Practice problems:

Chapter 10, Problems 7, 16, 17, 18

Chapter 11, Problems 1, 2, 3, 21, 22, 28

 Chapter 10: Vapor/Liquid Equilibrium: Introduction
Note: it is the same sign
Mass fraction mole fraction molar concentration

 
m m n n n n
xi  i   i
m m xi  i  i Ci  i  i q: Volumetric flow rate
n n V q

Gibbs Phase Rule (intensive property) Duhem’s theorem (include intensive and
extensive properties)
Independent Restrictions Independent Restrictions
variables variables
Concentrations for each phase N-1 N-1

Concentrations for

Temperature and pressure 2 2

Chemical potential equilibriums -1 -1

for each chemical

Chemical potential equilibriums N(-1) N(-1)

for N chemicals
Number of masses ( have
different masses)
Mass balance for each species N

Total degree of freedoms F=N(-1) = 2- F=N(-1) -= 2

Above equations can be used for non-reaction system (without specific restriction)
Phase rule and Duhem’s theorem for reacting
systems
• For reacting systems
– Phase rule variables in each phase: F 2    N

– With r chemical reactions: F 2    N  r

– With s special constraints, F 2    N  r  s
 Simple models for VLE
• The simplest are Raoult’s law and Henry’s law.
• Raoult’s law: It based on the following three assumptions:
– the vapor phase is an ideal gas (apply for low to moderate pressure)
– the liquid phase is an ideal solution (apply when the species that are chemically similar)
• Ideal-solution behavior is often approximated by liquid phases wherein the
molecular species are not too different in size and of the same chemical nature. A
mixture of ortho- meta- and para-xylene is very closely to ideal-solution behavior.
A mixture of n-hexane/n-hyptane, or ethanol/propanol can also be treated as ideal
solution.

Pi  yi P  xi Pi sat (i 1, 2, ..., N )

–
• it is valid for any species present at a mole fraction xi approaching unity (saying, >
about 90%), provided that the vapor phase is an ideal gas.
1
yi P  xi Pi sat (i 1, 2, ..., N )
yi P
 yi P / Pi sat 1 P
 yi / Pi sat
(i 1, 2, ..., N )

y 1 xi  sat x i 1 i i

i
i
Pi i
For dew point calculation where liquid
sat
P  xi Pi (i 1, 2, ..., N ) composition is unknown (dew point is
i
defined where the last drop disappears.
Binary system X2 = 1-x1 In other words, this point is saturated
vapor so from vapor fraction y.
P P2sat  ( P1sat  P2sat ) x1
If one plots P vs x1, it should be a linear line
For bubble point calculation where the
(see Figure 8) with x1 = 0, P = P2sat.)
vapor composition is unknown
 For bubble
point
P P2sat  ( P1sat  P2sat ) x1

will be used to calculate bubble pressure because

one only knows the liquid fraction (the up region in
the figure) so the calculated point is b but not c

Same reason, For dew

1 point
P (i 1, 2, ..., N )
 yi / Pi sat
i

Acetonitrile(1)/nitromethane(2) 75 oC
Example 10.1. Binary system acetonitrile (1)/nitromethane (2) conforms closely to Raoult’s
law. Vapor pressures for the pure species are given by the following Antoine equations:

sat 2945.47 sat 2972.64

ln P1 / kPa 14.2724   ln P2 / kPa 14.2043  
t / C  224.00 t / C  209.00
(a) Prepare a graph showing P vs. x1 and P vs. y1 for a temperature of 75°C.
(b) Prepare a graph showing t vs. x1 and t vs. y1 for a pressure of 70 kPa.

(a) BUBL P P P2sat  ( P1sat  P2sat ) x1

At 75°C P1sat 83.21 P2sat 41.98
e.g. x1 = 0.6 x1 P1sat (0.6)(83.21)
P 41.98  (83.21  41.98) x1 y1   0.7483
P 66.72 P 66.72

At 75°C, a liquid mixture of 60 mol-% (1) and 40 mol-% (2) is in equilibrium with a vapor
containing 74.83 mol-% (1) at pressure of 66.72 kPa.
Give a different x1, a different P and y1 If x1 is known, for example x1 =0.6
can be calculated, and curve of P vs X1
and y1 can be plotted.
Note: actually it is not accurate
This is the liquid phase composition at point b’
because Raoult’s law can only be
in Figure 10.11
good if x1 is close to unity
Another method: one can give different y1
then calculate P, following by calculating x1.

1
P sat
y1 / P
1  y2 / P2sat

At y1 = 0.6, t= 75 oC,
1
P 59.74kPa
0.6 / 3.21  0.4 / 41.98

Also y1 P 0.6 X 59.74

x1   0.4308
p1sat 83.21

This is the liquid phase composition at point c’.

 (b) BUBL T, having P = 70 kPa
2945.47 2972.64
ln P1sat / kPa 14.2724  ln P2
sat
/ kPa 14.2043 
t /  C  224.00 t /  C  209.00

If P is fixed, P1sat P  P2sat

say 70 kPa x1  sat T vs. x1 T vs. y1
Select T
P2sat P1  P2sat xP
1 1
sat
y1 
P

This is temperature
but not pressure
 Henry’s law
Consider water in contact with air at equilibrium, from Raoult’s law
y2P = X2P2sat (1 is air and 2 is water)
If no air is dissolved in water (liquid water is treated as pure water)
y2P = P2sat
at 25 oC,
y2 = P2sat/P = 3.166/101.33 = 0.0312
However, it cannot be used to calculate the concentration in the liquid phase because
Roault’s law can only be used for xi approaching unity (i.e. y2 is ok, but cannot use y2
to calculate x2)
• For a species present as a very dilute solute in the liquid phase, the partial pressure
of the species in the vapor phase is directly proportional to its liquid-phase mole
fraction:
yi P  xi H i At 25 oC, the fraction of air
y1 = 1-y2 = 1 - 0.0312 = 0.9688

Air fraction in water:

y1 P (0.9688)(101.33)
x1   1.35 X 10  5
H1 72,950
Assuming that carbonated water contains only CO2 (species 1) and H2O (species 2) ,
determine the compositions of the vapor and liquid phases in a sealed can of “soda” and
the pressure exerted on the can at 10°C. Henry’s constant for CO2 in water at 10°C is about
990 bar.

Henry’s law for species 1: y1 P  x1 H1 (1)

Raoult’s law for species 2: y2 P  x2 P2sat (2)

P  x1 H1  x2 P2sat (3)

Assuming x1 = 0.01
P (0.01)(990)  (0.99)(0.01227) 9.912

To (1) solve y1

Apply y1 to (2) to solve x2

Apply x2 and x1 = 1-x2 to (3) to solve another P

Continue till convergent. Final solution: x1 = 0.01, y1 = 0.9988, y2 = 0.012

 VLE modified Raoult’s law
• Account is taken of deviation from solution ideality in the liquid phase by a factor
inserted into Raoult’s law:
The activity coefficient, f (T, xi)

yi P  xii Pi sat (i 1, 2, 3, ... N )

yi P
xi 
i Pi sat
P  xii Pi sat
i
yi P y
x
i 1  (
i Pi sat
) P  ( isat )
i Pi

1
P
 yi / i Pi sat
i
Example 10.3 For the system methanol (1)/methyl acetate (2), the following equations
provide a reasonable correlation for the activity coefficients:
ln 1 (2.771  0.00523T ) x22 ln 2 (2.771  0.00523T ) x12
The Antoine equations provide vapor pressures:
3643.31 2665.54
ln P1sat / kPa 16.59158 ln P2sat / kPa 14.25326 
T ( K )  33.424 T ( K )  53.424
Calculate
(a): P and {yi} for T = 318.15 K and x1 = 0.25
(b): P and {xi} for T = 318.15 K and y1 = 0.60
(c): T and {yi} for P = 101.33 kPa and x1 = 0.85
(d): T and {xi} for P = 101.33 kPa and y1 = 0.40
(e): the azeotropic pressure and the azeotropic composition for T = 318.15 K
(a) A BUBL Pressure calculation
for T = 318.15, and x1 = 0.25

P1sat 44.51 P2sat 65.64 1 1.864 2 1.072

P  xii Pi sat (0.25)(1.864)( 44.51)  (0.75)(1.072)(65.64) 73.50

i

yi P  xii Pi sat y1 0.282 y2 0.718

(b): A DEW Pressure calculation,
for T = 318.15 K and y1 = 0.60
sat
Iteration process
P 44.51
Find: 1

P sat
65.64 1
2
P
Start with
 2 1  yi / i Pi sat
assumption 1 i

P
y1 P
x1 
1 P1sat

x1 , x2

ln 1 (2.771  0.00523T ) x22

ln 2 (2.771  0.00523T ) x12

1,2

Converges at: P 62.89 kPa 1 1.0378 2 2.0935 x1 0.8169

(c): A BUBL temperature calculation T1sat 337.71 T2sat 330.08 Here we need to use
physical-chemistry
for P = 101.33 kPa and x1 = 0.85 T  x1T1sat  x2T2sat handbook to find
For initial T, assuming it can be estimated by T1sar and T1sar
mole-fraction weighted average, i.e
T (0.85)T1sat  (0.15)T2sat 336.57

Iterative process (Start with T=336.57)

1 1 1
P  
y / i Pi sat y1 y2 y1 (1  y1 )
i  
i 1 P1sat 2 P2sat 1 P1sat 2 P2sat

1
P x11 P1sat
y1

(1  y1 ) y1 
ln 1 (2.771  0.00523T ) x22 1 P1sat 2 P2sat P
1,2 y1, y2 P1sat
2
ln 2 (2.771  0.00523T ) x 1 x22 P2sat
y2 
P

3643.31
ln P1sat / kPa 16.59158
T ( K )  33.424

Converges at: T 331.20 K 1 1.0236 2 2.1182 y1 0.670 y2 0.330

(d): for P = 101.33 kPa and y1 = 0.40 From physical-chemistry handbook to find T1sar and T1sar

T1sat 337.71 T2sat 330.08

Start at T (0.40)T1sat  (0.60)T2sat 333.13

And assuming 1 2 1

P1sat , P2sat

y1P
x1  3643.31
1 P1sat ln P1sat / kPa 16.59158 
T ( K )  33.424
y2 P
x2  2665.54
2 P2sat ln P2sat / kPa 14.25326 
T ( K )  53.424

yi P
x1 , x2 T
Pi sat 
i xi

ln 1 (2.771  0.00523T ) x22

ln 2 (2.771  0.00523T ) x12

1 , 2
Converges at: T 326.70 K 1 1.3629 2 1.2523 x1 0.4602 x2 0.5398
 (e): the azeotropic pressure and the azeotropic composition for T = 318.15 K

y1
x1 yi P  xii Pi sat 1 P1sat
Define the relative volatility: 12  12 
y2 2 P2sat
x2

Azeotrope y1  x1 y2  x2 12 1

ln 1 (2.771  0.00523T ) x22 1 exp[(2.771  0.00523T ) x22 ]

ln 2 (2.771  0.00523T ) x12 2 exp[(2.771  0.00523T ) x12 ]

If x1=0, x2=1 If x2=0, x1=1

1 P1sat P1sat exp(2.771  0.00523T )
P1sat
12   2.052 12 x1 1  0.224
x1 0
2 P2sat P2sat P2sat exp(2.771  0.00523T )

Since α12 is a continuous function of x1: from 2.052 to 0.224, α12 = 1 at some point

There exists the azeotrope!

 2665.54
At azeotropic point ln P2sat / kPa 14.25326
T ( K )  53.424
3643.31
az sat ln P1sat / kPa 16.59158 
P
1 1
sat

1 P
2
T ( K )  33.424
1az P2sat
12  sat
1 az
 sat  1.4747
P
2 2  P 2az P1sat
2 1

ln 1 (2.771  0.00523T ) x22

ln 2 (2.771  0.00523T ) x12

1
ln (2.771  0.00523T )( x2  x1 )( x2  x1 ) ln(1.4747)
2
x2  x1 1

1
ln (2.771 0.00523T )(1  2 x1 ) ln(1.4747)
2

Solve x1, which is x1az

The Dewpoint and bubblepoint
calculations are readily made with x1az 0.325  y1az
software packages such as
ln 1 (2.771  0.00523T ) x22
Mathcad and Maple.
1az 1.657
P az 1az P1sat 73.76kPa
 VLE from K-value correlations
• A convenient measure, the K-value:
y
– Define: K i  xi
i
Ki > 1, the I component in the vapor phase is greater than that in the liquid phase (Called
Lightness)

xi P sat  yi P Pi sat
Raoult’s law so Ki 
P
– The modified Raoult’s law:

sat i Pi sat
yi P  xii Pi (i 1, 2, 3, ... N ) Ki 
P

yi  xi K i so K x i i 1 (10.13, used to calculate bubblepoint,

i amount of gas is ignorable)

Also xi  yi / K i x 1 yi
i
i
K
i
1
(10.14, used to calculate dew point,
i
amount of liquid is ignorable)
The K-value depends only on T and P but independent on the compositions of the liquid
and vapor phase
Low temperature
range
Example 10.4 For a mixture of 10 mol-% methane, 20 mol-% ethane, and 70 mol-% propane
at 50°F, determine: (a) the dewpoint pressure, (b) the bubblepoint pressure. The K-values are
given by Fig. 10.13.

(a) at its dewpoint, only an insignificant amount of liquid is present (amount of liquid is
negligible). The gas phase should satisfy Equation 10.14. yi
i K 1
i
This can be done by simply trails to find at which pressure the equation 10.14 can be satisfied

(b) at bubblepoint, the system is almost completely condensed. Same as above, the
system should satisfy the Equation 10.13
 i
K x 1
i i
 Flash calculations
• A liquid at a pressure equal to or greater than its bubblepoint pressure “flashes” or
partially evaporates when the pressure is reduced, producing a two-phase system
of vapor and liquid in equilibrium.
• Consider a system containing one mole of nonreacting chemical species:

L V 1 zi  xi L  yiV zi  xi (1  V )  yiV
Solve yi and
yi  xi K i

The moles of vapor The vapor mole fraction zi K i

yi 
The moles of liquid The liquid mole fraction 1  V ( K i  1)

zi K i
 1  V ( K  1) 1
i
Example 10.5 The system acetone (1)/acetonitrile (2)/nitromethane(3) at 80°C and
110 kPa has the overall composition, z1 = 0.45, z2 = 0.35, z3 = 0.20, Assuming that
Raoult’s law is appropriate to this system, determine L, V, {x i}, and {yi}. The vapor
pressures of the pure species are given.
Do a BUBL P calculation, with {zi} = {xi} (i.e. all materials are in their liquid form):
Pbubl  x1 P1sat  x2 P2sat  x3 P3sat (0.45)(195.75)  (0.35)(97.84)  (0.20)(50.32) 132.40 kPa
Do a DEW P calculation, with {zi} = {yi} :
1
Pdew  sat sat sat
101.52 kPa
y1 / P1  y2 / P2  y3 / P3 L 1  V 0.2636 mol
Since Pdew < P = 110 kPa < Pbubl, the system is in the two-phase region,
K1 1.7795 zi K i
Pi sat
Ki 
P K 2 0.8895  1  V ( K  1) 1 V 0.7364 mol
i
K 3 0.4575
zi K i
yi 
1  V ( K i  1)
yi
x1 0.2859 Ki  y1 0.5087
xi
x2 0.3810 y2 0.3389
x3 0.3331 y3 0.1524
 Chapter 11
Solution Thermodynamics: Theory
 (nG ) 
i  
 ni  P ,T ,n j
(11.1)
 G 
 G 
V   (11.4) S   
 T  P , x (11.5)
 P  T , x

   dn     dn  0
i i i i Constant T and P,
i i
such as phase
i i (11.6) equilibrium

 (nM ) 
M i   (11.7)
 ni  P ,T ,n j

M  xi M i (11.12)
i
 For binary system
M  x1M 1  x2 M 2

dM  x1dM 1  M 1dx1  x2 dM 2  M 2 dx2

Const. P and T, using Gibbs/Duhem equation, equ 11.14  x dM
i
i i 0
dM M 1dx1  M 2 dx2
x1  x2 1
x1  x2 1 dM
dM dM x2 (1  x1 ) M 1  x2 M 2 M 1  ( x1M 1  x2 M 2 ) M 1  M
M 1  M 2 x2  x2 M 1  x2 M 2
dx1 dx1 dx1

dM
M 1 M  x 2
dx1 (11.15)

similar M 2 M  x1
dM
dx1 (11.16)
 At x1 = 0, I 2 M 2 M M 2 (see the draw)

Corresponding I 1 M 1 M 1 (the partial property at infinite dilute)

These two equations can be plot as the follows

I1(x1=1) I2(x2=1)

(the last part of this equation can be figured out from the geometry of the draw)
If draw a tangent line at point x1 = 0,
The intercept of the draw at x1 = 0 is I2 (see the figure)
I2 and M 2 approach to the same point, which means
M 2 M M 2

Corresponding M 1  I1 M 1 (the partial property at infinite dilute)

similar
or at x2=0, I1 M 1 M 1 M

I 2 M 2

Note: partial properties are x dependent. Draw a line at different x point, one has
different intercept so different partial properties.
Example 11.3. The need arises in a laboratory for 2000 cm 3 of an antifreeze solution consisting of
30 mol-% methanol in water. What volumes of pure methanol and of pure water at 25°C must be
mixed to form the 2000 cm3 of antifreeze at 25°C? The partial and pure molar volumes are given
3
Vmethanol 40.727cm3 / mol Vmethanol 38.632cm 3 / mol Vwater 18.068cm / mol Vwater 17.765cm / mol
3

V x1V1  x2V2 V (0.3)(38.632)  (0.7)(17.765) 24.025 cm 3 / mol

n1 (0.3)(83.246) 24.974 mol
Vt 2000
n  83.246 mol
V 24.025 n2 (0.7)(83.246) 58.272 mol

V1t n1V1 (24.974)( 40.727) 1017 cm 3 V2t n2V2 (58.272)(18.068) 1053 cm 3

Example 11.4: The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is:
H 400x1  600 x2  x1 x2 (40x1  20 x2 )
Determine expressions for H1 and H 2 as functions of x1, numerical values for the pure-species enthalpies H1
 
and H2, and numerical values for the partial enthalpies at infinite dilution Hand
1 H2

H 400x1  600 x2  x1 x2 (40x1  20 x2 )

H 2 H 2 600 J / mol H1 H1 400 J / mol
x1  x2 1
x1 0 x1 1
H 600  180 x1  20 x13 x1  x2 1
3
H 2 600  40x 1 H1 420  60 x12  40x13
dH dH
H 2 H  x1
dx1
 180  60 x12 H 1  H  x2
dH
dx1 dx1
x1 1 x1 0

J  J
 H1 420
H 2 640 mol
mol

dM dM
(11.16) M 2 M  x1
dx1 (11.15) M 1 M  x 2
dx1
  (Gi )   (Gi ) 
 (V )   ( S )     
      P  Vi  T   S i
 T  P ,n  P T ,n  T , x   P, x

H i U i  PVi

p
i
i P

Gibbs’s theorem M iig (T , P) M iig (T , pi ) (11.20)

ig ig ig
However, V (T , P ) V (T , P )
i but V i (T , P ) V i (T , pi )

ig ig
H iig (T , P ) H iig (T , pi ) H iig (T , P ) H ig  yi H i  yi H iig Also for energy U ig  yi U i  yiU iig
i i i i

More simply
dSiig  Rd ln P const .T S ig  yi Siig  R  yi ln yi (11.26)
i i

Gi ig H iig  T ( Siig  R ln yi ) H iig  TS iig  RT ln yi

iig Gi ig Giig  RT ln yi (11.27)

At constant T, RT
dGiig Vi ig dP  dP RTd ln P
P
Integration gives
Giig i (T )  RT ln P (11.28)
i (T ) is an integration constant at temperature T. It is a species-dependent constant

iig i (T )  RT ln( yi P )

G ig  yi i (T )  RT  yi ln yi P (11.30)
i i

For ideal gas mixing: H mix H ig  yH i i

ig
0
i

1
S mix S ig  yS i
i i
ig
R  yi ln
i yi
1

Also ig
V ig V i Vi ig
ig
Vmix V ig  yV i
i i V ig   yV
i
i
ig
V ig (1   y ) 0
i
i
 Fugacity and fugacity coefficient
a quantity that takes the place of μi. It is defined as it is from
Gi i (T )  RT ln f i (11.31) called Fugacity, with unit of pressure

If it is ideal gas, from (11.28)

Giig i (T )  RT ln P One has fi = P for a pure ideal gas
fi
Gi  Giig RT ln
P

From divination of Residual property (6.41)

fi
GiR RT ln i (11.33) Where i 
P Fugacity coefficient
residual Note: it is P but not Pi
For idea gas f i P i 1
GiR 0

Also, for real gas fi

lim i lim 1
P 0 P 0 P

Combine (11.33) and (6.49) GR P dP

  Z  1 (const. T )
RT 0 P

P dP
One has ln i  ( Z i  1) (const . T ) (11.35)
0 P
Above equations apply to pure species i in any phase at any condition.
 Bi P
Because Z  1
RT

Bi P dP Bi P
Bi is a function of T only ln i    (const. T ) Generic Cubic Equation is another way
RT 0 P RT

VLE for pure species

Saturated vapor: Giv i (T )  RT ln f i v
Saturated liquid: Gil i (T )  RT ln f i l

fi v
Giv  Gil RT ln
fi l

At equilibrium
fiv
Giv  Gil RT ln 0
fil
fi
i 
P
iv il isat f i v  f i l  f i sat

At Phase equilibrium, liquid and vapor phase of a pure species have the same temperature,
pressure, fugacity and fugacity coefficient.
Fugacity of a pure liquid
• The fugacity of pure species i as a compressed liquid:
fi P
Gi  Gisat RT ln sat Gi  Gisat sat Vi l dP (isothermal process )
fi Pi

fi 1 P
ln sat
  Vi l dP
fi RT Pi sat

Since Vi is a weak function of P

fi V l ( P  Pi sat )
ln  i
f i sat RT

V l ( P  Pi sat ) 
or f i  f i sat exp  i
 RT



sat
Fugacity of sat f
  i sat
pure species at i
Pi
saturated
pressure
 Vi l ( P  Pi sat ) 
(11.44)
sat sat
f i i Pi exp 
 RT


(Used for liquid)
Example: From data in the steam tables, determine a good estimate for
f/fsat for liquid water at 150 oC and 150 bar, where fsat is the fugacity of
saturated liquid at 150 oC.

This is <150 bar=15,000kPa, so

it is subcooled liquid

(11.44)

Note: For liquid, we can use equation

11.44. But if it is vapor, we cannot use
it. See next example
 Example 11.5. For H2O at a temperature of 300°C and for pressures up to 10,000 kPa (100
bar) calculate values of fi and ϕi from data in the steam tables and plot them vs. P.

For a state at P: Gi i (T )  RT ln f i

For a low pressure reference state: Gi* i (T )  RT ln f i *

fi 1  H i  H i* 
ln
fi 1
(G G *
)
ln *    ( Si  Si* ) Gi H i  TS i
 i  i
fi R T  f i * RT

The low pressure (say 1 kPa, it can be treated as idea gas) at 300°C:
f i * P * 1 kPa Si* 10.3450 J H i* 3076.8 J
gK g

For a given P and T, one can find Hi and Si from Steam Table, so fi can be calculated
For different values of P up to the saturated pressure 8,592.7kPa at 300°C, one obtains the values of fi,
and hence ϕi
For example: at P = 4,000 kPa, T = 300 oC, superheated steam: Hi = 2,962.0 J g-1and Si =6.3642 J g-1 K-1

from fi 1  H i  H i* *  f i 3,611( f i * ) 3,611 .0 * (1kPa) 3,611 .0kPa

ln    ( S i  S i ) Find
f i* R  T 
f i 3,611
i   0.9028
Similar calculations for other pressures, and also for saturated pressure P 4,000
sat
 i 0.7843 f i sat 6,738.9kPa
Fugacity and fugacity coefficient: species in solution
For species i in a mixture of real gases or in a solution of liquids (Eq. 11.29)
i i (T )  RT ln fˆi Fugacity of species i in solution

Multiple phases at the same T and P are in equilibrium when the fugacity of each constituent species
is the same in all phases:
fˆi  fˆi ...  fˆi
  

Gi R Gi  Gi ig

i i (T )  RT ln fˆi
iig i (T )  RT ln yi P
fˆi
i  iig RT ln
yi P
 (nG ) 
 i   Gi
 ni  P ,T ,n
j

For ideal gas Gi R RT ln ̂i

Gi R 0 The fugacity coefficient
fˆ
ˆi  i of species i in solution
fˆ yi P
ˆi  i 1 fˆi  yi P  pi
yi P
  nG R  nV R nH R Gi
R
 nG R  nV R nH R
d    dP  2
dT   dni d    dP  2
dT   ln ̂i dni
 RT  RT RT i RT  RT  RT RT i

Fix T and composition: V R  (G R / RT ) 

 
RT  P T , x

Fix P and composition: HR  (G R / RT ) 

 T  
RT  T  P,x

Fix T and P: ˆ  (nG R / RT ) 

ln i  
 ni  P ,T ,n j
Develop a general equation for calculation of ln ̂i values from compressibility-factor data.

R
 ( nG / RT ) 
ln ˆi  
 ni  P ,T , n j

nG R P dP
 (nZ  n) (Eq 6.49)
RT 0 P

P  ( nZ  n)  dP
ˆ
ln i   
0
 ni  P ,T ,n j P

 n   ( nZ ) 
  1   Z i
n
 i  P ,T ,n j  ni  P ,T , ni

ˆ P dP
ln i  ( Z i  1)
0 P Integration at constant temperature and composition

How to use Z or Z i to solve ̂i will not be tested

 The ideal solution
For ideal gas, we have iig Gi ig Giig (T , P )  RT ln yi
Similar to ideal solution:
G id  xi Gi  RT  xi ln xi
i i

Siid Si  R ln xi S id  xi Si  R  xi ln xi
i i

V id  xiVi
i
id
H id
H i H  xi H i
i
i

The Lewis/Randall Rule

fˆi id  xi f i ˆiid i
 Excess properties
• The mathematical formalism of excess properties is analogous to that of the residual
properties: E id
M M  M
 The excess Gibbs energy and the activity coefficient

E fˆi E
Gi RT ln i iid Gi  RT ln xi iig Giig  RT ln yi
Gi RT ln
xi f i
i Gi  RT ln i xi Gi R RT ln ̂i

Gi  xi Gi E  xi RT ln i

V R  (G R / RT )  (11.57)
V E  (G E / RT )   
  RT  P T , x Residual properties
RT  P Excess properties can
T , x can be solved by
be solved by HR  (G R / RT ) 
 T   their relationship
HE  (G E / RT ) 
 T   experimental VE, HE RT  T  P,x (11.58)
RT  T  P,x with PVT
and γi (will be  (nG R / RT ) 
E
 (nG / RT )  ln ˆi  
ln i   discussed in Chapter  ni  P ,T ,n j
 ni  P ,T ,n j
12) (11.59)

Gibbs/Duhem Equation  x d ln 
i
i i 0 (const . T , P )
Note the difference
f1 fˆ1
fi fˆ fˆi
i  ˆi  i i 
P yi P xi f i

Mi Mi M

iig Giig  RT ln yi iid Gi  RT ln xi

(11.24) (11.75) i Gi  RT ln i xi (11.92)

Gi E RT ln i Gi R RT ln ̂i

V E  (G E / RT ) 
 
RT  P T , x
Experimental accessible values:
HE  (G E / RT ) 
 T   activity coefficients from VLE data,
RT  T  P,x
VE and HE values come from mixing experiments.
 (nG E / RT ) 
ln i  
 ni  P ,T ,n j

GE
 xi ln i
RT i
Important application in phase-equilibrium
 x d ln 
i i 0 (const . T , P ) thermodynamics.
i