Thermodynamic relations

Clausius-Clapeyron's Equation.
When the change is from solid to liquid state, the characteristic temperature is called the melting point of the solid
and when it is from liquid to vapour state, the temperature is called the boiling point of the liquid. The melting point or
boiling point have got a specific value at a specific pressure and vice versa.
It is possible to obtain a relation showing how the melting and boiling points vary with pressure, by applying
the second law of thermodynamics. The relation thus obtained is known as Clausius Clapeyron equation or the first
latent heat equation.

Let ABCD and EFGH represent the two isothermals at P E

infinitely close temperatures T and (T + dT ) respectively.
Referring to fig.1, the parts AB and EF correspond to the
liquid state of the substance. At B and F, substance is A
F G
purely in the liquid state. Along BC and FG, the change of P+dP T+dT H
state is in progress and the liquid and vapour states coexist
C
in equilibrium. At C and G the substance is purely in vapour P M T N
B D
state. From C to D and G to H, the substance is in the
vapour state. Let P and (P + DP ) be the saturated vapour P
pressures of the liquid at temperatures T and (T + dT )
V
respectively. Let V1, and V2 be the volumes of the V1 V2
substance at F and G respectively.
Let us draw two adiabatics from F and G meeting the lower isothermal at M and N respectively. Let us suppose
that 1 gm. of the substance is taken round a reversible Carnot cycle FGNMF, allowing it to expand isothermally
along FG, adiabatically along GN, compressing it isothermally along NM and adiabatically along MF.
The amount of heat Q1 absorbed along FG is equal to the latent heat of vaporization (L + dL) at
temperature (T + dT ), as substance changes completely from liquid state at F to the vapour state at G. Also
the quantity of heat Q2 rejected along the isothermal compression NM, is L, the latent heat at temperature
T. Here latent heat is supposed to vary with temperature.
Applying the principle of Carnot's reversible cycle

Q1 Q2 Q T
= or , 1 = 1
T1 T2 Q2 T2
Q1 − Q2 T1 − T2
or , =
We have
Q2 T2
Q1= L+dL, Q2=L, T1= T+dT & T2=T

L + dL − L T + dT − T
=
L T
dL dT
or , =
L T
 L
or , dL = dT .........(i )
T
The amount of heat converted into work during the cycle FGMNF,

Q1 - Q2 = L + dL - L = dL…………….(ii)
But the work done during the Carnot cycle is given by the area FGNMF, which may be treated
as a parallelogram.
Hence
dL (in work units) = Area FGNMF.
= FG X Perpendicular distance between FG and NM
=(V2-V1)dP…………..(iii)

where V1, and V2, are the specific volumes (i.e volume per unit mass) in vapour and liquid states
respectively, dP expresses the difference of pressure between FG and NM.
 Substituting this value of dL in (1),

L
or , (V2 − V1 )dP = dT
T
dP L
or , = ..........(iv)
dT T (V2 − V1 )
This is called the Clapeyron's latent heat equation and holds for both the changes of state, i.e., from
liquid to vapour and solid to liquid. In the latter case L will represent the latent heat of fusion, V1 and
V2 the volume occupied by 1 gm. of substance in solid and liquid states respectively. It may be
noted that L in eq. (iv) is to be expressed in work units i.e. in ergs/gm. or Joules/ kg.

Applications.
(i) Effect of pressure on boiling points of liquids. When a liquid boils i.e. changes from liquid state to
gaseous state, there is an increase in its volume so that V2 > V1, or the quantity (V2 - V1) is positive.
Hence from eq. (iv) above, dP/dT is a positive quantity which means the boiling point of a liquid rises with
increase in pressure or vice versa. Thus a liquid will boil at lower temperature under reduced pressure.
Hence water will boil at a temperature less than 100°C, when the atmospheric pressure is less than 76
cm. of mercury – the normal pressure.
(ii) Effect of pressure on melting points of solids. When a solid melts, there may be an increase in
volume as in the case of certain substances like wax and sulphur or there may be a decrease in
volume as in the case of certain substances like ice, gallium and bismuth.
(a) When V2> V1 (As for wax and sulphur ) dP/dT is a +ve quantity. This means that melting point of
such substances rises with increase in pressure.

(b) When V2 < V1 (As for ice, gallium and bismuth), (V2 – V1) is a negative quantity. Hence dP/dT is
also negative which means that melting point of such substances decreases with increase in
pressure. Thus ice will melt at a temperature lower than 0°C when the pressure is higher than the
normal pressure, 76 cm. of mercury.

H.W. Explain why volume of the ice decreases during melting?

Second Latent Heat Equation.
The second latent heat equation, or the equation of Clausius, gives the
variation of latent heat of a substance with temperature and connects it
with the specific heat of the substance in the two states.
Let C1 denote the specific heat of a liquid in contact with its vapours
and C2 the specific heat of saturated vapours in contact with its liquid.
Referring to fig.1, let us consider that 1 gm. of the substance is taken round the
cycle BFGCB. The quantity of heat absorbed by the substance (liquid) in
passing from B to F, when its temperature rises by dT is C1dT. In passing along
FG, when the substance changes from liquid to vapour at constant
temperature T + dT, it absorbs a quantity of heat L + dL.
In passing from G to C, the temperature of the substance (vapours) falls by dT and hence it gives out a quantity of
heat C2dT, while in passing along CB, when it condenses from vapour to liquid at constant temperature T, gives out
a quantity of heat L.
Hence the net amount of heat absorbed during the cycle is
C1dT + L + dL - C2 dT - L = (C1-C2) dT + dL.
This must be equal to the work done which is equal to the area of the cycle or the area FGNMF in the limiting case
and hence, L
(V2 − V1 )dP = dT
T
L
or , (C1 − C2 )dT + dL = dT
T
 L
(V2 − V1 )dP = dT
T
L
or , (C1 − C2 )dT + dL = dT
T
L
or , (C1 − C2 )dT = dT − dL
T
dL L
or , C2 − C1 = −
dT T
This is the latent heat equation of Clacusius

H.W.
1. Calculate the latent heat of ice given that change of pressure by one atmosphere changes the
melting point of ice by 0.0074°C and when one gm. of ice melts its volume changes by 0.0907 C.C.
 Triple point D D’

In thermodynamics, the triple point of a substance is the temperature and pressure at

which the three phases (gas, liquid, and solid) of that substance coexist in C’ B
C
thermodynamic equilibrium. At the triple point, all three phases (solid, liquid, and gas) M
are in equilibrium. It is that temperature and pressure at which the sublimation curve, F O A
fusion curve, and the vaporization curve meet. The temperature and pressure at which a
substance can exist in equilibrium in the liquid, solid, and gaseous states. For example,E
the triple point of mercury occurs at a temperature of −38.83440 °C and a pressure of
0.2 mPa.

i) The boiling point of water increases with increase in pressure and vice versa. The curve AB
represents the relation between temperature and is called the steam line or vaporization line. The
liquid and vapour are in stable equilibrium together only along the line AB. All points above AB
the substance is all liquid and below it there exist vapour only. If at a point M, pressure is raised
keeping temperature constant, boiling point will consequently increase and all vapour will
condensed into liquid. Similarly if at M, pressure is decreased, all the liquid will vaporize and only
vapour will remain.
ii) The melting point of ice decreases with increase in pressure i.e. ice melts below 0°C at a
pressure higher than the atmospheric pressure. The pressure temperature relationship can be
represented by a curve CD or C'D' which is called the ice line or fusion line.
The curve CD, which slopes to the left, is for ice type substances whose melting point is lowered with
increase in pressure ; while C'D', which slopes to the right, is for wax type substances whose melting point
is raised with increase in pressure. The substance is entirely solid on the left of the curve while entirely
liquid on the right. The curve represents the equilibrium between the solid and liquid states.

iii. When the pressure on ice is raised, evaporation from its surface slows down.
The equilibrium between the solid and vapour states of a substance can be
represented by a curve EF called the Hoar Frost line or sublimation line. Above the
curve EF, the substance is all solid and below it all vapour.
These three curves, when plotted on the same diagram, are found to meet in
a single point O as shown in fig. . This point is called the triple point. At the
triple point, the pressure and temperature are such that the solid, liquid and
vapour states of the substance can exist simultaneously in equilibrium.
 D
To show that there is only one triple point. Suppose that the three Pressure
curves do not meet at a point but intersect enclosing an area ACF
Ice line
shown shaded in Fig. Then according to ice line CD, the substance Liquid

must be entirely solid in the shaded area as it is to the left of CD. Solid
According to the steam line AB the substance must be entirely C B
liquid as it is above AB and according to hoar frost line EF the F Stem line

substance in the shaded portion must be entirely vapour as it is A Vapour

Hoar Frost line
E
below EF. But these three conclusions contradict one another and
hence the shaded triangle ACF cannot exist. Thus the three curves Temperature
should meet in a single point O called the triple point.
It should be noted that the triple point of water is not fixed but
is different for different allotropic forms of ice.
 Thermodynamic potentials
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

Four common thermodynamic potentials are:

1. Internal Energy
In thermodynamics, internal energy (also called the thermal energy) is defined as the energy associated
with microscopic forms of energy. It is an extensive quantity, it depends on the size of the system, or on
the amount of substance it contains. The SI unit of internal energy is the joule (J). It is the energy contained
within the system, excluding the kinetic energy of motion of the system as a whole and the potential
energy of the system. Microscopic forms of energy include those due to the rotation, vibration,
translation, and interactions among the molecules of a substance. None of these forms of energy can be
measured or evaluated directly, but techniques have been developed to evaluate the change in the total
sum of all these microscopic forms of energy.
2. Enthalpy
In thermodynamics, the enthalpy is a measurement of energy in a thermodynamic system. It is the
thermodynamic quantity equivalent to the total heat content of a system. The enthalpy is defined to be the sum
of the internal energy U plus the product of the pressure P and volume V. In many thermodynamic analyses the
sum of the internal energy U and the product of pressure p and volume V appears, therefore it is convenient to
give the combination a name, enthalpy, and a distinct symbol, H.
H = U + PV

3. Helmholtz free energy

In thermodynamics, the Helmholtz free energy is a thermodynamic potential that is defined as the internal
energy of the system minus the product of the temperature times the entropy of the system. it measures the
“useful” work obtainable from a closed thermodynamic system at a constant volume and pressure. The
Helmhotz free energy is defined as:
4. Gibbs Free Energy
In thermodynamics, the Gibbs free energy is a thermodynamic potential that is defined as the enthalpy of the
system minus the product of the temperature times the entropy of the system. Since the enthalpy is defined to be
the sum of the internal energy E plus the product of the pressure p and volume V, the Gibbs free energy is defined
as:
 Thermodynamical potentials and their relation with
thermodynamical variables

The first and second law of thermodynamics provides two relations which may respectively be
stated as;

dQ = dU + PdV
& dQ = TdS

Combining the two laws, we have

TdS = dU + PdV
or , dU = TdS − PdV
This expresses the change in internal energy of the system in terms of four thermodynamical
variables. However for a complete knowledge of the system, certain other relations are required and
for this purpose we introduce some functions of the variables P, V, T and S, known as
thermodynamical potentials or the thermodynamic functions. There are four principal
thermodynamic potentials and we shall discuss them one by one.
1. Internal or intrinsic energy.
We have seen already that according to first law of thermodynamics, there is a certain function, U, of
the variables which characterizes the system and this function may be called the intrinsic energy or the
internal energy. When the system passes from one state to another, the change in the internal energy is
independent of the route followed between the two states. The internal energy of a system is defined by
the equation,
dU = dQ − dW

where dW is the external work done and may be replaced by PdV while dQ may be put equal to TdS by
second law of thermodynmaics.

dU = TdS − PdV
Taking partial differentials of the intrinsic energy with respect to variables S, and V, we get,

 U   U 
  = T &  = −P
 S V  V  S

These are the relations connecting the internal energy U with the thermodynamical variables S, V, T and P.
 Now since dU is a perfect differential, we must have

  U    U 
  =  
V  S V S  V  S
 T   P 
  = − 
 V  S  S V
This result is the first thermodynamical relation of Maxwell.

2. Helmholtz's function F.
The first and second law of thermodynamics combined together provide
dU = TdS - dW
If we consider processes in which the system exchanges heat with the surrounding and is thereby
maintained at a constant temperature T, then TdS = d (TS) and we can write
dU = d (TS ) − dW
or , d (U − TS ) = −dW
0r , dF = −dW
where F = U - TS is known as the Helmholtz free energy or more appropriately the work function
(because eq. dF = - dW shows that for reversible changes the work done by the system is equal to the
decrease in this function F). Thus the Helmholtz free energy is defined by the equation.

F = U - TS,
where the value of F depends only on the state of the substance and dF is a perfect differential. Now
dF = −dW
or , dF = dU − d (TS )
or , dF = dU − TdS − SdT
 dF = TdS − PdV − TdS − SdT  dU = TdS − PdV
= − PdV − SdT
Here T and V are independent variables. Taking partial differentials of
 F   F 
  = −P &   = −S
 V T  T V
and since dF is a perfect differential
  F    F 
  =  
V T V T  V T
 S   P 
  = 
 V T  T V
This is the second thermodynamical relation of Maxwell.
3. Enthalpy or total heat H.
Enthalpy is an extensive thermodynamical property and is of particular significance. It is mathematically
defined as
H = U + PV.

The differentiation of which yields

dH = dU + d (PV)
= (T dS - PdV) + PdV + V dP
= T dS + V dP.
At a constant pressure (dP = O), dH = T dS = dQ, the quantity of heat given to the system from an external
source. This explains the name of heat function given to it. It also shows that for an isobaric process,
change in enthalpy is equal to the heat given to the system.
 Now taking partial differentials of H treating S and P as independent variables.
 H   H 
  = T &  =V
 S  P  P  S
And since dH is a perfect differential

  H    H 
  =  
P  S  P S  P  S
 T   V 
  = 
 P  S  S  P
This is the third thermodynamical relation of Maxwell.

4. Gibb's Potential G.
From the definition of enthalpy, we have

H = U + PV
Or,dH = dU + PdV + VdP
 which on putting, dU = T dS – PdV , becomes

dH = T dS - P dV + PdV + V dP
= T dS + V dP

So that if the process be isothermal T dS = d (TS) ) as well as isobaric (dP = O), we get

d (H - TS) = 0 or dG = 0
i.e., G = H - TS = constant.
The function G = H - TS = U + PV – TS
= U - TS + PV
= F + PV
is known as the Thermodynamic potential at constant pressure or Gibb's function. It is obvious that the
function G remains constant if a thermodynamic process remains isothermal as well as isobaric. Thus
the fundamental equation defining Gibb's function G is

G = U − TS + PV
 dG = dU − d (TS ) + d ( PV )
= dU − TdS − SdT + PdV + VdP  dU = TdS − PdV
= VdP − SdT
Here the independent variables are P and T. Taking partial differentials

 G   G 
  =V &  = −S
 P T  T  P
And since dG is a perfect differential

  G    H 
  =  
T  P T P  T  P
 V   S 
  = − 
 T  P  P T
This is the fourth thermodynamical relation of Maxwell,
Thus we see that the four thermodynamical potential U (S. v. F (T, V); H (S. P) and G (T, P) lead us to four
thermodynamical relations - known as Maxwell's relations.
The four functions can be expressed in terms of mesurable quantities P, V, T and S as follows:
dU = T dS - PdV,
dF = -P dV - S dT
dH = T DS + V DP
and dG = V dP - S dT.

The four quantities U (S, V), H (S, P), F (T, V) and G (T, P) are called thermodynamic potentials because
the thermodynamic variables S, T. P and V can be derived from them by their differentiations with respect
to the independent variables associated with them in the same manner as the components of a force are
deduced from a force potential. These have already been derived in the equations above but are once
again listed below :
 F   G   G   H 
S = − V =  = 
 = −   P T  P  S
 T V  T  P
 F   U 
 H   U  P=  = − 
T =  =   V T  V  S
 S  P  S V
The above equations give the values of thermodynamical variables in terms of thermodynamical potentials.
Deductions of Clausius Clapeyron's Equation from Maxwell's Thermodynamical Relation
The Maxwell second thermodynamical relation is, This means that at constant temperature the heat
absorbed or liberated brings out simply a change in
 S   P  the volume of the substance. Therefore, this quantity
  =  of heat absorbed or liberated at constant temperature
 V T  T V must be the latent heat and the change in volume
must be due to a change of state. Considering a unit
mass of the substance, let L be the latent heat when
Multiplying both sides by T we get,
the substance changes in volume from V1 to V2 at
constant temperature, then
 S   P 
T  = T  Q = L & V = V2 − V1
 V T  T V
Substituting these values in the above expression
But Tds=dQ,
 L   P 
 Q   P    = T  
  = T   V2 − V1 T  T V
 V T  T V L dP
=T
Here  Q  V2 − V1 dT
 V T
dP L
represents the quantity of heat absorbed or liberated =
per unit change in volume at constant temperature. dT T (V2 − V )1