-

counts for long-range attractive interaction. Exclusion volume, nb, ac-
counts for short-range repulsive interaction.
 
nRT n  n 2
Virial expansion: p = 1 + B2 (t) + B3 (T ) + . . . .
V V V

Systematic generalization of ideal gas. The virial coefficients Bn (T ),

accessible to specialized methods of analysis, represent particle inter-
action effects, which gain traction as the density n/V increases.

Encoding thermodynamic information:

The most concise way of encoding the complete specification of a thermody-
namic system at equilibrium is in the form of a thermodynamic potential.
All thermodynamic quantities of interest about a given system can directly
be derived from a thermodynamic potential.
Strategies commonly pursued:

B Equilibrium thermodynamics:
Construct a thermodynamic potential from the empirical information
contained in the thermodynamic and caloric equations of state. Then
derive any thermodynamic quantity of interest from the thermody-
namic potential.
B Equilibrium statistical mechanics:
Derive a thermodynamic potential (or partition function) from the mi-
croscopic specification of the system in the form of a many-body Hamil-
tonian. Then derive any thermodynamic quantity of interest from the
thermodynamic potential.

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Thermodynamic contacts:
The primary criterion in a classification of thermodynamic systems is the
combination of thermodynamic contacts between system and environment.

1 Mechanical interaction (with work source).

Exchange of energy via work performance.
2 Thermal interaction (with heat reservoir).
Exchange of energy via heat transfer.
3 Mass interaction (with particle reservoir).
Exchange of energy via matter transfer.

Major types of thermodynamic systems:

isolated system: contact 1,

closed system: contacts 1, 2,
open system: contacts 1, 2, 3.

Additional combinations do exist. Superfluid helium confined by a porous

material permits contacts 1 and 3 and prohibits contact 2.

Zeroth law of thermodynamics:

Mathematically speaking, thermodynamic equilibrium is an equivalence re-
lation: it is postulated to be reflexive, symmetric, and transitive.

– Reflexivity: A ≡ A
A thermodynamic system A is in equilibrium with itself.
– Symmetry: A ≡ B ⇒ B ≡ A
If system A is in equilibrium with system B, then system B is in equi-
librium with system A.
– Transitivity: A ≡ B, B ≡ C ⇒ A ≡ C
If system A is in equilibrium with system B and system B with system
C, then system A is also in equilibrium with system C.

The zeroth law makes it possible to design a device (thermometer) that

measures an attributes (empirical temperature) characteristic of systems in
thermodynamic equilibrium with each other.

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First law of thermodynamics:
Thermodynamic equilibrium states have a definite internal energy U with no
memory about the source (work, heat, radiation, ...) of the energy content.
Internal energy is a state variable, but work and heat are not state variables.
Energy conservation in a thermodynamic process means that the internal
energy may change if energy is imported or exported via work performance,
heat transfer, radiation, or other means energy exchange.

Second law of thermodynamics:

Heat flows spontaneously from high to low temperatures.
This empirical fact limits the use of the energy contained in a thermodynamic
system for work performance. It puts a limit to the efficiency of heat engines.
It makes some thermodynamic processes irreversible.
The second law establishes the entropy S and the absolute temperature T as
state variables.

Third law of thermodynamics:

The entropy difference between any two equilibrium states approaches zero
as their absolute temperature approaches zero.
A consequence of this empirical fact (grounded in quantum mechanics) is
that there exists no thermodynamic process by which T = 0 can be reached
in a finite number of steps.

In a nutshell, the zeroth, first, second, and third laws are encapsulated in an
equivalence, an equality, an inequality, and a limit, respectively.

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Thermodynamic processes:
The study of equilibrium thermodynamics cannot do without processes that
connect equilibrium states. Processes necessarily disturb the equilibrium.
Generic process:

– During a generic process between equilibrium states, some of the ther-

modynamic variables may not be defined.
– Information about changes in all thermodynamic variables during a
generic process can be obtained if we connect the same initial and final
equilibrium states by a quasi-static process.

Quasi-static process:

– A quasi-static process involves infinitesimal steps between equilibrium

states along a definite path in the space of state variables.
– The equations of state remain satisfied as the thermodynamic variables
change during a quasi-static process.

Adiabatic process:

– During an adiabatic process the system is thermally isolated. There is

no heat transfer. Changes are caused by work performance.
– An adiabatic process must not be too fast in order not to produce
entropy within the system.
– In some practical applications, an adiabatic process must not be too
slow in order to prevent significant heat exchange between the system
and the environment.

Reversible and irreversible processes:

– In an isolated system, the entropy (to be defined) stays constant during

a reversible process and increases during an irreversible process.
– Quasi-static processes can be reversible or irreversible.

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Differentials:
The differential,
dF = c1 (x1 , x2 )dx1 + c2 (x1 , x2 )dx2 ,
expresses the infinitesimal change of some quantity along an infinitesimal
step of a path in the plane of the independent variables x1 , x2 .
We assume that c1 and c2 are arbitrary differentiable functions.
In general, the integral of dF between any two points (a1 , a2 ) and (b1 , b2 )
depends on the path. For paths (i) and (ii) we can write,
Z Z b1 Z b2
dF = dx1 c1 (x1 , a2 ) + dx2 c2 (b1 , x2 ).
(i) a1 a2

Z Z b2 Z b1
dF = dx2 c2 (a1 , x2 ) + dx1 c2 (x1 , b2 ).
(ii) a2 a1

Xt
If the functions c1 and c2 satisfy the condition,
∂c1
=
∂c2
,
bz
(i;)
n
∂x2 ∂x1 $-j
Qa

then dF is an exact differential, x

or b,
∂F ∂F
dF = dx1 + dx2 ,
∂x1 ∂x2
of a function F (x1 , x2 ), and its integration between two point is guaranteed
to be path-independent:
Z (b1 ,b2 )
dF = F (b1 , b2 ) − F (a1 , a2 ),
(a1 ,a2 )

The distinction between exact and inexact differentials is important in ther-

modynamics.

– The differentials of state variables are exact. Integrating the differential

of a state variable along a closed path is then zero as it must be.
– Thermodynamics also deals with differentials that are not state variable
such as dQ (heat) and dW (work). In cyclic processes (along closed
paths), the net heat transfer and work performance are nonzero, in
general.

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Exercises:

B Fast heat [tex143]

B Expansion and compression of nitrogen gas [tex144]
B Bathtub icebreaker [tex145]
B Exact and inexact differentials I [tex5]
B Exact and inexact differentials II [tex146]
B Exact and inexact differentials III [tex168]

Additional materials:

B Thermodynamics overview [tln2]

B Equations of state for ideal gas and real fluid [tsl12]
B Physical constants [tsl47]
B Relevant textbooks [tln90]