Derivation of Clapeyron equation • other system properties by an exact

from phase-change principle of pure thermodynamic equation. (equation

substances 1) :
 When a pure substance is liquefied
from the solid state or vapourized dP sat
H  T  V (1)
from the liquid at constant pressure, dT
no change in temperature occurs.
 However, the process requies the
transfer of a finite amount of heat to
where for a pure species at temperature,
the substance. These heat effects are T.
called the latent heat of fusion and
the latent heat of vapourization.
∆H= latent heat
• According to the phase rule, atwo-
∆V = volume change accompanying the
phase system consisting of a simgle phase change
species is univariant. And its
∆Psat = vapour pressure
intensive state is deiermined by the
specification of just one intensive
property. Equation 1 is called Clapeyron equation.
The derivation of the equation is as
• Thus, the latent heat accompanying a follows:
phase change is a function of Since the molar or specific values of the
temperature only, and is related to extensive thermodynamic
 properties change abruptly when a
phase transition at constant temperature
and pressure occurs; the molar or
specific volume of a saturated liquid is
very different from that for a saturated
vapour at the same temperature and
pressure.
 This is true as well for internal energy,
enthalpy and entropy. The exception is
the molar or specific Gibbs energy,
which for a pure species does not
change during a phase transition such as
melting, vapourization or sublimation.
 Consider a pure liquid in equilibrium
with its vapour in a piston/cylinder
arrangement at temperature T and the
corresponding vapour pressure Psat.
 Since a phase change represents a
transition between two phases that
coexist in equilibrium, equation (2),
which is a t criterion of equilibrium
( dG )T ,P  0 (2)
applies to the process of change.
• Equation 2 implies that at the
equilibrium state, the differential
variation may occur in the system at
constant T and P without producing a
change in G.
• In other words, for a pure substance T
and P are indeed constant, and
according to equation 2, the total Gibbs
energy for the closed system in which
the transition occurs must also be
constant. This can be true only if the
molar gibbs energy is the same for both
phases.
• Thus for two coexisting phases α and β

of a pure G  G  , equation(3)
substance 3 must be
fulfilled.
• If T and P are mow simultaneously
changed by dT and dP in such a way as
to maintain equilibrium between the two

dGforthis 
dGchange, equation
(4)
phase, then 4
is obeyed.
• Now applying the fundamental • Substituting the property changes of
property relation for Gibbs energy phase transitions (equations 8 and 9)
(assuming one mole of a in equation 7, the resulting expression
homogeneous pure material) given in is given in equation 10
Equation (5).
S   S   S   (8)
dG   S dT  VdP (5)
V   V   V   (9)
• Substituting equation 5 in equation 4
dP sat ( S   )
 S  dT  V  dP   S  dT  V  dP (6)  (10)
dT ( V   )
 S  dT  S  dT  V  dP  V  dP

dT ( S   S  )  dP (V   V  ) • A phase transition occurring at

constant temperature and presure
dP ( S   S  ) requires an exchange of heat between
 (7)
dT (V   V  )
the substance taken as the system and
its surrounding.
• Since the pressure in this equation is • When the transition is carried out
always a saturation pressure on the reversibly, this heat, known as the
appropriate phase boundary, Psat can latent heat. Is equal

to the enthalpy
Q   H
change; that is (11)
replace P.
• In addition, for a reversible process • When Equation 14 is applied to the
at constant temperature process, vaporization of a pure liquid., the
equation 12 gives the entropy following is assumed:
change. dP sat
 slope of the vapour versus temperature
Q dT
S    (12) curve at the temperature of int erest
, T
 Since the phase transition is carried V  difference between molar volumes of
out at constant temperature and saturated vapour and saturated liquid
pressure, equations 11 and 12 may
H  latent heat of vapourisation
be combined to get equation 13.
• Equation 14 may be written for each
 H   of the three phase transitions as
S  (13)
T follows:
Fusion :
 Substituting equation 13 in equation
dP sat H sl Hl  Hs
10 gives the expression for the   (15)
dT T ( V ) T (V l  V s )
sl
Clapeyron equation (equation 14)
Vaporisation :
dP sat H   dP sat H lv Hv  Hl
 (14)   (16)
dT T ( V   ) dT T ( V lv ) T (V v  V l )
 Sub lim ation : • A vapour-pressure equation of the
dP sat H sv Hv  Hs form:
  (17)
dT T ( V sv ) T (V v  V s ) B
In P sat  A 
where, T
s=solid; l= liquid; v=vapour; where A and B are constants. Is a useful
sl=fusion; lv= vaporisation; equation for many purposes since the
sv= sublimation equation is a plot of In Psat versus 1/T
which yields a line that is nearly
 straight.
Clapeyron equation provides a vital
connection between the properties of
different phases. It is usually applied Example
to the calculation of latent heats of From the data that follows, estimate the
vaporisation and sublimation from latent heat of vaporisation, ∆Hlv for
vapour-pressure and volumetric data benzene at 340K. At this temperature,
 For the Claperon
 equation:
  dP
sat
Psat = 66.15kPa, Vf = 0.0012 m3/kg, Vg =
 H  T V
dT 2.5332 m3/kg. In addition , at 350K,
Psat = 91.62kPa

acurate representations of Psat as a Solution

function of temperature is needed. Clapeyron equation is applied:
 dP sat • Substituting:
H lv
 T V lv

dT ( BP sat )
H lv
 T V lv

T2
• The volume change of vaporisation • →
is : ( BP sat )
H lv
 V lv

∆Vlv= 2.5332 -0.012= 2.5212 m3/kg T

• To find the constant B, equation
Over the small interval from 340 to below is used.
350K, the vapour pressure should be
well represented by the following In P sat  A 
B
equation: T
• For T = 340K:
B
In P sat  A In 66.15 = A – B/340 (i)
T
From which For T = 350K:
sat sat
In 91.62 = A – B/350 (ii)
dP BP
 From equation (i),
dT T2
Note that: 4.1919 = A- B/340 (iii)
From equation (ii),
d ( InP sat ) 1 dP sat 4.51765 = A – B/350 (iv)
 sat
dT P dT
 From equation (iii):
1425.25 = 340A - B (v)
• From equation (iv):
1581.18 = 350A – B (vi)
• Equation (vi) minus Equation (v):
1581.18 – 1425.25 = 350A – 340A – B + B
→ 155.93 = 10A
→ A = 15.593
 Substituting A = 15.593 in either
equation (iii) or (iv):
B = 3876.37K
 Subtituting B in the equation below:
( BP sat )
H lv
 V lv

T
(3876.37)(66.15)
H lv  (2.5212)
340
• ∆H = 1901.44kJ/kg