06 Chapter 12 (Compiled) PDF

CHAPTER 12
Solution Thermodynamics
(Application)
Muhammad Tahir
Faculty of Chemical and Energy Engineering
Universiti Teknologi Malaysia, 81310 UTM
Johor, Johor Bahru, Malaysia
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Topic Outcomes
Week Topic Topic Outcomes
10-11 Solution Thermodynamics: Application It is expected that students are able to:
• Liquid Phase Properties from VLE data • Define the terms of fugacity and fugacity
o Fugacity and fugacity coefficient coefficient, activity, and activity
o Activity and activity coefficient coefficient.
o Excess Gibbs energy and activity
coefficient • Analyze experimental VLE data for
o Models for excess Gibbs energy getting a simple model of excess Gibbs
energy.
• Property changes of mixing
o Heat effects of mixing processes • Identify at which the fluid can be
o Heat of solution assumed as an ideal or non-ideal
o Enthalpy/concentration Diagram solution.
• Derive and calculate the activity

coefficient from experimental data and
model excess Gibbs energy.
• Evaluate the property changes due to

mixing of given system and conditions.
• Calculate the heat requirement for given

process and conditions.

Scope of Lecture
Liquid Phase Properties from VLE data
Other Empirical Models for i
Property Changes of Mixing
Heat Effects of Mixing Processes

Introduction
Objective: To obtain below information from

experimental data:
• Vapor/liquid equilibrium (VLE) data

• Activity coefficient
• Activity coefficient correlations

Liquid-phase Properties
From VLE Data

VLE Data Collection
For species i in the vapor mixture
fî v  î y iP P T
VLE criteria (Chap. 11)

Sampling point {yi}
fî l  fî v {xi}
Therefore,
fî l  î y iP
VLE measurements are very often made at pressure low enough

(P≤ 1 bar) that the vapor phase may be assumed as ideal gas.
î  1 fî l  fî v  y iP

Fugacity
Thus the fugacity of species i (in both the liquid & vapor phases) is
equal to the partial pressure of species i in vapor phase. Its value
increase from “0” at infinite dilution ( xi = yi → 0 ) to Pisat for species i.
Note : For pure substance

fî l  fî v  y iP  y iPisat
x i  y i  1  fî l  fî v  P  Pisat
Fugacity in ideal solution,
fî id  x i f i Lewis/Randall rule

Activity Coefficient
VLE criteria (previous)
fî l  fî v
 i x i f i  î y iP
x iPisat 1
If gas phase is an ideal-gas mixture, we get modified Raoult’s Law
y iP
i  Chap. 10
x iPisat
→ Easy calculation of activity coefficient (i) from experimental low-P

VLE data

VLE Data for M.E Ketone(1)/ Toluene(2) at 50 C
P/kPa xl y1 fˆ1  y 1P fˆ2  y 2P 1 2

12.30( P2sat) 0.0000 0.0000 0.000 12.300 1.000
15.51 0.0895 0.2716 4.212 11.298 1.304 1.009
18.61 0.1981 0.4565 8.496 10.114 1.188 1.026
21.63 0.3193 0.5934 12.835 8.795 1.114 1.050
24.01 0.4232 0.6815 16.363 7.697 1.071 1.078
25.92 0.5119 0.7440 19.284 6.636 1.044 1.105
27.96 0.6096 0.8050 22.508 5.542 1.023 1.135
30.12 0.7135 0.8639 26.021 4.099 1.010 1.163
31.75 0.7934 0.9048 28.727 3.023 1.003 1.189
34.15 0.9102 0.9590 32.750 1.400 0.997 1.268
36.09(P1sat) 1.0000 1.0000 36.090 0.000 1.000
y iP
 i x iP  î y iP i 
x iPisat
Note: M.E Ketone, methyl ethyl ketone Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Fugacities for M.E Ketone(1)/ Toluene(2) at 50 C
Lewis/Randall rule fî id  x i f i

Henry’s Law
In the limit, xi → 0, fî becomes zero. Thus the ratio fî /x i is

indeterminate in this limit and application of 1’Hôpital’s rule yields :
fî  dfîi 
lim   Hi
x i 0 x  
i  dx i  x i 0
The equation of the tangent line to the curve at xi = 0 express

Henry’s law:
fî  x iHi
Henry’s law applies to a species as it approaches infinite dilution in

a binary solution, and the Gibbs/Duhem equation insures validity of
the Lewis/ Randell rule for the other species as it approaches purity.
Composition Dependence of Fugacity for
Species i in a Binary Solution

Method to Predict i
Let’s go to the lab and carry out an experiment to get VLE data
(P, x1, y1) for Methyl Ethyl Ketone(1)/ Toluene(2) at T = 50 C.
Note: P is low, so we could assume an ideal-gas mixture,

hence could use the Modified Raoult’s Law.
Plot of Px1y1 diagram

Method to Predict i (Cont.)
First we will use the VLE data for the binary system to,
y iP
1. Calculate 1 and 2 from Modified Raoult’s Law  i 
x iPisat
E
GE G
2. Calculate and for binary system from
RT x 1x 2RT
GE Divide by x1x2 GE 1
 x 1ln  1  x 2ln  2  x1ln  1  x 2ln  2 
RT x 1x 2RT x 1x 2
GE GE
3. From VLE data, tabulate ln  1 , ln 2, , vs. x1
RT x 1x 2RT

P/kPa x1 y1 lnγ1 lnγ2 GE/RT GE/x1x2RT

sat
12.3(P2 ) 0 0 0 0
15.51 0.0895 0.2716 0.266 0.009 0.032 0.389
18.61 0.1981 0.4565 0.172 0.025 0.054 0.342
21.63 0.3193 0.5934 0.108 0.049 0.068 0.312
24.01 0.4232 0.6815 0.069 0.075 0.072 0.297
25.92 0.5119 0.744 0.043 0.1 0.071 0.283
27.96 0.6096 0.805 0.023 0.127 0.063 0.267
30.12 0.7135 0.8639 0.01 0.151 0.051 0.248
31.75 0.7934 0.9048 0.003 0.173 0.038 0.234
34.15 0.9102 0.959 -0.003 0.237 0.019 0.227
sat
36.09(P1 ) 1 1 0 0

Diagram (Experimental Data)
Pxy data Liquid-phase properties

40 0.4
GE/x1x2RT
30 P-x1 0.3
P/kPa
20 0.2
P-y1 lnγ1 lnγ2
10 0.1
GE/RT
0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x1
x1, y1

(a)
P1sat = 0.1799 bar, P2sat = 0.2290 bar EtOH/Acetonitrile
4.0
y iP
γi  3.5
x iPisat 3.0
Activity coeficient
2.5
GE g1
 x 1lnγ1  x 2lnγ 2 2.0
RT 1.5
g2
GE  8.314J/mol .K 313.15K x 1lnγ1  x 2lnγ 2 

Poly. (g1)
1.0
0.5 Poly. (g2)
P (bar) x1 y1 1 2 E
G /RT G
E 0.0
sat 0.0 0.2 0.4 0.6 0.8 1.0 1.2
P2 0.2290 0.0000 0.0000 1 0 0
x1
0.2402 0.0281 0.0663 3.1503 1.0077 0.0397 103.3123
0.2558 0.0831 0.1596 2.7309 1.0238 0.1051 273.5792
0.2661 0.1415 0.2435 2.5454 1.0239 0.1525 397.0878 EtOH/Acetonitrile
0.2742 0.2314 0.3117 2.0531 1.0723 0.2201 573.0318
0.2784 0.2884 0.3442 1.8469 1.1204 0.2578 671.2813 0.6
0.2801 0.3330 0.3684 1.7225 1.1582 0.2791 726.5211 0.5
0.2809 0.4040 0.4115 1.5904 1.2112 0.3017 785.3650
0.4
0.2812 0.4140 0.4140 1.5631 1.2279 0.3053 794.7298 GE/RT
0.2810 0.4813 0.4376 1.4202 1.3305 0.3169 825.1209 0.3
GE/RT
0.2766 0.5623 0.4753 1.2996 1.4479 0.3094 805.4809
0.2
0.2681 0.6965 0.5344 1.1434 1.7960 0.2711 705.7658 Poly. (GE/RT)
0.2580 0.7885 0.5987 1.0889 2.1377 0.2279 593.2164 0.1
0.2418 0.8681 0.6687 1.0353 2.6521 0.1588 413.4602 0
0.2189 0.9252 0.7708 1.0137 2.9290 0.0930 242.1242 0.0 0.2 0.4 0.6 0.8 1.0
0.2012 0.9659 0.8664 1.0032 3.4423 0.0452 117.7528 X1
sat
P1 0.1799 1.0000 1.0000 1 0 0
17
Method to Predict i (Cont.)
We will now develop a correlation of i from the data.
We are doing to see specifically how the Margules equation

was developed.
This is DATA REDUCTION METHOD (empirical)

Data Reduction
Note: GE/x1x2RT vs x1 is more linear than others
Let’s gives the following mathematical linear relation
GE
 A 21x 1  A 12 x 2
x 1x 2RT
GE
When, x1  1, x2  0  A 21 1  A 12 0   0.198
x 1x 2RT
GE
x1  0, x2  1  A 210   A12 1  0.372
x 1x 2RT
So, A 21  0.198
i.e. intersections on vertical axis at both ends
A12  0.327
Mathematical Linear Relation
Rearrange
GE GE
 A 21x 1  A 12 x 2  A 21x 1  A 12 x 2 x 1x 2
x 1x 2RT RT
Multiply n on left side and nn2/n2 on the right side x1=n1/(n1+n2)

x2=n2/(n1+n2)
E
nG nx nx nn
 A 21x1  A 12 x 2  1 2 2  A 21n1  A 12 n2  1 2 2
RT n n n1=(n1+n2)
Substitute into
 n1n2 
E
 nG /RT    A n
21 1  A n
12 2  2 
ln  i   i
 ln  1   n
n 
 i  P,T,n j  n1 
  P,T,n2

Correlation for i
n  nn A
ln  1  A 21n1  A 12 n2  22  n1n2  2n 3   1 22 21
n  n
For ni = xin
ln 1  x 2 A 21x1  A12 x 2 1 2x 1   x1A 21 

 x 2 A 21x1  2A 21x12  A 12 x 2  2A 12 x1x 2  x1A 21 

 x 2 2A 21x1  2A 21x12  2A 12 x1x 2  A 12 x 2 
 x 2 2A 21x11  x1   2A 12 x1x 2  A12 x 2 
 x 2 2A 21x1x 2  2A 12 x1x 2  A12 x 2 
ln  1  x 22 2A 21  A 12 x1  A 12 

Margules Equation
We get the correlation for activity coefficient
ln  1  x 22 A 12  2A 21  A 12 x1 
Similarly, differentiate GE with respect to

 A 21x 1  A 12 x 2 x 1x 2
component 2 RT
ln  2  x12 A 21  2A 21  A 21 x 2 
GE
Note: All these were derived from  A 21x 1  A 12 x 2
x 1x 2RT
All these equations (above) are the Margules Equation

→ They represent a commonly used empirical model of solution
behavior
Step 1
For various values of x1 and the experimental data for vapor
pressure (Psat), and using A12 = 0.372 and A21 = 0.198,
1. Recalculate y1 and P using BULB P (Chap. 10) calculation and

Modified Raoult’s Law
y1P  x1 1P1sat y 2P  x 2 2P2sat
P  x1 1P1sat  x 2 2P2sat
x 1 1P1sat
y1 
x 1 1P1sat  x 2 2P2sat

Step 2
2. Recalculate ln 1, ln 2, GE/RT, GE/x1x2RT using the Margules
correlations.
GE
 0.198x 1  0.372x 2 x1x 2
RT
ln  1  x 22 0.372  20.198  0.372 x1 
ln  2  x12 0.198  20.132  0.198 x 2 
Replot the VLE diagrams for Methyl Ethyl Ketone(1)/ Toluene(2) at T

= 50 C (New Data: Highlighted with yellow color).
This are represented by solid lines in Figure (Pxy Data & Liquid-
phase Properties)
→ Correlations fit the data very well

E E
A12 A21 x1 y1 (M) P/kPa (M) lnγ1 (M) lnγ2 (M) G /RT (M) G /x1x2RT (M)
0.372 0.198 0 0 12.3 0.372 0 0 0.372
0.372 0.198 0.0895 0.2759 15.5302 0.2826 0.0041 0.0290 0.3564
0.372 0.198 0.1981 0.4637 18.7375 0.1949 0.0187 0.0536 0.3375
0.372 0.198 0.3193 0.5977 21.7564 0.1209 0.0443 0.0688 0.3164
0.372 0.198 0.4232 0.6835 24.0788 0.0748 0.0714 0.0728 0.2984
0.372 0.198 0.5119 0.7453 25.9589 0.0462 0.0964 0.0707 0.2829
0.372 0.198 0.6096 0.8057 27.9793 0.0244 0.1241 0.0633 0.2659
0.372 0.198 0.7135 0.8638 30.1136 0.0102 0.1516 0.0507 0.2479
0.372 0.198 0.7934 0.9052 31.7630 0.0041 0.1699 0.0383 0.2339
0.372 0.198 0.9102 0.9609 34.1993 0.0004 0.1899 0.0175 0.2136
0.372 0.198 1 1 36.09 0 0.198 0 0.198
Note: M, Calculated using Margules equation Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Diagram (Margules Equation)

40 0.4
A12
GE/x1x2RT
30 0.3
P-x1
P/kPa
20 0.2 A21
P-y1 lnγ1 lnγ2
10 0.1
GE/RT
0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x1
x1, y1

VLE Data for Chloroform/1,4-Dioxane at 50 C
P/kPa x1 y1 lnγ1 lnγ2 GE/RT GE/x1x2RT

15.79(P2sat) 0.0000 0.0000 0.000 0.000
17.51 0.0932 0.1794 -0.722 0.004 -0.064 -0.758
18.15 0.1248 0.2383 -0.694 -0.000 -0.086 -0.790
19.30 0.1757 0.3302 -0.648 -0.007 -0.120 -0.825
19.89 0.2000 0.3691 -0.636 -0.007 -0.133 -0.828
21.37 0.2626 0.4628 -0.611 -0.014 -0.171 -0.882
24.95 0.3615 0.6184 -0.486 -0.057 -0.212 -0.919
29.82 0.4750 0.7552 -0.380 -0.127 -0.248 -0.992
34.80 0.5555 0.8378 -0.279 -0.128 -0.252 -1.019
42.10 0.6718 0.9137 -0.192 -0.355 -0.245 -1.113
60.38 0.8780 0.9860 -0.023 -0.824 -0.120 -1.124
65.39 0.9398 0.9945 -0.002 -0.972 -0.061 -1.074
69.36(P1sat) 1.0000 1.0000 0.000 0.000

Diagram (Experimental Data)

80 0 0.2 0.4 0.6 0.8 1
0
60 -0.2
GE/RT
-0.4 lnγ1
P/kPa
40 P-x1 -0.6
P-y1 -0.8 lnγ2
20
-1
-1.2 GE/x1x2RT
0
0 0.2 0.4 0.6 0.8 1 -1.4
x1
x1, y1

VLE Data for Chloroform/1,4-Dioxane at 50 C
E E
A12 A21 x1 y1 (M) P/kPa (M) lnγ1 (M) lnγ2 (M) G /RT (M) G /x1x2RT (M)
-0.72 -1.27 0 0 15.79 -0.72 0 0 -0.72
-0.72 -1.27 0.0932 0.1871 17.5715 -0.6763 -0.0024 -0.0652 -0.7713
-0.72 -1.27 0.1248 0.2461 18.2423 -0.6567 -0.0048 -0.0861 -0.7886
-0.72 -1.27 0.1757 0.3373 19.4227 -0.6205 -0.0112 -0.1183 -0.8166
-0.72 -1.27 0.2 0.3793 20.0374 -0.6016 -0.0156 -0.1328 -0.8300
-0.72 -1.27 0.2626 0.4826 21.8044 -0.5486 -0.0316 -0.1674 -0.8644
-0.72 -1.27 0.3615 0.6294 25.2587 -0.4556 -0.0742 -0.2121 -0.9188
-0.72 -1.27 0.475 0.7674 30.4829 -0.3425 -0.1562 -0.2447 -0.9813
-0.72 -1.27 0.5555 0.8430 35.1350 -0.2630 -0.2410 -0.2532 -1.0255
-0.72 -1.27 0.6718 0.9205 43.2581 -0.1572 -0.4102 -0.2402 -1.0895
-0.72 -1.27 0.878 0.9867 60.1916 -0.0251 -0.8756 -0.1288 -1.2029
-0.72 -1.27 0.9398 0.9950 65.0998 -0.0064 -1.0632 -0.0700 -1.2369
-0.72 -1.27 1 1 69.36 0 -1.27 0 -1.27

Diagram (Margules Equation)

80 0 0.2 0.4 0.6 0.8 1
0
60 -0.2
GE/RT
-0.4 lnγ1
P-x1
P/kPa
40 -0.6
lnγ2
P-y1 -0.8
20
-1
-1.2 GE/x1x2RT
0
0 0.2 0.4 0.6 0.8 1 -1.4
x1, y1 x1

Other Empirical Models for
i

Redlich/Kister Expansion
GE
 A  Bx 1  x 2   Cx 1  x 2  
2
x 1x 2RT
GE
For truncation after 1 term, A
x 1x 2RT
 nGEi /RT 
Apply equation ln  i    to give
 ni  P,T,n j
ln  1  Ax 22 ln  2  Ax 12
Where infinite dilution
ln  1  ln  2  A

Van Laar Equations
GE
For truncation after 2 term,  A  Bx 1  x 2 
x 1x 2RT
If we define
A  B  A 21
we can show that this equal
A  B  A12 to Margules equation.
Substitute into
Margules eqn.
GE
 A 21x 1  A 12 x 2
x 1x 2RT
GE
 A  B x 1  A  B x 2  Ax 1  Bx 1  Ax 2  Bx 2
x 1x 2RT
GE
 A x 1  x 2   Bx 1  x 2   A  Bx 1  x 2 
x 1x 2RT
Van Laar Equations (Cont.)
x1x 2
E
 A   Bx1  x 2   A   Bx 1  A   Bx 2
G /RT
Let
1 1
A   B  and A   B 
A 21 A 12
So,
x 1x 2 x1 x2 A 12 x 1  A 21x 2
  
GE /RT A 21 A 12 A 21A 12
GE A 21A 12

x 1x 2RT A 12 x 1  A 21x 2

Fit GE/RT data to Van Laar eqn. by linear least squares
x 1x 2 x1 x2 1 1
E
   x 1  x2
G /RT A 21 A 12 A 21
   A 12

y  mx  c
Slope Intercept
1 1
A 21  A 12 
Slope  intercept Intercept

 nGEi /RT 
Apply equation ln  i    we get
 ni  P,T,n j
2 2
 A 12 x1   A 21x 2 
ln  1  A 12 1
   ln  2  A 21 1
  
 A 21x 2   A 12 x1 
At infinite dilution
x1  0 ln  1  A 12
x2  0 ln  2  A 21

Features
Features of Margules, Redlich/Kister & van Laar Equations
Applicable to binary mixture only
Empirical (fitting VLE data)
No theoretical foundation
i is independent of P
Applicable at constant T

Local Composition Models
Theoretical development in the molecular thermodynamics of
liquid-solution behavior are often based on the concept of local
composition.
Local compositions →presumed to account for the short-range order

& non random molecular orientations that results from differences
in molecular size and intermolecular forces.
Improved version
of UNIQUAC
Wilson UNIQUAC
G.M. Wilson (1964) NRTL Abrams & Prausnitz UNIFAC
Renon & Prausnitz Based on molecular

groups’ contribution
Note: NRTL, Non-Random-Two-Liquid; UNIQUAC, Universal Quasi-Chemical

Wilson Equation
GE  
  x i  ln  x j  ij 
RT i  j 
From this we will get the correlation for gamma
  x 
ln  i  1 ln  x j  ij    k ki
 j  k  x j  ij
j
Where
ij  1 for i  j
Binary parameter
Vj  a ij
 ij  exp i  j
Vi RT
Molar volume of pure liquid i at T

Wilson Equation for Binary System
GE
  x1 lnx1  x 2 12   x 2 lnx 2  x1 21 
RT
That gives,
 12  21 
ln  1   lnx1  x 2 12   x 2   
 x1  x 2 12 x 2  x 1 21 
 12  21 
ln  2   lnx 2  x1 21   x1
  
 x1  x 2 12 x 2  x1 21 
Where,
ln  1   ln 12  1   21 ln  2   ln  21  1  12

Parameter Values
Note: a12, a21, b12, b21 (units, cal mol–1); V1, V2 (units, cm3 mol–1 (Refer table 12.5 in the text book)
NRTL Equation
Containing 3 parameter for binary And

system,
b12 b 21
 12   21 
GE G21 21 G21 12 RT RT
 
x 1x 2RT x 1  x 2G21 x 2  x 1G12
  2
 , b12, b21, parameters specific to
2 G21  G12 12
lnγ1  x  21     a particular pair of species, are
  x 1  x 2G21  x 2  x 1G12  
2 2
independent of comp. & temp.
2
  G12  G21 21 
2
ln  2  x 1  21    
  x 2  x 1G12   x 1  x G
2 21 2
 For infinite dilution,
Here, ln  1   21   12 exp  α 12 
G12  exp α 12 
ln  2   12   21exp  α 21 
G21  exp  α 21 
UNIQUAC & UNIFAC
More information on UNIQUAC equation

and UNIFAC method in APPENDIX H

Tutorial 1
The following is a set of VLE data for the system methanol(1)/water(2) at
333.15 K.
P/kPa x1 y1 P/kPa x1 y1
19.953 0.000 0.000 60.614 0.528 0.809
39.223 0.169 0.571 63.998 0.604 0.838
42.984 0.217 0.627 67.924 0.680 0.873
48.852 0.304 0.694 70.229 0.726 0.892
52.784 0.368 0.735 72.834 0.778 0.914
56.652 0.446 0.774 84.560 1.000 1.000
Find parameter values for the Margules equation that provide the best fit
of GE/RT to the data, and prepare a Pxy diagram that compares the
experimental points with curves determined from the correlation.

Tutorial 2
The following is a set of VLE data for the system acetone(1)/methanol(2) at
55 C.
Find parameter values for the Margules equation that provide the best fit
of GE/RT to the data, and prepare a Pxy diagram that compares the
experimental points with curves determined from the correlation.
Tutorial 3
The following is a set of VLE data for the system methanol(1)/water(2) at

333.15 K.
P/kPa x1 y1 P/kPa x1 y1
19.953 0.000 0.000 60.614 0.528 0.809
39.223 0.169 0.571 63.998 0.604 0.838
42.984 0.217 0.627 67.924 0.680 0.873
48.852 0.304 0.694 70.229 0.726 0.892
52.784 0.368 0.735 72.834 0.778 0.914
56.652 0.446 0.774 84.560 1.000 1.000
a. Repeat Tutorial 1 for the Wilson Equation

b. Repeat Tutorial 1 for the Van Laar Equation

Tutorial 4
The following is a set of VLE data for the system acetone(1)/methanol(2) at
55 C.
a. Repeat Tutorial 2 for the Wilson Equation

b. Repeat Tutorial 2 for the Van Laar Equation
Property Changes of
Mixing

Excess Properties
Equations in Chap.11 are expressions for the properties of ideal

solutions.
Each may be combined with the defining equation for an excess

property:
ME  M  Mid
GE  G   x iGi  RT x ilnx i

i i
SE  S   x iSi  R x ilnx i
i i
VE  V   x i Vi
i
HE  H   x iHi
i

Property Change of Mixing (Mmix)
Property changes of mixing,
Mmix  M   x iMi
i
Molar (or unit–mass) Molar (or unit-mass) All at the

solution property pure species property same T & P
GE  Gmix  RT x ilnx i

i
Energy SE  Smix  R x ilnx i

change of i
mixing
VE  Vmix
HE  Hmix

Mmix for Ideal Solution
For ideal solution, excess property, ME = 0, so
mix  RT x ilnx i

Gid Sidmix  R x ilnx i
i i
id
Vmix 0 Hidmix  0
Mid
mix  Mid
  x iMi ― Mmix  M   x iMi
i i
Mmix  Mid
mix  M  M
id
Mmix  M   x iMi ME  M  Mid

i ME  Mmix  Mid
mix

Example for Ideal Solution
A, 25 C
Solution A + B 25 C
B, 25 C Q
Energy balance,
 W
Q   H
  E  E  H

k p
 H
Q  H  m H id  m  m
 AH 
 BH
out in A B A B
 H
Q   iHi   m iHi   m iHi
 id  m Hidmix  0
 0
Q
Example for Non-Ideal Solution
A, 25 C
Solution A + B 25 C
B, 25 C Q
Energy balance,
 W
Q   H
  E  E  H

k p
 m
Q  m
 A BH  m
 AHA
 m
 BHB
 A BH   iHi
 m

  H
Q   m
mix 
  iHi   m iHi
  H
Q 
m ix
If the system is adiabatic, what will be the outlet temperature?

Example for Non-Ideal Solution
Non-ideal solution of a + b flow in a pipe. Determine the

stream enthalpy (H).
H  H0f, 298  CP T
We need,
Heat of formation of the solution
Heat capacity of solution

Heat Effects of Mixing
Processes

(1) Enthalpy of Solution
2 ways to solve energy balance involving the heat of mixing
1. Use the enthalpy of solution (H)
2. Use the heat of mixing (Hmix)
From equation 12.39
H  Hmix   x iHi
i
H could be found by using Hx diagram such as Fig. 12.17

(H2SO4) and Fig. 12.19 (NaOH/H2O)

Hx Diagram H2SO4/H2O

Hx Diagram NaOH/H2O

59
60
Example 1
A single-effect evaporator concentrations 10,000 (lbm)(hr–1) of 10% (by
weight) aqueous solution NaOH to 50%. The feed enters at 70 (F). The
evaporator operates at an absolutes pressure of 3 (inHg), and under
these conditions the boiling point of a 50% solution of NaOH is 190 (F).
What is the heat-transfer rate in the evaporator?

Solution 1
8000 (lbm) of superheated
steam at 3 (inHg) and 190 (F)
Feed at 70 (F) 10,000

(lbm) of 10% NaOH
2000 (lbm) of 50% NaOH at

190 (F)
Q
Steady-state, steady flow mass balance: In = Out
Overall mass balance: m

1m
 2 m
3
Component i mass balance: x i,1m

 1  x i,2m
 2  x i,2m
3
For NaOH: 0.110,000   0.5m

 2   0m
 3
For H2O: 0.910,000   0.52,000   1m

 3

Solution 1 (Cont.)
Energy balance,
 H
Q  H  m  m
 3H  m
 2H 
 1H
out in 3 2 1
From Hx diagram (Fig. 12.19) and steam table

Fig. 12.19
  8000 1146   2000 215   10000 lb /hr 34 BTU/lb 
Q m m
steam table
  9260000 BTU/lb Heat duty of evaporation

Q m
Note: Reference conditions for H2O for the NaOH Hx diagram (Fig. 12.19) is similar to the textbook’s Steam Table
(2) Heat of Solution
If we do not have Hx diagram, calculate Hmix using heat of
solution (͠H298) or heat of formation of solution (Hof, 298 )

Heat of solution H298
~
 diagram, Fig. 12.14
Solute 25 C
Solution 25 C
Liquid 25 C Q
  H
As shown before, Q   H
mix xH i i
Example, LiCl s  12H2Ol  LiCl 12H2O

~
H298  33,614J (basis per mol solute) See Fig. 12.14
~
Hmix,298  nsoluteH 298
Heat of Formation of Solution (Hof, 298)
Elements
Solute 25 C
Solution 25 C
Liquid 25 C Q
Example, Li  1/2Cl 2  12H2Ol  LiCl 12H2O
H0f,298  442,224J (Basis per 1 mol of LiCl in 12 mols H2O)
Note: Referent condition for H2O is liquid at 25 C (not its elements)

Calculate Hof, 298 from ͠H298
To calculate heat of formation of solution (Hof, 298) from heat of

~
solution H 298,
Li  1/2Cl 2  LiCl s H0f,298  408,610
~
+ LiCl s  12H2Ol  LiCl 12H2O H298  33,614J
Li  1/2Cl 2  12H2Ol  LiCl 12H2O H0f,298  442,224J

Calculate ͠H298 from Hof, 298
To calculate heat of solution H~ 

298
from heat of formation of
solution (Hof, 298),
Li  1/2Cl 2  12H2Ol  LiCl 12H2O H0f,298  442,224J
+ LiCl s  Li  1/2Cl 2  H0f,298  408,610
~
LiCl s  12H2Ol  LiCl 12H2O H298  33,614J

Example 2 (Example 12.5)
A single-effect evaporator operating at atmospheric pressure concentrates
a 15% (by weight) LiCl solution to 40%. The feed enters the evaporator
at the rate of 2 kg s-1 at 25 C. The normal boiling point of a 40% LiCl
solution is about 132 C, and its specific heat is estimated as 2.72 kJ kg-1
C–1. What is the heat-transfer rate in the evaporator?

Solution 2
Basis: 1 s operation
Single effect
evaporator
This example uses Fig. 12.14 for Hmix

Solution 2 (Cont.)
This example uses Fig. 12.14 for Hmix
Steady-state, steady flow mass balance: In = Out
Overall mass balance: m

1m
 2 m
3
Component i mass balance: x i,1m

 1  x i,2m
 2  x i,2m
3
For LiCl: 0.152  0.4m

 2   0m
 3 m
 2  0.75kg/s
For H2O: 0.852  0.60.75   1m

 3 m
 3  1.25kg/s

Heat of Solution at 25 C

Solution 2 (Cont.)
SSSF Energy balance,
  H
Q  m  m
 3H  m
 2H 
 1H
3 2 1
Where
H2  Hmix   x iHi at 132 C
H1  Hmix   x iHi at 25 C We do not have enthalpy

of solution data
H3  Enthalpy water vapor at 132 C
Since we only have heat of solution data at 25 C (Fig. 12.14), we

need to apply hypothetical or calculational path.
Note: SSSF, Steady-state, steady flow mass balance Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Solution 2 (Cont.)

Solution 2 (Cont.)
Energy balance, 1.7kg 1000g/kg  molH 2O
 94.366
  H
 m  m  m  18.015g/mo l s
Q  3H3
 2H2
 1H 1
  H
t So,
Q
  H
 t  H
 t  H
 t  H
t ~  moles H2O  94.366  13.33
n
Q a b c d
moles solute 7.077
 t : Unmixing process
H From Fig. 12.14
a
~
Mole entering Hmix  33800J/mol solute
0.3kg 1000g/kg 
42.39g/mol
 7.077
molLiCl
s
~
 t  7.077  H
H a 
mix  239,250J/s 

Solution 2 (Cont.)
 t : Mixing process
H b
Mole entering
0.3kg 1000g/kg  molLiCl
 7.077
42.39g/mol s
0.45kg 1000g/kg  molH 2O

 24.98
18.015g/mo l s
So, ~  mols H2O  24.98  3.53

n
mols solute 7.077
From Fig. 12.14,

~
Hmix  23260J/mol solute
 ~
 t  7.077  H
H b 
mix  164630J/s

Solution 2 (Cont.)
 t : Heating the solution Sensible heat 

H c
We need heat capacity data for the solution
kg  kJ 
t m
Hc
 Cp T  0.75  2.72  132  25  C
s  kg C 
 t  218.28 kJ J
H c  218280
s s

Solution 2 (Cont.)
 t : Heating liquid water until it becomes superheate d water

H d
Interpolation
Using steam table
kg  kJ 
t m
Hd
 Hout  Hin   1.25
 H  m  2740.3  104.8 
s  kg 
Use saturated liquid at 25 C

 t  3294.4 kJ  3294400 J
H d
s s
Or, Use Riedel
t m
Hd
 H  m
 H
25 100 C
  Hn
 H100 132  C 
Sensible heat
Solution 2 (Cont.)
So,
  H
Q  t  H
 t  H
 t  H
t
a b c d
  239250  164630  218280  3294300

Q
  3587300J
Q
The rate of heat supply (heat duty)

  3587.3kJs
Q 1
needed to concentrate the solution in
the evaporator.

Tutorial 5
If LiCl.2H2O(s) and H2O(l) mixed isothermally at 25 C to form a solution

containing 10 mol of water for each mole of LiCl, what is the heat effect
per mole of solution.
Tutorial 6:
A liquid solution of LiCl in water 25 C contains 1 mol of LiCl and 7 mol of

water. If 1 mol of LiCl.3H2O(s) is dissolved isothermally in this solution,
what is the heat effect?

Homework
Chapter 12 : 12.1, 12.3, 12.8, 12.28, 12.30
Dateline :

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CHAPTER 12

• Derive and calculate the activity

• Evaluate the property changes due to

• Calculate the heat requirement for given

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Liquid Phase Properties from VLE data

Other Empirical Models for i

Property Changes of Mixing

Heat Effects of Mixing Processes

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Objective: To obtain below information from

• Vapor/liquid equilibrium (VLE) data

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

VLE criteria (Chap. 11)

fˆi l  fˆi v {xi}

VLE measurements are very often made at pressure low enough

î  1 fî l  fî v  y iP

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Note : For pure substance

Fugacity in ideal solution,

fˆi id  x i f i Lewis/Randall rule

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

VLE criteria (previous)

If gas phase is an ideal-gas mixture, we get modified Raoult’s Law

→ Easy calculation of activity coefficient (i) from experimental low-P

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

P/kPa xl y1 fˆ1  y 1P fˆ2  y 2P 1 2

Lewis/Randall rule fˆi id  x i f i

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

In the limit, xi → 0, fˆi becomes zero. Thus the ratio fˆi /x i is

The equation of the tangent line to the curve at xi = 0 express

Henry’s law applies to a species as it approaches infinite dilution in

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Note: P is low, so we could assume an ideal-gas mixture,

Plot of Px1y1 diagram

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

P/kPa x1 y1 lnγ1 lnγ2 GE/RT GE/x1x2RT

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Pxy data Liquid-phase properties

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

GE  8.314J/mol .K 313.15K x 1lnγ1  x 2lnγ 2 

We will now develop a correlation of i from the data.

We are doing to see specifically how the Margules equation

This is DATA REDUCTION METHOD (empirical)

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Note: GE/x1x2RT vs x1 is more linear than others

Let’s gives the following mathematical linear relation

Multiply n on left side and nn2/n2 on the right side x1=n1/(n1+n2)

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

ln 1  x 2 A 21x1  A12 x 2 1 2x 1   x1A 21 

 x 2 2A 21x1x 2  2A 12 x1x 2  A12 x 2 

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Similarly, differentiate GE with respect to

All these equations (above) are the Margules Equation

1. Recalculate y1 and P using BULB P (Chap. 10) calculation and

y1P  x1 1P1sat y 2P  x 2 2P2sat

P  x1 1P1sat  x 2 2P2sat

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

ln  1  x 22 0.372  20.198  0.372 x1 

ln  2  x12 0.198  20.132  0.198 x 2 

Replot the VLE diagrams for Methyl Ethyl Ketone(1)/ Toluene(2) at T