MODULE 4

MAXWELL’S EQUATIONS

A pure substance existing in a single phase has only two independent variables .Of the
eight thermodynamic properties P, v, T, s, u, h, f & g any one may be expressed as a
function of any two others.

For a pure substance undergoing an infinitesimal reversible process;

a) du = Tds – Pdv

b) dh = du + Pdv + vdP = Tds + vdP

c) df = du - Tds – sdT = -Pdv – sdT

d) dg = dh – Tds – sdT = vdP – sdT

Since u, h, f & g are thermodynamic properties and exact differentials of the type.

dz = Mdx + Ndy, then

(M/y)x = (N/x)y

Applying this relation to the four equations;

(T/v)s = - (P/s)v

(T/P)s = (v/s)P

(P/T)v = (s/v)T

(v/T)P = - (s/P)T

These equations are known as Maxwell’s equations.

FIRST Tds EQUATION

Let s = f (T,v)

ds = (s/T)v dT + (s/v)T dv
1
Tds = T(s/T)v dT + T(s/v)T dv

But ds = q/T

Tds = q

CV dT = q

 Tds = CV dT

 T(ds/dT) = CV

ie CV = T(s/T)v

(s/v)T = (P/T)v by Maxwell’s equations

Tds = CVdT + T (P/T)vdv

This is known as first Tds equation.

SECOND Tds EQUATION

If s = f (T, P)

ds = (s/T)P dT + (s/P)T dP

Tds = T(s/T)PdT + T(s/P)T dP

Since T(s/T)P = CP

(s/P)T = - (v/T)P by Maxwell’s equation

 Tds = CPdT - T (v/T)P dP

This is known as the second Tds equation

 = 1/v (v/T)P

Tds = CPdT - Tv dP

2
THIRD Tds EQUATION

Let s = f (P, v)

ds = (s/P)v dP + (s/v)P dv

Tds = T(s/P)vdP + T (s/v)P dv

= T(s/T)v (T/P)vdP + T(s/T)P (T /v)P dv

But, T(s /T)v = CV

T(s/T)P= CP

Tds = CV (T/P)v dp + CP (T/v)Pdv (1)

Consider;

Volume expansivity  = 1/v (v/T)P

Therefore, 1/v = (T/v)P (2)

Isothermal compressibility, KT = -1/v(v/P)T

Therefore, KT/ = {-1/v (v/P)T} / -1/v(v/T)P}

= - (v/P)T . (T/v)P (a)

Again consider;

(p/v)T.(v/T)P .(T/P)v = -1

(T/P)v = -(v/P)T (T/v)P (b)

From (a) and (b)

(T/p)v = KT/  (3)

Substituting (2) & (3) in (1)

Tds = CV (KT/)dP + CP (1/v)dv

3
EXPANSION COEFFICIENT AND COMPRESSIBILITY

The coefficient of expansion or volume expansivity () and compressibility (KT & K3)
are measured thermodynamic properties of materials.

Coefficient of expansion or volume expansivity ()

The coefficient of expansion is defined as increase of volume per unit volume for unit
increase in temperature when the gas is maintained at constant pressure.

If the volume increases from v to (v + dv) when the increase in temperature is from T to
T + dT at constant pressure, then the coefficient of expansion is given by;

 = 1/v(v/T)P

It is a measure of the change in volume with temperature at constant pressure.

4
The (v/T)P is the slope of the curve representing the variation of v with respect to T at
constant pressure on v- T diagram.

COMPRESSIBILITY OR COEFFICIENT OF COMPRESSIBILITY

It is the decrease of volume per unit volume for unit increase in pressure and there are
two values, one when temperature remains constant and other when entropy remains
constant.

Isothermal compressibility, KT = -1/v (v/P)T

Adiabatic compressibility, Ks = -1/v (v/P)s

The negative sign is used to make right hand side positive as (v/P)T is always

negative.

The reciprocal of isothermal compressibility is called isothermal bulk modulus whereas

(P/T)v = /KT

ie the variation of pressure (at constant volume) with variation of temperature can be
easily measured.

5
The slope of the curve representing the variation of v with respect to P is given by
(v/P)T and is shown plotted on P-v diagram for constant temperature.

DIFFERENCE IN HEAT CAPACITIES

Tds = CV dT + T (P/T)Vdv First Tds equation

Tds = CP dT - T(v/T)PdP Second Tds equation

Equating the above two

CPdT – T(v/T)PdP = CV dT + T(P/T)vdv

(CP – CV)dT = T(P/T)vdv + T (v/T)PdP

dT = {T(P/T)v}/{(CP – CV)}dv + {T(v/T)P}/{(CP – CV)}dP (a)

T = f (v, P)

dT = (T/v)Pdv + (T/P)vdP (b)

From (a) & (b)

{T(P/T)v}/ {CP – CV} = (T/v)P gives (CP – CV) = T(P/T)v (v/T)P

{T(v/T)P}/{CP – CV} = (T/P)v gives (CP – CV) = T(P/T)v (v/T)P

6
ie From both the above equations,

CP – CV = T(P/T)v (v/ T)P

But (P/T)v (T/v)P (v/P) T = -1

 (P/T)v = - (v/T)P (P/V)T

This is a very important equation in thermodynamics. It indicates the following

a) Since (v/T)p2 is always (+ve) and (P/v)T for any substance is (-ve), CP – CV
is always +ve. Therefore CP is always greater than CV.

b) As T 00K, CP  CV or at absolute zero, CP = CV

c) When (v/T)P = 0, CP = CV

Writing equation (1) again

CP – CV = -T (v/T)P2 (P/v)T

 = 1/v (v/T)P

Therefore v = (v/T)P

KT = -1/v (v/P)T

ie (P/v)T = -1/ (KTv)

Substituting in (1)

CP – CV = - T (v)2 . (-1/KTv)

ie CP – CV = T2v/ KT Mayer relation

For an ideal gas, Pv = RT

(v/T)P = R/T = v/T

7
P = RT/v

(P/v)T = RT /v(1/v) = RT . - 1 v -1 – 1 = - RT/ v2

Therefore CP – CV = -T x (v2/T2) x (– RT/ v2)

ie, CP – CV = R

EXPRESSION FOR INTERNAL ENERGY

Let u = f (v, T)

du = (u/T)v dT + (u/v) T dv

CV = (u/T)v

du = CV dT + (u/v)T dv (1)

According to first and second laws of thermodynamics,

dq = T. ds = du + Pdv

du = Tds – Pdv

(u/v)T = T (s/v)T - P (a)

By Maxwell’s third relation

(s/v)T = (P/T)v

Substituting in (a)

(u/v)T = T (P/T)v - P

Substituting in (1)

du = CvdT + {T (P/T)v - P}dv (2)

This is the required equation.

For any substance which obeys the ideal gas equation;

Pv = RT

8
 (P/T)v = /T (RT/v)v = R/v

Substituting in (2)

du = CVdT + {T. (R/v) - P}dv

Pv = RT

R/v = P/T

 du = CVdT + { T. (P/T) - P}dv

ie du = CVdT

EXPRESSION FOR ENTHALPY

Let h = f (T, P)

dh = (h/T)P dT +(h/P)T dP

But CP = (h/T)P

dh = CPdT + (h/P)T dP (1)

According to first law & second law of thermodynamics;

dq = Tds = dh - vdP

dh = Tds + vdP

 (h/P)T = T(s/P)T + v (a)

By fourth Maxwell’s equation

(s/P)T = -( v/T)P

Substituting in (a)

(h/P)T = - T(v/T)P + v

Substituting in (1)

dh = CPdT + {-T(v/T)P + v}dP

9
ie, dh = CPdT + {v – T(v/T)p}dP (2)

which is the required equation.

For a substance which follows the gas law, Pv = RT, then

(v/T)P = /T(RT/P)P = R/P

Substituting in (2)

dh = CPdT + {v - T. R/P}dP

Pv = RT

R/P = v /T

dh = CPdT + {v - T. v/T}dP

ie dh = CpdT

CLAUSIUS – CLAPERYON EQUATION

This equation enables us to determine the enthalpy change associated with a phase
change (such as the enthalpy of vaporization hfg) by knowing P, v and T alone.

Consider the third Maxwell relation

(P/T)v = (s/v)T

During a phase changing process, the pressure is the saturation pressure which depends
on the temperature only and is independent of the specific volume. That is,
Psat = f(Tsat). Therefore, the partial derivative (P/T)v can be expressed as a total
derivative (dP/dT)sat, which is the slope of the saturation curve on a P-T diagram at a
specified saturation state.

10
Let us consider the change of state from saturated liquid to saturated vapour of a pure
substance which takes place at constant temperature. During the evaporation, the
pressure and temperature are independent of volume.

(dP/dT)sat = (sg - sf)/ (vg – vf)

sg = entropy of saturated vapour

sf = entropy of saturated liquid

Similarly vg and vf

Also, (sg - sf) = sfg = hfg/ T

and vg – vf = vfg

 (dP/dT)sat = (sg - sf) / (vg - vf) = (sfg/vfg) = hfg /(T.vfg)

This equation is Claperyon equation for evaporation of liquids.

11
This is an important thermodynamic relation since it enables us to determine the
enthalpy of vaporization hfg at a given temperature by simply measuring the slope of
saturation curve on a P-T diagram, and the vg and vf at the temperature.

The Clapreyon equation is applicable to any phase change process that occurs at constant
temperature and pressure. In general forms:-

(dP/dT) sat = h12 /(T.v12)

where the subscripts 1 & 2 indicate the two phase.

At very low pressures vg >> vf, so if we assume vg ≈ vfg, and taking vapour as an ideal
gas, then

vg = RT/P

 (dP/ dT)sat = hfg/(T.vg) = hfg.P/RT2

hfg = RT2/P (dP/dT)sat

(dP/P)sat = hfg/R (dT/T2 )sat

Integerating,

ln (P2/P1)sat ≈ hfg/R{(1/T1) – (1/T2)}sat

This equation is called Claperyon equation and is used to determine the variation of
saturation pressure with temperature.

12