Chapter four

Thermodynamics
 Contents
◆ Laws of thermodynamics and basic statistical relations
◆ Statistical calculation of thermodynamic quantities
◆ Thermodynamic potential
◆ Gibbs-Duhem’s and Maxwell’s relations
◆ Response functions
◆ Condition for equilibrium
◆ Thermodynamics of phase transitions
 Laws of thermodynamics and basic statistical relations

❖ The discussion of this chapter encompasses all the fundamental results of classical
thermodynamics and all the essential results of statistical mechanics.
❖ These results in the form of very general statements and group them into two
categories.
1. The macroscopic statements : thermodynamic laws.
2. The microscopic statements : statistical relations

Thermodynamic laws
❖ Zeroth law: If two systems are in thermal equilibrium with a third system, they must
be in thermal equilibrium with each other.
❖ First law: expressing the conservation of energy
❖ First law: An equilibrium macrostate of a system can be characterized by a quantity
Ē (called internal energy) which has the property that or an isolated system,

Ē = constant

❖ If the system is allowed to interact and goes from one macrostate to another, the
resulting change in Ē can be written in the form

where W is the macroscopic work done by the system as a result of the system’s
change in external parameters.

❖ The quantity Q is called the heat absorbed by the system.

❖ Second law: An equilibrium macrostate of a system can be characterized by a
quantity S (called entropy).
❖ Entropy has the following properties:
A. In any process in which a thermally isolated system goes from one macrostate to
another, the entropy tends to increase, i.e.,

B. If the system is not isolated and undergoes a quasi-static infinitesimal process in

which it absorbs heat dQ, then

where T is a quantity characteristic of the macrostate of the system.

❖ Third law: The entropy S of a system has the limiting property that

where S0 is a constant independent of all parameters of the particular system.

Statistical relations
❖ There is first the general connection
❖ This allows one to relate the quantities entering in the thermodynamic laws to one's
microscopic knowledge of the system.
❖ Indeed, if one knows the nature of the particles constituting the system and the
interactions between them, then one can in principle use the laws of mechanics to
compute the possible quantum states of the system and thus to find Ω.
❖ Furthermore, the probability P of finding an isolated system in a situation
characterized by certain parameters y1, . . . , yn. If the corresponding number of
accessible states is Ω., then in equilibrium
 Statistical calculation of thermodynamic quantities

◆ The quantity Ω =Ω(E; x1,...,xn) is a function of the energy of the system under
consideration and of its external parameter.
◆ The relations of particular interest are

◆ These allow to compute the absolute temperature and the mean generalized forces of
the system from a knowledge of Ω.
◆ The above equations permit to find relations connecting the generalized forces, the
external parameters, and the absolute temperature and such relations are called
equations of state.
◆ For example: in the particular case when xɑ= V is the volume of the system, the
corresponding mean generalized force is the mean pressure, which is given by

◆ The relations used to find how the mean pressure depends on the temperature and
volume of the system.
◆ For an infinitesimal quasi-static process the entropy change

◆ The entropy S is a function of the energy and the external parameters

◆ For example: An ideal gas of N molecules in a volume V the quantity Ω is of the
form

◆
◆ The mean pressure of the gas is given by

◆
◆ The mean energy of an ideal gas depends only on its temperature and is independent
of its volume.
 Thermodynamic potential

◆ Thermodynamic potentials are state functions that, together with the

corresponding equations of state, describe the equilibrium behavior of a system as
a function of so-called natural variables.
◆ The natural variables are a set of appropriate variables that allow to compute other
state functions by partial differentiation of the thermodynamic potentials.
◆ The functions of the state variables, pressure (P), Volume (V), Temperature (T)
and entropy (S), together with the two laws of thermodynamics that gives the
complete knowledge of the state of a system are called thermodynamic functions
or thermodynamic potentials.
◆ Thermodynamic potential is a scalar quantity used to represent the
thermodynamic state of a system.
◆ We introduce an auxiliary state functions which are useful in determining the
equilibrium state of a system is not isolated.
◆ Thermodynamic potentials are extensive state variables of dimensions of
energy.
◆ These functions are the energy functions formed by combining the basic
thermodynamic variables.
◆ So far, we have been using the total internal energy (U) and, sometimes, the
enthalpy (H) to characterize various macroscopic systems.
◆ These functions are called the thermodynamic potentials: all the
thermodynamic properties of the system can be found by taking partial
derivatives of the thermodynamic potential.
◆ The four fundamental thermodynamic potentials are
● Internal energy (U)
● Enthalpy or total heat function (H),
● Helmholtz free energy or function (A) and
● Gibbs free energy or function (G)
 Gibbs-Duhem’s and Maxwell’s relations

◆ Gibbs–Duhem equation describes the relation among changes in temperature,

pressure and chemical potential for components in a thermodynamic system .
◆ It is regarded as one of the fundamental equations in thermodynamics, together with
the differential equations of internal energy, enthalpy, free energy, and Gibbs
function .
◆ Let us consider the internal energy of an open system

where µ is chemical potential of the substance in the system/ molecules and N is the

number of particles.
◆ For an infinitesimal change in internal energy becomes

◆ First law of thermodynamics for an open system is

◆ Therefore, for consistency the external term should be zero.

◆ This is the Gibbs-Duhem equation and it show that the three intensive state
variables are not independent.
Maxwell relations

❖ The Maxwell relations can be expressed based upon the fundamental thermodynamic
relation
❖ From this statement we derived the important Maxwell relations
 Response functions
◆ The experimental important response functions are obtained by the second order
differential of the internal energy.
◆ Consider the entropy S expressed as a function of T, V, and N :

❖ Dividing by dT, multiplying by T, and assuming dN = 0 throughout, we have

❖ Appealing to a Maxwell relation derived from F (T, V, and N), and then we get:
❖
❖ Thermodynamics response functions are derivatives of one thermodynamics
parameter with respect to another specific conditions on the remaining
parameters or variables.
❖ Some examples of response functions are given below:
 Condition for equilibrium

What is equilibrium system and characteristics of thermodynamic equilibrium system?

◆ Macroscopic systems often exhibit some memory of their recent history.

◆ A hot cup of coffee cools and takes on the temperature of its surroundings regardless
of its initial temperature.
◆ The final states of such systems are called equilibrium states, which are characterized
by their time independence, history independence, and relative simplicity.
◆ Time independence means that the measurable macroscopic properties of equilibrium
systems do not change with time except for very small fluctuations that we can
observe only under special conditions.
❖ The equilibrium situation of a macroscopic system is simple because
➢ The macrostate of a system in equilibrium is time-independent, except for
ever-present fluctuations.
➢ The average values of all its macroscopic parameters remain constant in time,
although the parameters themselves may exhibit fluctuations (ordinarily quite
small) about their average values.
➢ The equilibrium situation of a system is simpler to treat than the more general
non-equilibrium case where some macroscopic parameters of the system tend to
change in time.
 Thermodynamics of phase transitions

◆ Phase transition is a process of change of state of matter.

◆ For example from solid to liquid state or liquid to vapour state or vapour state
to solid state i.e. Melting, vaporization and sublimation.
◆ Other known phase transition is change of system of one crystalline
modification to another.
◆ A first order phase transition is one in which a system absorbs heat or releases
heat without any change in pressure or temperature but the entropy and
volume of the system changes.
Characteristics of first order phase transition

1. During the phase transition, pressure and temperature remains constant and both
entropy and volume undergoes change.
2. The Gibbs energy remains constant in both the phases but the first derivative of
Gibbs energy with respect to pressure and temperature is discontinuous at the
transition point.

● The solid lines delineate boundaries

between distinct thermodynamic phases.
● These lines are called coexistence curves.
❖ Along these curves, we can have coexistence of two phases, and the thermodynamic
potentials are singular.
❖ The order of the singularity is often taken as a classification of the phase transition.
i.e. if the thermodynamic potentials U, G, A, and H have discontinuous or divergent
mth derivatives, the transition between the respective phases is said to be mth order.
❖ Modern theories of phase transitions generally only recognize two possibilities:
➢ first order transitions, where the order parameter changes discontinuously
through the transition, and
➢ second order transitions , where the order parameter vanishes continuously at
the boundary from ordered to disordered phases.
Phase transformations of a simple substance

❖ Simple substances are capable of existing in phases of three types: solid, liquid, and
gas.
❖ Triple point: That macrostate of a pure substance where its solid, liquid, and gaseous
forms can coexist in equilibrium.
❖ Latent heat : The heat which must be absorbed to transform a given amount of one
phase into an equivalent amount of another phase when the two phases are in
equilibrium with each other.
❖ Vapor pressure: The pressure of the gaseous phase in equilibrium with a liquid (or
solid) at a specified temperature.
❖ Phase-equilibrium curve: The curve of corresponding values of temperature and
pressure where two phases can coexist in equilibrium with each other.
❖ Clausius-Clapeyron equation: The equation dp/dT = ΔS/ΔV which relates the slope
of a phase equilibrium curve to the entropy change ΔS and volume change ΔV
between the two phases at the given temperature and pressure.
❖ In this case the Clausius-Clapeyron equation asserts that the slope of the solid-liquid
equilibrium line (i.e., of the melting curve) is positive.
❖ There are some substances, like water, which contract upon melting so that ΔV < 0.
❖ For these the slope of the melting curve must be negative.