Lec 6-Solution Thermodynamics - Applications

Thermodynamics II
Lec 6-Solution Thermodynamics:

Applications-part 1
Dr.-Eng. Zayed Al-Hamamre
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

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Content

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VLE data collection
 The temperature T and P are uniform throughout the

vessel, and can be measured with appropriate
instruments.
 Vapor and liquid samples may be withdrawn for
analysis, and this provides experimental values for
mole fractions in the vapor {yi} and mole fractions
in the liquid {xi}
vapor mixture and a liquid
solution coexist in
vapor/liquid equilibrium

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Liquid phase property from VLE data
 For species i in the vapor mixture fî v  yiîv P (Fugacity cannot be measured directly)
 The criterion of vapor/liquid equilibrium, as given by Eq.

(11.48), is that
fî  fî
l v
fˆ li  y i îv P
 VLE measurements are very often made at pressure low enough (P ≤ 1 bar) that the vapor
phase may be assumed an ideal gas
fˆ l
i  fˆ v
i  yiP

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 Thus, the fugacity of species i (in both the liquid and vapor phases) is equal to the partial
pressure of species i in the vapor phase.
 Its value increases from zero at infinite dilution to Pisat for pure species i. this is illustrated by
the data of Table 12.1 for the methyl ethyl ketone(1)/toluene(2) system at 50Ԩ

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 The fugacities are plotted as solid lines.

 The straight dashed lines represent the
Lewis/Randall rule which expresses the
composition dependence of the constituent
fugacities in an ideal solution:
fˆ idi  x1 f i
 The Lewis-Randall rule provides the simplest
possible model for the composition dependence,
to which actual behavior may be compared

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Activity Coefficient
 The activity coefficient as defined by Eq. (11.90) formalizes this comparison:
fî fî
i   id
xi f i fî
 Thus the activity coefficient of a species in solution is the ratio of its actual fugacity
to the value given by the Lewis/Randall rule at the same T, P, and composition
 For the calculation of experimental values, both fî and fî are eliminated in favor of
id
measurable quantities:
yi P yP
i   i sat (i  1, 2,  , N ) (12.1)
xi f i xi Pi
 This is a restatement of Eq. (10.5), modified Raoult’s law, and is adequate for present
purposes, allowing easy calculation of activity coefficients from experimental low pressure
VLE data. Values from this equation appears in the last two columns of Table 12.1. 7

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 Experimental VLE data (measured P xi yi ) and vapor
pressures of pure-species determine activity coefficient
i
 The solid lines in both Figs 12.2 and
12.3, representing experimental values
of fî , become tangent to the
Lewis/Randall rule lines at xi = 1.
 This is a consequence of the
Gibbs/Duhem equation.
 Thus, the fî xi is indeterminate in
this limit, and application of
L’Hopital’s rule yields:
fî  dfî  (12.2)
lim   Ή
x i  dx i  x  0
i
xi  0
i 8

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 Equation (12.2) defines Henry’s constant Hi as the limiting slope of the fî  xi curve
at xi = 0. as shown by Fig. 12.3, this is the slope of a line drawn tangent to the curve
at xi = 0.
fî  xi H i
 It is of approximate validity for small values of xi
 Lewis-Randall rule (or Rault’s law) is for very rich component while Henry’s law is for dilute
component

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 Henry’s law is related to the Lewis/Randall rule through the Gibbs/Duhem equation.
ˆ by Gˆ i  μi gives:
 Writing Eq. (11.14) for a binary solution and replacing M
i
x1 d1  x2 d2  0 (const T, P)
 Differentiation of Eq. (11.46) at constant T and P yields: d  RTd ln fî

whence
x1 d ln fˆ1  x2 d ln fˆ2  0
Divide by dx1 and use: dx1 = -dx2
d ln fˆ1 d ln fˆ2 (12.4) OR

x1  x2 0
dx1 dx2
This is a special form of the Gibbs/Duhem equation.
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See Eq. (12.4)
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Excess Gibbs Energy
 For a binary system

GE
 x1 ln  1  x2 ln  2
RT
lim ln  i  ln  i
lim ln  i  0 xi  0
x i 1
 i : infinite dilution activity
coefficient
GE
lim  (0) ln  1  (1)(0)  0
x1 0 RT
GE
lim 0
x1 1 RT 13

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Excess Gibbs Energy

GE
 The limiting values of are equal to the infinite dilution limits of ln  1 and
x1 x2 RT
ln  2
GE GE
lim  ln  1 lim  ln  2
x10 x x RT x1 1 x x RT
1 2 1 2
Proof
x1  0 L’Hopital’s rule gives

d G E / RT 
GE G E / RT dx1
lim  lim  lim
x1  0 x x RT
1 2
x1  0 x1 1 x1  0 1
GE
Differentiating  x1 ln  1  x2 ln  2 with respect to x1
RT 14

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Excess Gibbs Energy
d (G E / RT ) d ln  1 d ln  2
 x1  ln  1  x2  ln  2 (B)
dx1 dx1 dx1
Recalling that the Gibbs-Duhem equation is
x1 d ln  1  x2 d ln  2  0 (const T, P)
Dividing by dx1 (It is not differentiation !)
d ln  1 d ln  2
x1  x2 0 (const T, P)
dx1 dx1
( 1 and 2 are related to each other)
Substituting into (B) d (G E / RT ) 

 ln 1
dx1 2
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Excess Gibbs Energy

 The limiting behaviors is to be
lim
GE
 lim

d G E / RT 
 lim ln 1  ln  1
x1 0 x x RT
1 2
x1 0 dx1 x1 0 2
Similarly,
GE
lim  ln  2
x2 0 x x RT
1 2
 Because the activity coefficient of a species in solution becomes unity as the species becomes
pure, each ln i (i  1,2) tends to zero as xi → 1.
 At the other limit, where xi → 0 and species i becomes infinitely dilute, ln i approaches a
finite limit, namely, ln i 
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Data Reduction with Margules Equation
One-parameter Margules equation
GE
 A = constant
x1 x2 RT
 This symmetric behavior is not sufficient for most nonideal mixtures)
Two-parameter Margules equation
GE
 A21 x1  A12 x2
x1 x2 RT (12.9a) a linear composition dependence
or
GE
 (A 21 x1  A12 x2 ) x1 x2
RT
A21, A12 fitting constants for experimental VLE data
A reasonable approximation for many types of binary mixtures
A commonly used empirical model of solution behavior 19

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 Expressions for ln1 and ln2 are derived from Eq. (12.9b) by application of Eq.
(11.96).

  nG E / RT 
ln  i  


 ni  P,T ,n j
 Converting mole fractions into mole numbers in the two-parameter Margules equation
2 2
nG E A21n1 n2  A12 n1n2
  A21n1  A12 n2 
n1n2

RT n1  n2 2 n1  n2 2
Differentiating with respect to n1
ln  1  

  nG E / RT   
2 A21n1n2  A12 n2
2
2
2
A21n1 n2  A12 n1n2
2

 n 1  P ,T ,n2 n1  n 2 2
n1  n2 3
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Converting to mole fractions
2
 2 2

 2 A21 x1 x2  A12 x2  2 A21 x1 x2  A12 x1 x2  x2 A12  2 A12 x1  2 A21 x1 
2

  nG E / RT 
ln  1  
  x22 A12  2( A21  A12 ) x1 

 n1  P ,T ,n2
Similarly

  nG E / RT 
ln  2  

 x12  A21  2 ( A12  A21 ) x 2 

 n 2  P ,T , n1
 For the limiting conditions at infinite dilution
ln  1  A12 (as x1 0)
ln  2  A21 (as x2 0)
 Infinite dilution activity coefficient has a significant meaning ! 21

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A12 = 0.372 A21 = 0.198
MEK / toluene system
Fig. 12.6
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MEK / toluene system A12 = 0.372 A21 = 0.198
nG E
  0.198 x1  0.372 x2  x1 x2
RT 23

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Correlation of P-x-y data
Modified Raoult’s law
P  x1 1 P1sat  x2 2 P2sat

x1 1 P1sat
y1  (at fixed T )
x1 1 P1  x2 2 P2
sat sat
 Vapor phase is assumed to be an ideal gas mixture

 Liquid phase nonideality is described by two-para
meter Margules equation
ln  1  x22  A12  2( A21  A12 ) x1 
( solid lines obtained from
ln  2  x12  A21  2( A12  A21 ) x 2  BUBL P calculation )
 Optimal values of A21, A12 reproduce experimental Pxy data 26

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Margules equation with A21 = –0.72 A12 = –1.27

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Models for the excess Gibbs energy
 GE/RT is a function of T, P and composition, but is a very weak function of P

( almost independent)
GE
 g x1 , x2 ,, xN  const T
RT
Redlich/Kister expansion (power series)
GE
 A  B x1  x2   C  x1  x2   
2
const T
x1 x2 RT
If B = C = ··· = 0
GE
A one-parameter Margules equation
x1 x2 RT
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Redlich/Kister expansion
ln  1  Ax22 ln  2  Ax12 symmetric
Infinite dilution activity coefficient
ln  1  A ln  2  A
If C = ··· = 0
GE
 A  B x1  x2 
x1 x2 RT
GE/x1x2 RT is linear in x1. It is equivalent to
GE
 A21x1  A12 x2 two-parameter Margules equation
x1 x2 RT
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Van Laar equation
Two-parameter model
 The first theoretical model for activity coefficient
 A  Bx1  x2   Ax1  x2   B x1  x2    A  Bx1   A  Bx2

x1 x2
G E / RT
A  B  1 A21
 A  B  1 A12
x1 x2 x x
 1  2 GE A12 A21

 or 
G / RT
E
A21 A12 x1 x2 RT A12 x1  A21 x2
From 
  nG E / RT 
ln  i  


 ni  P,T ,n j
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Van Laar equation

2 2
 A x   A x 
ln  1  A12 1  12 1   1  21 2 
ln  2  A21
 A21 x2   A12 x1 
Infinite dilution activity coefficient
ln  2  A21

ln   A12

1
Concept of local composition models

 In liquid solutions, local compositions are different from overall mixture composition. Local
compositions account for the short-range order, nonrandom orientations of molecules resulting
from differences in molecular size and intermolecular forces.
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Bulk composition Local composition Red(1) / Blue(2)
x1 = 10 / 25 x11 = 2 / 4
x11  x1
 Nonrandom behavior caused by intermolecular interaction ( e.g.
red-red pairing is more favored than red-blue pairing)
Wilson equation
GE
  x1 ln  x1  x2 12   x2 ln  x2  x1 21 
RT
 12  21 
ln  1   ln x1  x2 12   x2   
x 
 1 2 12
x  x 2  x 
1 21 
 12  21 
ln  2   ln x2  x1 21   x1   
x 
 1 2 12
x  x2  x 
1 21 
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 For infinite dilution
ln  1   ln 12  1   21 ln  2   ln  21  1  12
 Local composition models can be generalized to multicomponent systems only with binary
parameters.
NRTL equation (Non-Random-Two-Liquid)
GE G21 21 G12 12
 
x1 x2 RT x1  x2G21 x2  x1G12
  G 
2
G12 12    G 
2
G21 21 
ln  1  x2  21   
2 21
 ln  2  x1
2
 12  12
  
  x1  x2G21   x2  x1G12     x2  x1G12   x1  x2G21  
2 2
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G12  exp  12  G21  exp  21 
b12 b21
 12   21 
RT RT
, b12, b21 are parameters independent of T and composition
 Infinite dilution activity coefficient
ln  1   21   12 exp 12  ln  2   12   21 exp  21 

 
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Thermodynamic Consistency Tests
 The Gibbs–Duhem equation provides a general relation for the partial molar properties of
different species in a mixture that must always be true.
 The activity coefficient of different species can be related to one another.
 Such interrelation can be used to judge the quality of experimental data.
 The development that follows is based on the relation between activity coeffi cients in a
binary mixture of species a and b
the excess Gibbs energy for a binary mixture can be written as:
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 Therefore, to evaluate experimental data for thermodynamic consistency.
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Excursion
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Excursion
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Excursion
Bubble point calculations
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Excursion
Bubble P calculations
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Excursion
Bubble T calculations
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Excursion
Dewpoint caclulations
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Excursion
Dew p calculations
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Excursion
Dew T calculations
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Excursion
Flash caclulations
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Excursion
Flash caclulations
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Excursion
Flash caclulations
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Project
The experimental VLE data for 2-propanol (1)/Water (2) at 45 oC are given in the table
below.
1- Check the consistency of these data using the
area test.
2- Is it possible to use the two-parameters
Margules model for such system? Why? If yes,
estimate the best parameters: A12 and A21.
3- Is it possible to use Van Laar model for such
system ? Why? If yes, estimate best parameters:
 and A21
A12 .
4- Construct the P-x-y diagram from the above
two models and using the experimental data .
5- Plot ln1, ln2 , and GE/RT versus x1 from the
above two models and using the experimental data
- Comment on the results.

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Thermodynamics II

Lec 6-Solution Thermodynamics:

Dr.-Eng. Zayed Al-Hamamre

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

 The temperature T and P are uniform throughout the

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Liquid phase property from VLE data

 The criterion of vapor/liquid equilibrium, as given by Eq.

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Liquid phase property from VLE data

 The fugacities are plotted as solid lines.

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Liquid phase property from VLE data

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Liquid phase property from VLE data

x1 d1  x2 d2  0 (const T, P)

 Differentiation of Eq. (11.46) at constant T and P yields: d  RTd ln fˆi

Divide by dx1 and use: dx1 = -dx2

d ln fˆ1 d ln fˆ2 (12.4) OR

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

See Eq. (12.4)

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Liquid phase property from VLE data

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

 For a binary system

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Excess Gibbs Energy

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Recalling that the Gibbs-Duhem equation is

Substituting into (B) d (G E / RT ) 

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Excess Gibbs Energy

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Liquid phase property from VLE data

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Two-parameter Margules equation

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Data Reduction with Margules Equation

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

 Infinite dilution activity coefficient has a significant meaning ! 21

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Data Reduction with Margules Equation

A12 = 0.372 A21 = 0.198

MEK / toluene system

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Data Reduction with Margules Equation

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Correlation of P-x-y data

Modified Raoult’s law

P  x1 1 P1sat  x2 2 P2sat

 Vapor phase is assumed to be an ideal gas mixture

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Margules equation with A21 = –0.72 A12 = –1.27

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan

Correlation of P-x-y data

Chemical Engineering Department | University of Jordan | Amman 11942, Jordan