Lecture 2

• Basic Concepts of thermodynamics

• Thermodynamic potentials

• Maxwell’s relations
Big Picture
Both thermodynamics and statistical physics deal with systems having large number of particles
(atoms, molecules, etc.) at equilibrium or equivalently called Macroscopic systems .

Microscopic picture: Motion of individual particles

Macroscopic picture: Interested in variables like pressure

Can describe systems at thermodynamic equilibrium

The microstate of a macroscopic system at thermodynamic equilibrium is permanently
changing. However, these changes are irrelevant, whereas the important macroscopic state of
the system does not change. Typically, pressure and temperature become the same across the
system and remain constant as a function of time.

Both thermodynamics and statistical physics lead to a number of results at equilibrium that
do not depend on the exact nature of the system and thus are universal.
Thermodynamics is pheonmenological in nature:
o Works exclusively with macroscopic quantities only and does not go down to the micro-
level of description.
o Formulates a number of principles taken from observations based on which one can arrive
at many other important conclusions.
Entire subject of Thermodynamics is based on 4 laws that you are familiar with:
Zeroth law: Two bodies, each in thermal equilibrium with a third body, are in equilibrium with
each other. The zeroth law implies the existence of a universal property of systems in thermal
equilibrium and allows us to identify this property as the temperature of a system without a
direct comparison to some standard.
First law: There is a system property called energy that is conserved, but can take several
different forms that interconvert.
Second law: Heat flows spontaneously from high temperature to low temperature. There is a
system property called entropy, that is the system is isolated from its environment, either
increases or stays constant during thermodynamic processes.
Third law: The entropy of a system is a universal constant (set to zero) at the absolute zero of
temperature.
Statistical physics, to the contrary, uses the microscopic quantities to calculate
macroscopic quantities that thermodynamics has to take from the experiment.
The microscopic approach of the statistical physics is still much less detailed than
the full dynamical description based on Newton's equations. Instead of finding
trajectories of the particles, statistical physics operates with the probability for
the system to be in a certain microscopic state.
 Basic notions
State variables: State of thermodynamic equilibrium can be specified completely
in terms of a few parameters called state variables. When the thermodynamic
state of a system changes, the amount by which state variables change is
independent of the path taken (equivalent to saying this change is an exact
differential).

Examples:
Pressure, Volume: variables describing mechanical state of a system
Temperature, Entropy: variables describing heat content of a system
Number of particles, chemical potential: variables describing chemical nature of
a system
Response functions like heat capacity, compressibility, magnetic susceptibility
Thermodynamic potentials (to be talked about later in this lecture)
Basic notions
• System and environment:
oMacroscopic systems
oEnvironment (or surrounding , or bath, or heat reservoir ) is a special type of a
system that has a very large size. The system under consideration can change
its state as a result of its contact to the bath but the state of the bath does not
change due to the interaction with a much smaller system.
Human Body: Heat reservoir/bath
Thermometer: System
• Open: can exchange mass and energy with the environment.
• Close: cannot exchange the mass but it can receive or lose energy in the form of
heat due to the thermal contact with the bath or through the work done on the
system.
• Isolated: An isolated system cannot exchange neither mass nor energy, there is
no contact between the system and the environment.
Extensive, intensive, and specific quantities:
o Intensive quantities (pressure P, temperature T ) do not depend on the
size (mass) of the system
o Extensive quantities (mass M, volume V, energy E or U) scale with the
system size.
o Specific quantities are obtained from an extensive quantity by division by
#
another extensive quantity. 𝜌 =
$
• Quasi-static, reversible and irreversible processes
o Thermodynamic processes must be quasi-static or quasi-equilibrium. This
means that the external parameters that control the system change with time so
slowly that the system at any moment of time is very close to the equilibrium,
corresponding to the instantaneous values of the control parameters. The
process can be depicted as a continuous line in P,V space.
o Reversible processes are quasi-static processes that can go in both directions
along the same line in the space of thermodynamic quantities. Most quasi-
static processes are reversible. A process is reversible if it is possible to
restore the system and its surroundings to their original condition. (The
surroundings include any body that was affected by the change.) That is, if the
change is reversible, the status quo can be restored everywhere.

o All non-quasi-static processes are irreversible or spontaneous.

• Temperature
• For most of substances isotherms corresponding to different temperatures do
not cross.

• Define the empirical temperature T as a parameter labeling isotherms:

𝜙 𝑃, 𝑉 = 𝑇
Basis of thermometers using substances such as alcohol, mercury, ideal gas, etc.
• Existence of the temperature as the new (non-mechanical) quantity that
equilibrates in the case of systems in thermal contact, is called the zeroth law of
thermodynamics .
• Equation of state
𝑓 𝑃, 𝑉, 𝑇 = 0
• Valid for simplest thermodynamic systems such as gas or liquid that are
characterized by pressure and volume. There are many other systems
described by other macroscopic quantities. For example, equation of state for
magnetic systems has the form f (B,M, T ) = 0:
• Ideal gas equation of state
𝑃𝑉 = 𝑁𝑘. 𝑇
Thermodynamic coefficients: As thermodynamic quantities are related by the
equation of state, changing some quantities causes changing the others.

𝑉 = 𝑉 𝑃, 𝑇

𝜕𝑉 𝜕𝑉
𝑑𝑉 = 𝑑𝑃 + 𝑑𝑇
𝜕𝑃 1 𝜕𝑇 3

6 7$ 6 7$
Isothermal compressibility, 𝜅 1 = − Adiabatic compressibility, 𝜅: = −
$ 73 1 $ 73 :

Mechanical stability constrains 𝜅 1 > 0

6 7$ 6 7$
Isobaric expansivity, 𝛽3 = Adiabatic expansivity, 𝛽: =
$ 71 3 $ 71 :
• Work and internal energy: The system and environment can exchange energy with
each other. One of the ways to exchange energy is doing work that can be described in
mechanical terms.
d𝑊 = 𝑃𝑑𝑉
• Work done is not a state variable. State variable is any thermodynamic quantity that
has a well-defined value in any particular state of the system. In particular, for cyclic
process es the system returns to the same state at the end of the cycle, so that all
state variables assume their initial values. However, nonzero work can be done in
cyclic processes (the area circumscribed by the cycle in the P; V diagram), so that one
cannot ascribe an “amount of work" to any particular state of the system.

Internal energy is a state variable and equal to the total energy of the system minus
any bulk translational or rotational kinetic energy. One can express it as a function of
two basic quantities, 𝑈 = 𝑈 𝑇, 𝑉 which is also called Caloric equation of
state. Within the thermodynamics, the only way to obtain this is to take it from the
experiment, as described above. Statistical physics provides the caloric equation of
state in the analytical form in many cases.
• Heat and first law of thermodynamics
Energy conservation 𝛿𝑄 = 𝑑𝑈 + 𝛿𝑊

AB
Heat Capacity, 𝐶 = C1
AB
Isochoric heat capacity, 𝐶$ =
C1 $
AB
Isobaric heat capacity, 𝐶3 = C1 3
Can prove from general thermodynamic considerations that 𝐶3 > 𝐶$ always

(You can justify this also intuitively: A system typically expands on increasing temperature
and therefore does work on the surroundings. When a system is heated at constant
pressure, energy is needed to both increase the temperature of the system and do work.
In contrast, if volume is kept constant then no work is done on the surrounding and all of
the heat goes into increasing the temperature of the system )
• Heat Engines: Major application of thermodynamics in the 19th century
General design: Two reservoirs with different temperatures and a system that
exchanges heat with the two reservoirs and does work in a cyclic process.

Second law of thermodynamics implies that

for any cyclic quasi static process,
𝛿𝑄
D =0
𝑇
Integrand must be a differential of state variable.
Define state variable entropy, S, which
AB
satisfies 𝑑𝑆 = where 𝛿𝑄 is
1
reversible heat change
• For an arbitrary cyclic process which contains an irreversible part, one has
AB AB
∮ < 0 . That is, for such processes is not an exact differential.
1 1

For an irreversible path between two TD states, the heat absorbed by the system
will be less than the heat absorbed along a reversible path between the same 2
AB AB
TD states. ∫IJJKL 1 < ∫JKL 1

AB
For an irreversible process does not contain all contributions to the
∫IJJKL 1
entropy change. Some of it comes from the uncertainity created by spontaneity.
AB
𝑑𝑆 = + dM S where 𝑑I 𝑆 denotes the entropy production due to spontaneous
1
processes. For a reversible process, dM S =0. For spontaneous (irreversible process),
dM S > 0.
• For an isolated system, 𝛿𝑄 = 0 and
𝑑𝑆 = 𝑑𝑆I ≥ 0 where equality sign is for reversible processes and inequality is
for irreversible processes.

Equilibrium state is a state which is stable against spontaneous changes,

for an isolated system, the above equation tell us that, the equilibrium
state is a state of maximum entropy. This fact provides an important
criterion for determining the stability of an equilibrium state for an isolated
system.
• Heat capacities are related to entropy
7: QR 7: QS
• = and =
71 $ 1 71 3 1
• Combining entropy with first law, 𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉
• 𝑈 = 𝑈(𝑆, 𝑉)
Maxwell’s relations:
7V 7V
oWe know 𝑇 = 7: $
and P = − 7$ :
7XV 7XV
oWe know, = implies
7: 7$ 7$ 7:
71 73
o =− which is one of the Maxwell’s relation
7$ : 7: $

Maxwell’s relation connect hard to measure quantities to quantities that can be

measured with direct/simple experiments. For example, here how entropy
changes with change in pressure is related to adiabatic volume expansivity.
 Thermodynamics potentials
• Any two of P,V and T are good enough to specify the state of a system.
Equivalently, you could also use internal energy U and entropy S to specify the
state of the system.

You can create many other state functions by simply adding to U various
combinations of P, V, T and S in such a way that resulting quantity has dimensions
of energy. Out of many possibilities, three are of special relevance.
Enthlapy, H=U+PV
Helmholtz free energy, F=U-TS
Gibbs free energy, G=U-TS+PV

PV and TS are pairs which are products of an intensive and extensive

variable with units of energy
Legendre Transformation
• All 3 TD potentials can be obtained my performing Legendre transformation of
U with respect to two out of T, S, P, and V

What is Legendre transform? Say you have a function f(x). Legendre transform
gives you an alternative way to represent the same function.
Specify the function by giving the
value of local tangent at each
point as well as the intercept
𝐿 𝑠 =𝐹 𝑥 𝑠 − 𝑠 𝑥 𝑥(𝑠)

𝐿 𝑠] , 𝑠^ = 𝐹 𝑥, 𝑦 − 𝑠] 𝑥 − 𝑠^ 𝑦
Enthalpy
• Express U= U(S,V)
• Keeping entropy fixed (equivalent to taking a partial Legendre transform),
7V
𝐻=𝑈− V = U + PV using 𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉
7$ :
𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
= 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
= 𝑇𝑑𝑆 + 𝑉𝑑𝑃
For isobaric (constant Pressure) process, 𝑑𝐻 = 𝑇𝑑𝑆
For reversible isobaric (constant Pressure) process, 𝑑𝐻 = 𝑑𝑄JKL = 𝐶3 𝑑𝑇
Enthalpy change is heat absorbed or lost by a system during a reversible
isobaric process. The enthalpy of a substance increases when its temperature
is raised.
• If a phase transformation (i.e. melting or transformation to another solid
polymorph) takes place within the system, heat may be adsorbed or released
without a change in temperature. At constant pressure the heat merely
transforms a portion of the substance (e.g. from solid to liquid – ice–water).
• Enthalpy change accompanies physical transformations and chemical
reactions
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃

𝜕𝐻 𝜕𝐻
𝑇= 𝑉=
𝜕𝑆 3 𝜕𝑃 :

71 7$ Second Maxwell’s
=
73 : 7: 3 relation
 Helmholtz free energy
• Legendre transform of U keeping V fixed
𝜕𝑈 𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉
𝐹 =𝑈− 𝑆
𝜕𝑆 $

= 𝑈 − 𝑇𝑆

𝑑𝐹 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇

= −𝑃𝑑𝑉 − 𝑆𝑑𝑇
Change in Helmholtz free energy for an isothermal process is equal to the reversible work
done on/by the system

𝜕𝐹 𝜕𝐹 73
=
7: Third
𝑃=− 𝑆=− 71 $ 7$ 1 Maxwell’s relation
𝜕𝑉 1 𝜕𝑇 $
 Gibbs Free Energy
• Legendre transform of U with respect to S and V
𝜕𝑈 𝜕𝑈 𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉
𝐺 =𝑈− 𝑆− 𝑉
𝜕𝑆 $ 𝜕𝑉 :
= 𝑈 − 𝑇𝑆 + 𝑃𝑉

𝑑𝐺 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃

= −𝑆𝑑𝑇 + 𝑉𝑑𝑃
Gibbs free energy remains constant during isothermal and isobaric processes.

𝜕𝐺 𝜕𝐺 𝜕𝑉 𝜕𝑆 Fourth
𝑉= 𝑆=− =−
𝜕𝑃 1 𝜕𝑇 3 𝜕𝑇 𝜕𝑃 Maxwell’s relation
3 1
 Consider an example of a two-phase
equilibrium: Liquid in equilibrium with vapor
phase at constant temperature and under
constant pressure
Gibbs free energy 𝐺 = 𝑛6 𝑔6 + 𝑛f 𝑔f
for the system

𝑔I is Gibbs free energy/mole of phase 𝑖 and

𝑛I is number of moles of phase 𝑖
Atoms would traverse interface between liquid and vapor phases in such a
way that net rate of transfer is zero at equilibrium
𝑑𝑛 = 𝑑𝑛6 + 𝑑𝑛f = 0
As we will show later, at equilibrium G has a minimum value
𝑑𝐺 = 0 𝑔6𝑑𝑛6 + 𝑔f𝑑𝑛f = 0 𝑔6 = 𝑔f
 Excercise
Show that
f 7(h/1)
•𝑈= −𝑇
71 $
f 7(j/1)
• 𝐻 = −𝑇
71 3

These equations are collectively called Gibbs Helmholtz equations and frequently
used in chemical thermodynamics

𝑈 = 𝐹 + 𝑇𝑆 H = 𝐺 + 𝑇𝑆
𝜕𝐹 𝜕𝐺
=𝐹−𝑇 =𝐺−𝑇
𝜕𝑇 𝜕𝑇 3
$
7(j/1)
𝜕(𝐹/𝑇) = −𝑇 f
= −𝑇 f 71 3
𝜕𝑇 $
Applying Maxwell’s relations: Overview
1) Write down a TD potential relevant to the problem.
2) Obtain Maxwell’s relation
3) Invert the Maxwell’s relation using reciprocal theorem:
𝜕𝑥 1
=
𝜕𝑧 ^ 𝜕𝑧
𝜕𝑥 ^
4) Combine partial differentials using reciprocity theorem:
7] 7^ 7n
= −1
7^ n 7n ] 7] ^
7] 7n 7]
Combining (3) and (4), =−
7^ n 7^ ] 7n ^
Excercise

• Find the ratio of isothermal and adiabatic compressibilities in terms of

experimentally determinable quantities.