Phase Equilibrium: Pure Substances Explained

Phase Equilibrium: Pure Substances
D.F. Mendoza
Universidad de Antioquia
D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 1 / 57

Introduction
Equilibrium and Spontaneity
Thermodynamic laws
dU = δQ − δW
δQ
dS = + S gen
T
from the first law we obtain:
δQ = dU + pdV
Replacing δQ in the second law

dU p
dS = + dV + S gen
T T

Introduction
Maximum entropy principle
The combined first and second law equation

dU p
dS = + dV + S gen
T T
for an isolated system where V and U are constant becomes
dS = S gen
since S gen ≥ 0, an spontaneous processes increases the entropy of the

isolated system, and reaches a maximum (dS = 0) where it attains the
thermodynamic equilibrium.

Introduction
Minimum internal energy principle
The combined first and second law equation using U -explicit formulation
is:
dU = T dS − pdV − T S gen
for a system at constant S and V , the internal energy change is
dU = −T S gen
since S gen ≥ 0, an spontaneous processes at constant S and V reduces the

internal energy of the system and this system attains the thermodynamic
equilibrium when U is minimum (dU = 0).

Introduction
Minimum enthalpy principle
The combined first and second law equation using H-explicit formulation
is:
dH = T dS + V dp − T S gen
for a system at constant S and p, the enthalpy change is
dH = −T S gen
since S gen ≥ 0, an spontaneous processes at constant S and p reduces the

enthalpy of the system and this system attains the thermodynamic
equilibrium when H is minimum (dH = 0).

Introduction
Minimum Helmholtz principle
The combined first and second law equation using A-explicit formulation
is:
dA = −SdT − pdV − T S gen
for a system at constant T and V , the Helmholtz energy change is
dA = −T S gen
since S gen ≥ 0, an spontaneous processes at constant T and V reduces the

Helmholtz energy of the system and this system attains the
thermodynamic equilibrium when A is minimum (dA = 0).

Introduction
Minimum Gibbs energy principle
The combined first and second law equation using G-explicit formulation
is:
dG = −SdT + V dp − T S gen
for an isolated system where T and p are constant becomes
dG = −T S gen
since S gen ≥ 0, an spontaneous processes at constant T and p reduces the

Gibbs energy of the system and this system attains the thermodynamic
equilibrium when G is minimum (dG = 0).

Introduction
Summary of equilibrium and spontaneity principles
Variable Constant Spontaneous Equilibrium

U S, V dU < 0 dU = 0; minimum
S U, V dS > 0 dS = 0; maximum
H S, p dH < 0 dH = 0; minimum
A T, V dA < 0 dA = 0; minimum
G T, p dG < 0 dG = 0; minimum

Introduction
Thermodynamic relations for open systems

The fundamental equation for an open-single phase system is:
1 p g
dS = dU + dV − dn
T T T
we note that the thermodynamic description of an open system requires the
number of moles as new variable, also we note that the molar Gibbs energy (also
known as chemical potential, µ) is a new ”intensive” potential in open systems.
The fundamental equation can be arranged in different forms:
Forms of the fundamental equation for open systems
dU = T dS − pdV + gdn
dA = −SdT − pdV + gdn
dH = T dS + V dp + gdn
dG = −SdT + V dp + gdn

Introduction
Phase equilibrium and the phase rule
For an isolated, heterogeneous system (involving π phases), the

thermodynamic equilibrium implies Thermal, mechanical, and chemical
equilibrium
T1 = T2 = ⋯ = Tπ
p1 = p2 = ⋯ = pπ
g1 = g2 = ⋯ = gπ
The thermodynamic degrees of freedom F to solve the intensive variables

of a phase equilibrium problem, involving one component, is given by the
phase rule:
F =3−π
where π is the number of phases.

Introduction
Gibbs-Duhem equation
The internal energy form of the fundamental equation, for single-phase,
open system is,
dU = T dS − pdV + gdn
integrating through an isothermal, isobaric path from n1 = 0 to n2 = n
moles, we obtain:
U = T S − pV + gn
deriving U :
dU = T dS + SdT − pdV − V dp + gdn + ndg
comparing with the fundamental equation we get:
SdT − V dp + ndg = 0

Introduction
Clapeyron equation
The equilibrium state between phases 1 and 2
requires:
g (1) (T sat , psat ) = g (2) (T sat , psat )
If we move along the equilibrium line we have
dg (1) = dg (2)
using Gibbs-Duhem (dg = −sdT + vdp) for each

phase,
−s(1) dT sat + v (1) dpsat = −s(2) dT sat + v (2) dpsat
grouping terms
dp sat s(2) − s(1) ∆sphase h(2) − h(1) ∆hphase

( ) = (2) = phase
= sat (2) = sat phase
dT v −v (1) ∆v T (v − v ) T ∆v
(1)

Introduction
Clapeyron equation can be used in any two-phase equilibrium

• Liquid-vapor equilibrium (liquid-vapor line)
dp sat s(v) − s(l) h(v) − h(l)

( ) = (v) = sat (v)
dT v −v (l) T (v − v (l) )
• Solid-gas equilibrium1 (sublimation equilibrium line)
dp sat s(v) − s(c) h(v) − h(c)

( ) = (v) = sat (v)
dT v −v (c) T (v − v (c) )
• Solid-liquid equilibrium (melting line)
dp sat s(l) − s(c) h(l) − h(c)

( ) = (l) =
dT v − v (c) T sat (v (l) − v (c) )
• Solid-solid equilibrium
dp sat s(c2 ) − s(c1 ) h(c2 ) − h(c1 )

( ) = (c ) = sat (c )
dT v 2 −v 1 (c ) T (v 2 − v (c1 ) )
1
c means solid phase
Introduction
psat empirical equations
• General approach
psat l
T αi
( ) = 1 + ∑ ai [1 − ( ) ]
pn i=1 Tn
psat l
T αi
ln ( ) = ∑ ai [1 − ( ) ]
pn i=1 Tn
where: Tn , pn are normalizing values for

temperature and pressure; ai and αi are
calculated fitting experimental data.
Wagner, Saul, Pruβ. International equation for the pressure along the melting
and along the sublimation curve for ordinary water substance. J. Phys. Chem.
Ref. Data, 23:515-527, 1994.

Introduction
• Sublimation line2 (water: 190 ≤ T ≤ 273.16 K)
psub
ln ( ) = a1 (1 − θ−1.5 ) + a2 (1 − θ−1.25 )
pt
where: θ = T /Tt , a1 = −13.928169, a2 = 34.7078238, Tt = 273.16 K,

pt = 611.657 Pa.
• Melting line (ice I: 251.165 ≤ T ≤ 256.164 K)
= 1 + a1 (1 − θ−3 ) + a2 (1 − θ21.2 )
pm
pt
where: θ = T /Tt , a1 = −0.626 × 106 , a2 = 0.197135 × 106 , Tt = 273.16

K, pt = 0.000611657 MPa.
2
Wagner, Saul, Pruβ. International equation for the pressure along the melting and
along the sublimation curve for ordinary water substance. J. Phys. Chem. Ref. Data,
23:515-527, 1994.
Introduction
• Vapor-liquid line
• Antoine equation
B
ln pvap = A −
C +T
where: A, B and C are constants obtained fitting experimental data.
• Wagner
aτ + bτ 1.5 + cτ 2.5 + dτ 5
ln pvpr =
Tr
where: Tr = 1/Tc , pvpr = pvap /pc , τ = 1 − Tr , a, b and c are constants
obtained fitting experimental data.

Introduction
Example
Obtain A, B, and C coefficients of the Antoine equation that represent the
following experimental data for n-decane.
T sat (°C) psat (mmHg)

1 16.5
5 42.3
10 55.7
20 69.8
40 85.5
60 95.5
100 108.6
200 128.4
400 150.6
760 174.1
Hint: linearize the Antoine equation y = a0 + a1 x1 + a2 x2

AC − B ln p
ln p = A + −C
T T
Introduction
Clausius-Clapeyron equation
This is a simplified equation derived from the Clapeyron equation for
(vapor-liquid and gas-solid phase equilibrium), where we assume:
• v (v) >> v (l) (vapor-liquid equilibrium case).

• v (v) >> v (c) (gas-solid equilibrium case).
• gas-phase follows the ideal gas behavior (i.e., v (v) = RT sat /psat ).
Vapor-liquid equilibrium
d ln p sat s(v) − s(l) h(v) − h(l)

( ) = =
dT RT RT 2
Gas-solid equilibrium
d ln p sat s(v) − s(c) h(v) − h(c)

( ) = =
dT RT RT 2

Introduction

Introduction
Example
Trimethyl gallium, Ga(CH3 )3 , can be used as a feed gas to grow films of
Gas. Use Clausius-Clapeyron equation to estimate the enthalpy of
vaporization of Ga(CH3)3 .3
−4222.1
ln psat = + 17.556
T
where psat in kPa, T in K.
3
Koretsky Engineering and chemical thermodynamics
Introduction
Molar Gibbs energy (chemical potential) of a pure

substance
The chemical potential (molar or specific Gibbs energy) of a pure

substance can be expressed as function of p and T , using the
Gibbs-Duhem expression
dg = dµ = −sdT + vdp
where s is the molar (or specific) entropy and v is the molar (or specific)
volume. µ (or g) is a state function, therefore:
∂µ ∂g ∂µ ∂g
( ) =( ) = −s and ( ) =( ) =v
∂T p ∂T p ∂p T ∂p T

Introduction
integrating this equation we get

T p
µ(T, p) = µ(T ref , pref ) − ∫ sdT + ∫ vdp
T ref pref
or
T p
g(T, p) = g(T ref , pref ) − ∫ sdT + ∫ vdp
T ref pref
where superscript ref denotes an arbitrary reference state. Grouping the two
terms at the right-hand,
p
µ(T, p) = µ(T, pref ) + ∫ vdp
pref
or p
g(T, p) = g(T, pref ) + ∫ vdp
pref
where:
T
µ(T, pref ) = µ(T ref , pref ) − ∫ sdT
T ref

Introduction
A way to calculate µ(T, pref ) (or g(T, pref )), using a reference state is:
µ(T, pref ) = g(T, pref ) = h(T, pref ) − T s(T, pref )
where:
h(T, pref ) = h(T ref , pref ) + [h(T, pref ) − h(T ref , pref )]
and
s(T, pref ) = s(T ref , pref ) + [s(T, pref ) − s(T ref , pref )]

Introduction
Chemical potential of an ideal gas

The chemical potential of an ideal gas at T and p, using T ref , pref as reference
state is given by:
p
µig (T, p) = µig (T, pref ) + RT ln ( ref )
p
The chemical potential at T and pref is calculated from the values of enthalpy and
entropy relative to a reference state
µ(T, pref ) = h(T, pref ) − T s(T, pref )
where:
T T cig
p
h(T, pref ) = ∫ cig
p dT and s(T, pref ) = ∫
dT
T ref T T ref
The chemical potential of an ideal gas with respect to a reference state is:
T T cig
p p
µig (T, p) = ∫ cig
p dT − T ∫ dT + RT ln ( )
T ref T ref T pref

Introduction
µig (T, p) for N2(g)
T ref = 298.15 K, pref = 1.01Phase

bar.Equilibrium: Pure Substances
D.F. Mendoza (Universidad de Antioquia) 25 / 57
Introduction
Fugacity
The change in µ of a pure substance with respect to the pressure through

an isothermal path is
p2 ∂µ
µ(T, p2 ) − µ(T, p1 ) = ∫ ( ) dp
p1 ∂p T
p2
µ(T, p2 ) − µ(T, p1 ) = ∫ vdp
p1
Special case: Ideal gas: The variation of µ with pressure keeping T

constant is
p2 p2 RT p2
µig (T, p2 ) − µig (T, p1 ) = ∫ v ig dp = ∫ dp = RT ln ( )
p1 p1 p p1

Introduction
for any real substance we arbitrarily define a thermodynamic function

(fugacity, f ), which preserves the same form of isothermal variation of the
chemical potential with pressure for an ideal gas
f2
µ(T, p2 ) − µ(T, p1 ) = RT ln ( )
f1
from this definition we note that:
• The fugacity of an ideal gas is p, f ig = p
• The fugacity of any real substance must be equal to f real = f ig = p as
p approaches to zero.
thus,
f
lim ( ) = 1
p→0 p

Introduction
Summarizing
• Ideal gas:
p2 RT p2 p2
µig (T, p2 ) − µig (T, p1 ) = ∫ dp = ∫ RT d ln p = RT ln ( )
p1 p p1 p1
• Real substance: (solid, liquid, gas)
f2 RT f2 f2
µ(T, p2 ) − µ(T, p1 ) = ∫ df ∫ RT d ln f = RT ln ( )
f1 f f1 f1
It is mandatory that:
f
lim ( ) = 1
p→0 p
for any real substance.

Introduction
It will be called the fugacity, represented by the symbol f and

defined by the following conditions: 1. The fugacity of a
molecular species is the same in two phases when these phases
are in equilibrium as regards the distribution of that species. 2.
The fugacity of a gas approaches the gas pressure as a limiting
value if the gas is indefinitely rarefied. In other words, the
escaping tendency of a perfect gas is equal to its gas pressure.
That these two conditions are sufficient to define a property of
every substance which is not a mathematical, fictitious quantity,
but a real physical quantity, capable of experimental
determination in every case, must now be shown. 4
4
Lewis G. N. The law of physico-chemical change. Proceedings of the American
Academy, 1901.
Introduction
The idea of fugacity is thus evolved from the use of vapor

pressure as a measure of escaping tendency. When a substance is
in equilibrium with its vapor, the fugacity, in order to fulfil the
laws of escaping tendency, must be the same in both. The
fugacity of a substance is therefore equal to its vapor pressure if
the vapor behaves like a perfect gas. Speaking in terms not very
precise, we may say that the fugacity of a substance is equal to
the vapor pressure that the substance would have if its vapor
were a perfect gas. It has been shown in the preceding paper
that for a given substance in a given state the fugacity is a
definite property of which the numerical value can in most cases
be readily determined, and which is well suited to serve as an
exact measure of the escaping tendency.5
5
Lewis G.N. Outlines of a new system of thermodynamic chemistry. Contributions
from the research laboratory of physical chemistry of the Massachusetts Institute of
Technology, No 17, 1907.
Introduction
Phase equilibrium and fugacity

The phase equilibria criterium between phases α and β is:
Tα = Tβ
pα = pβ
µα = µβ
if we compute µα from a reference state ◻ and µβ from a reference state △ (all

at T )
fα
µα = µ◻ + RT ln ( )
f◻
fβ
µβ = µ△ + RT ln ( △ )
f
if we subtract these expressions and arrange terms, we obtain
fα µα − µβ
ln ( β
)= =0
f RT
thus, in the equilibrium f α = f β , no matter what reference state is ◻ or △
Introduction
Phase equilibrium criteria

We have two general ways of stating the phase equilibrium criterion:
• Using chemical potential µ
Tα = Tβ = ⋯ = Tπ
pα = pβ = ⋯ = pπ
µα = µβ = ⋯ = µπ
Characteristics: µ depends on a reference state, numerically not

well-behaved.
• Using fugacity f
Tα = Tβ = ⋯ = Tπ
pα = pβ = ⋯ = pπ
fα = fβ = ⋯ = fπ
Characteristics: f does not depend on a reference state, numerically

well-behaved.
Introduction
The escaping tendency of a given molecular species in a given

state is therefore analogous to temperature, and the two laws of
escaping tendency are as follows: If the escaping tendency of a
given molecular species, X, is the same in two phases, then X will
not of itself pass from one phase to the other. If the escaping
tendency of X is greater in one phase, it will pass from this phase
into the other, when the two are brought together.6
6
Lewis G.N. Outlines of a new system of thermodynamic chemistry. Contributions
from the research laboratory of physical chemistry of the Massachusetts Institute of
Technology, No 17, 1907.
Introduction
Fugacity changes in homogeneous phase: Gas phase

To find the change in fugacity due to pressure changes we apply the equivalence
between µ and f :
ln f2v p2
RT ∫ d ln f = ∫ v v dp
ln f1v p1
• v-explicit or z-explicit EoS: (e.g., B truncated virial EoS, compressibility

factor EoS)
f v (T, p2 ) p2 v v p2 z p r2 z
ln ( v
) = ∫ dp = ∫ dp = ∫ dpr
f (T, p1 ) p1 RT p1 p p r1 p r
• p-explicit EoS: (e.g., cubic EoS). In this case we change the integration
variable:
f2 p2 v 2 v2 v2
RT ∫ d ln f = ∫ dpv − ∫ pdv = p2 v2 − p1 v1 − ∫ pdv
f1 p1 v 1 v1 v1
where v1 = v(T1 , p1 ) and v2 = v(T2 , p2 ).

f v (T, p2 ) 1 v2
ln ( ) = ∫ pdv + z2 − z1
f v (T, p1 ) RT v1
Introduction
Fugacity changes in homogeneous phase: liquid and solid

If we assume that liquid and solid phases are incompressible (constant v along the
isothermal integral):
Liquid phase:
f l (T, p2 ) 1 p2
l v l (T )(p2 − p1 )
ln ( ) = ∫ v dp =
f l (T, p1 ) RT p1 RT
thus,
v l (T )(p2 − p1 )
f l (T, p2 ) = f l (T, p1 ) exp ( )
RT
solid phase:
f c (T, p2 ) 1 p2 v c (T )(p2 − p1 )
ln ( c
)= ∫ v c dp =
f (T, p1 ) RT p1 RT
thus,
v c (T )(p2 − p1 )
f c (T, p2 ) = f c (T, p1 ) exp ( )
RT

Introduction
Fugacity as function of T and p

Chemical potential and fugacity are related by the following equation:
f (T, p)
µ(T, p) − µig (T, p) = RT ln ( )
p
from this equation we obtain
µ(T, p) − µig (T, p)

ln f (T, p) = + ln p
RT
• Fugacity as function of p: The derivative of fugacity with respect to

pressure at constan tempertare is:
∂ ln f (T, p) 1 ∂µ(T, p) 1 ∂µig (T, p) 1

( ) = ( ) − ( ) +
∂p T
RT ∂p T
RT ∂p T
p

Introduction
the partial derivatives of the chemical with respect to the pressure at constant
temperature are:
∂µ(T, p) ∂µig (T, p) RT

( ) = v(T, p); ( ) = v ig (T, p) =
∂p T
∂p T
p
thus,
∂ ln f (T, p) v(T, p)
( ) =
∂p T
RT
• Fugacity as function of T : The derivative of fugacity with respect to

temperature at constant pressure is:
∂ ln f (T, p) ∂ µ(T, p) ∂ µig (T, p)

( ) = ( ) − ( )
∂T p
∂T RT p
∂T RT p
The derivatives at the right-hand side are obtained using the

Gibbs-Helmholtz equation.

Introduction
Gibbs-Helmholtz equation
The chemical potential can be expressed as:
µ(T, p) = h(T, p) − T s(T, p)
dividing by T ,
µ(T, p) h(T, p)
= − s(T, p)
T T
The derivative with respect to the temperature
∂ µ(T, p) h(T, p)
( ) =−
∂T T p
T2
∂ ln f (T, p) h(T, p) − hig (T, p) hR (T, p)

( ) =− 2
=−
∂T p
RT RT 2

Introduction
• Fugacity as function of T and p: The total derivative of ln f using

T and p as independent variables is:
∂ ln f (T, p) ∂ ln f (T, p)
d ln f = ( ) dT + ( ) dp
∂T p ∂p T
hR v
d ln f = − 2
dT + dp
RT RT

Introduction
Fugacity coefficient
The fugacity coefficient, φ, is defined as the ratio between the fugacity of

a real substance and the fugacity of an ideal gas at the same temperature
and pressure:
f (T, p) f (T, p)
φ(T, p) = ig =
f (T, p) p
We can obtain this expression from calculating the chemical potentials of
the a real and an ideal gas from a very low pressure (p∗ → 0) to p along
the isotherm T :
µ(T, p) − µ(T, p∗ ) = RT ln (
f (T, p)
f (T, p∗ )
)
µig (T, p) − µig (T, p∗ ) = RT ln ( ∗ )

p
p

Introduction
under this circumstances
µ(T, p∗ ) = µig (T, p∗ )

f (T, p∗ ) = p∗
subtracting
f (T, p)
µ(T, p) − µig (T, p) = RT ln ( ) = RT ln φ(T, p)
p
we can notice that µ(T, p) − µig (T, p) is the residual Gibbs energy g R (T, p)
p p RT
g R (T, p) = RT ln φ(T, p) = ∫ (v − v ig )dp = ∫ (v − ) dp
0 0 p

Introduction
Fugacity coefficient using virial EoS (gas phase only)
Bp
z =1+
RT
where:
RTc 0
B= (B + ωB 1 )
pc
0.422
B 0 = 0.083 −
T r1.6
0.172
B 1 = 0.139 −
T r4.2
integrating
p z−1
RT ln φ(T, p) = RT ∫ dp = Bp
0 p

Introduction
Fugacity coefficient using Cubic EoS (gas and liquid

phases)
The general form of a CEoS is:
RT a(T )
p= −
v − b (v + δ1 b)(v + δ2 b)
where:
R2 Tc2 RTc
a(T ) = a(Tc )f (T ); a(Tc ) = Ωa ( ); b = Ωb ( )
pc pc
√ 2
f (T ) = [1 + m(1 − Tr )]
EoS δ1 δ2 Ωa Ωb m
SRK 1√ 0√ 0.42748 0.08664 0.48 + 1.574 ω - 0.176 ω 2
PR 1+ 2 1- 2 0.45724 0.0778 0.37464 + 1.54226 ω - 0.26992 ω 2

Introduction
using change of variable from dp to dv, we get:

p RT
RT ln φ = ∫ (v − ) dp
0 p
v RT
RT ln φ = RT (z − 1) − ∫ (p − ) dv
∞ v
This expression is integrated using p given by the general CEoS to obtain:
RT ln φ(T, p) =
v a(T ) δ1 b + v
RT ln ( )+ ln ( ) − RT ln(z) + RT (z − 1)
v−b (δ2 − δ1 )b δ2 b + v

Introduction
Fugacity coefficient using corresponding states principle7

pr dpr
RT ln φ = RT ∫ (z − 1)
0 pr
7
Fugacity coefficient (zc = 0.27). Hougen, Watson, Ragatz. Chemical process
principles, part. II, Wiley, 1959.
Introduction
Lee-Kesler corresponding states8
ln φ = ln φ(0) + ω ln φ(1)
8
Koretsky M. Engineering and chemical thermodynamics, 2 ed., US: Wiley, 2013.
Introduction
Lee-Kesler corresponding states9
9
Koretsky M. Engineering and chemical thermodynamics, 2 ed., US: Wiley, 2013.
Introduction
Calculation of fugacities
• Gas phase:
f v (T, p) = φv (T, p)p
where φ is calculated using any suitable EoS (e.g. virial, cubic,
corresponding states)
• Liquid phase:
1 Using any EoS able to model gas and liquid phases (e.g. cubic,
corresponding states):
f l (T, p) = φl (T, p)p
2 Incompressible fluid model:
v l (T )(p − psat )
f l (T, p) = φv,sat (T, psat )psat (T ) exp ( )
RT
• Solid phase: In this case we assume the incompressible solid model
v c (T )(p − psub )
f c (T, p) = φsub,sat (T, psub )psub (T ) exp ( )
RT

Introduction
Note that. . .
When we use the incompressible (fluid or solid) model:
• φv,sat is calculated from the EoS that describes the vapor phase and psat (T )
is calculated from a vapor pressure correlation (e.g. Antoine, Wagner, etc.)
• φsub,sat is calculated from the EoS that describes the gas phase and psub (T )
is calculated from a sublimation pressure correlation.
When we use a cubic EoS to calculate liquid and vapor phases:
• φv (T, p) is calculated using the gas (vapor) volume given by the CEoS at T
and p.
• φl (T, p) is calculated using the liquid volume given by the CEoS at T and p.

Introduction
Example
Calculate the gas-phase fugacity of propane at 85 bar and 444 K using:
• Virial EoS
• SRK EoS
• Corresponding states
Data: Tc = 369.8 K, pc = 42.5 bar, ω = 0.153, zc = 0.27.

Introduction
Example
Calculate the liquid fugacity of propane at 253.15 K and 10 bar and using:
• Virial EoS and incompressible fluid model.
• SRK EoS
• Corresponding states
Data: Tc = 369.8 K, pc = 42.5 bar, ω = 0.153, zc = 0.27, pvap (253.15 K) =
2.444 bar, v l,sat. (253.15 K) = 1.802 × 10−3 m3 /kg.

Introduction
Example
A compound has a solid molar volume of 85 cm3 /mol and at a pressure of
0.25 bar, it sublimates at T = 275 K. Estimate the fugacity of this
compound in the solid phase at T = 275 K and each of the following
pressures,
1 1 bar
2 10 bar
3 100 bar
4 1000 bar
Assume: φsub (275 K, 0.25 bar) ≈ 1 and incompressible solid model.
R = 83.1452 bar cm3 /(mol K)

Introduction
Phase equilibrium calculation

According to the Gibbs’ phase rule the solution10 of a two-phase problem has one
degree of freedom. This degree of freedom can be either T sat or psat .
Let’s suppose we are interested in calculating the equilibrium properties of phases
α and β.
1. Case 1: Given T α = T sat , calculate: T β , pα , pβ using the following
equations:
Tα = Tβ
pα = pβ
f α (T α , pα ) = f β (T β , pβ )
if we replace the first two equations into the third one, we only need to solve
the third equation
f α (T sat , psat ) = f β (T sat , psat )
where psat is the only unknown, since pα = pβ = psat , and T α = T β = T sat
10
by solution we mean finding the intensive properties in the equilibrium, i.e. T and p
of each phase.
Introduction
2. Case 2: Given pα = psat , calculate: T α , T β , pβ using the following

equations:
Tα = Tβ
pα = pβ
f α (T α , pα ) = f β (T β , pβ )
if we replace the first two equations into the third one, we only need
to solve the third equation
where T sat is the only unknown, since pα = pβ = psat , and

T α = T β = T sat

Introduction
In summary
1 Case 1: Given T sat find psat , solving:
then use the equality in temperature and pressure to assign values to
temperature and pressure in each phase:
T α = T β = T sat
pα = pβ = psat
2 Case 2: Given psat find T sat , solving:

then use the equality in temperature and pressure to assign values to
temperature and pressure in each phase:
T α = T β = T sat
pα = pβ = psat

Introduction
Application: Vapor-liquid equilibrium
Example
Find T vap of benzene at 20 bar using:
1 Virial equation (vapor phase) and incompressible fluid model (liquid phase).
2 Generalized fugacity coefficent charts (Corresponding states principle) for
both phases.
3 PR EoS to describe liquid and vapor phases.
Data: Tc = 562.2 K, pc = 48.9 bar, zc = 0.27.
2788.51
ln pvap (mmHg) = 15.9008 − ; (280K ≤ T ≤ 377K)11
T (K) − 52.36
11
Note that this expression is not suitable to solve our problem since
pvap (20 bar) = 494.5 bar.
Introduction
vap
To find T we need to solve the following phase equilibrium equation
f v (T vap , 20 bar) = f l (T vap , 20 bar)
The way we calculate fugacity depends on how we model each phase:

1 Virial equation (vapor phase) and incompressible fluid model (liquid phase).
φv (T vap , 20 bar) ⋅ 20 bar = φv (T vap , 20 bar) ⋅ pvap (T vap )
thus, we nee to find T vap , such that:
pvap (T vap ) − 20 bar = 0
2 Corresponding states principle and PR EoS follow the same approach to

describe liquid and vapor phases.
φv (T vap , 20 bar) ⋅ 20 bar = φl (T vap , 20 bar) ⋅ 20 bar
thus, we nee to find T vap , such that:
φv (T vap , 20 bar) − φl (T vap , 20 bar) = 0

Phase Equilibrium: Pure Substances Explained

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Phase Equilibrium: Pure Substances Explained

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Phase Equilibrium: Pure Substances

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 1 / 57

Equilibrium and Spontaneity

Replacing δQ in the second law

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 2 / 57

Maximum entropy principle

The combined first and second law equation

since S gen ≥ 0, an spontaneous processes increases the entropy of the

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 3 / 57

Minimum internal energy principle

since S gen ≥ 0, an spontaneous processes at constant S and V reduces the

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 4 / 57

Minimum enthalpy principle

since S gen ≥ 0, an spontaneous processes at constant S and p reduces the

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 5 / 57

Minimum Helmholtz principle

since S gen ≥ 0, an spontaneous processes at constant T and V reduces the

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 6 / 57

Minimum Gibbs energy principle

since S gen ≥ 0, an spontaneous processes at constant T and p reduces the

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 7 / 57

Summary of equilibrium and spontaneity principles

Variable Constant Spontaneous Equilibrium

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 8 / 57

Thermodynamic relations for open systems

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 9 / 57

Phase equilibrium and the phase rule

For an isolated, heterogeneous system (involving π phases), the

The thermodynamic degrees of freedom F to solve the intensive variables

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 10 / 57

dU = T dS + SdT − pdV − V dp + gdn + ndg

comparing with the fundamental equation we get:

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 11 / 57

g (1) (T sat , psat ) = g (2) (T sat , psat )

If we move along the equilibrium line we have

using Gibbs-Duhem (dg = −sdT + vdp) for each

−s(1) dT sat + v (1) dpsat = −s(2) dT sat + v (2) dpsat

dp sat s(2) − s(1) ∆sphase h(2) − h(1) ∆hphase

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 12 / 57

Clapeyron equation can be used in any two-phase equilibrium

dp sat s(v) − s(l) h(v) − h(l)

• Solid-gas equilibrium1 (sublimation equilibrium line)

dp sat s(v) − s(c) h(v) − h(c)

• Solid-liquid equilibrium (melting line)

dp sat s(l) − s(c) h(l) − h(c)

dp sat s(c2 ) − s(c1 ) h(c2 ) − h(c1 )

psat empirical equations

where: Tn , pn are normalizing values for

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 14 / 57

• Sublimation line2 (water: 190 ≤ T ≤ 273.16 K)

where: θ = T /Tt , a1 = −13.928169, a2 = 34.7078238, Tt = 273.16 K,

where: θ = T /Tt , a1 = −0.626 × 106 , a2 = 0.197135 × 106 , Tt = 273.16

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 16 / 57

T sat (°C) psat (mmHg)

Hint: linearize the Antoine equation y = a0 + a1 x1 + a2 x2

• v (v) >> v (l) (vapor-liquid equilibrium case).

d ln p sat s(v) − s(l) h(v) − h(l)

d ln p sat s(v) − s(c) h(v) − h(c)

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 18 / 57

D.F. Mendoza (Universidad de Antioquia) Phase Equilibrium: Pure Substances 19 / 57

Molar Gibbs energy (chemical potential) of a pure

The chemical potential (molar or specific Gibbs energy) of a pure