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Solution Thermodynamics
(Application)
• 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.
fˆi v ˆiyiP P T
Therefore,
fˆi l ˆiyiP
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.
fˆi l fˆi v
i xi f i ˆiyiP
xiPisat 1
yiP
i Chap. 10
xiPisat
yiP
i xiP ˆiyiP i
xiPisat
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
fˆi dfˆii
lim Hi
xi 0 x
i dxi xi 0
fˆi xiHi
First we will use the VLE data for the binary system to,
yiP
1. Calculate 1 and 2 from Modified Raoult’s Law i x P sat
i i
GE GE
2. Calculate and x x RT for binary system from
RT 1 2
GE Divide by x1x2 GE 1
x1ln 1 x2ln 2 x1ln 1 x2ln 2
RT x1x2RT x1x2
GE GE
3. From VLE data, tabulate ln 1 , ln 2, RT, x1x2RT vs. x1
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, y1 x1
GE
A 21x1 A 12x2
x1x2RT
GE
A 211 A 12 0 0.198
When, x1 1, x2 0 x1x2RT
GE
x1 0, x2 1 A 21 0 A 12 1 0.327
x1x2RT
So, A 21 0.198
i.e. intersections on vertical axis at both ends
A 12 0.327
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Mathematical Linear Relation
Rearrange
GE GE
A 21x1 A 12x2 A 21x1 A 12 x2 x1x2
x1x2RT RT
nGE nx nx nn
A 21x1 A 12x2 1 2 2 A 21n1 A 12n2 1 2 2
RT n n
Substitute into
n1n2
nG /RT
E
A n
21 1 A n
12 2 2
ln i i
ln 1 n
n
i P,T, nj n1
P,T, n2
For ni = xin
x2 A 21x1 2A 21x12 A 12x2 2A 12x1x2 x1A 21
x2 2A 21x1 2A 21x12 2A 12x1x2 A 12x2
x2 2A 21x11 x1 2A 12x1x2 A 12x2
ln 1 x22 2 A 21 A 12 x1 A 12
GE
Note: All these were derived from A 21x1 A 12x2
x1x2RT
x1 1P1sat
y1
x1 1P1sat x2 2P2sat
GE
0.198x1 0.372x2 x1x2
RT
This are represented by solid lines in Figure (Pxy Data & Liquid-
phase Properties)
→ Correlations fit the data very well
A12 A21 x1 y1 (M) P/kPa (M) lnγ1 (M) lnγ2 (M) GE/RT (M) GE/x1x2RT (M)
Note: M, Calculated using Margules equation Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Diagram (Margules Equation)
A21
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, y1 x1
60 -0.2
GE/RT
-0.4 lnγ1
P-x1
P/kPa
40 -0.6
P-y1 -0.8 lnγ2
20
-1
GE/x1x2RT
0 -1.2
0 0.2 0.4 0.6 0.8 1
x1
x1, y1
A12 A21 x1 y1 (M) P/kPa (M) lnγ1 (M) lnγ2 (M) GE/RT (M) GE/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
40 -0.6
-0.8 lnγ2
20 P-y1 -1
-1.2
GE/x1x2RT
0
0 0.2 0.4 0.6 0.8 1 -1.4
x1, y1 x1
x1x2RT
GE
For truncation after 1 term, A
x1x2RT
nGEi /RT
Apply equation ln i to give
ni P,T, n j
ln 1 ln 2 A
If we define
A B A 21
we can show that this equal
A B A 12 to Margules equation.
Substitute into
Margules eqn.
GE
A 21x1 A 12x2
x1x2RT
GE
A B x1 A B x2 Ax1 Bx1 Ax 2 Bx 2
x1x2RT
GE
A x1 x2 B x1 x2 A B x1 x2
x1x2RT
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Van Laar Equations (Cont.)
x1x2
E
A B x1 x2 A B x1 A B x2
G /RT
Let
1 1
A B and A B
A 21 A 12
So,
GE A 21A 12
x1x2RT A 12x1 A 21x2
x1x2 x1 x2 1 1
x1 x2
E
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, nj
2 2
A 12x1 A 21x2
ln 1 A 12 1
ln 2 A 21 1
A 21x2 A 12x1
At infinite dilution
x1 0 ln 1 A 12
x2 0 ln 2 A 21
No theoretical foundation
i is independent of P
Applicable at constant T
Improved version
of UNIQUAC
Wilson UNIQUAC
GE
xi ln x j ij
RT i j
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 aij
ij exp i j
Vi RT
GE
x1 ln x1 x2 12 x2 ln x2 x1 21
RT
That gives,
12 21
ln 1 ln x1 x2 12 x2
x1 x2 12 x2 x1 21
12 21
ln 2 ln x2 x1 21 x1
x1 x2 12 x2 x1 21
Where,
ln 1 ln 12 1 21 ln 2 ln 21 1 12
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 b21
12 21
GE G21 21 G21 12 RT RT
x1x2RT x1 x2G21 x2 x1G12
G
2
G21 21
ln 2 x1 21
2 12
x x
2 1 12 G 2
x1 x2G21 For infinite dilution,
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.
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.
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Tutorial 3
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
ME M Mid
GE G xiGi RT xilnxi
i i
S E S xiS i R xilnxi
i i
VE V xiVi
i
HE H xiHi
i
Mmix M xiMi
i
GE Gmix RT xilnxi
i
S E S mix R xilnxi
i
VE Vmix
HE Hmix
mix RT xilnxi
Gid mix R xilnxi
S id
i i
Vmix
id
0 Hid
mix 0
Mid
mix Mid
xiMi ― Mmix M xiMi
i i
Mmix Mid
mix M M
id
ME Mmix Mid
mix
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
0
Q
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
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 mix
m
iHi m
iHi
H
Q
mix
H H0f,298 C P T
We need,
Heat of formation of the solution
Heat of capacity of solution
H Hmix xiHi
i
weight) aqueous solution NaOH to 50%. The feed enters at 70 (F). The
these conditions the boiling point of a 50% solution of NaOH is 190 (F).
1m
Overall mass balance: m 2 m
3
1 xi,2m
Component i mass balance: xi,1m 2 xi,2m
3
Energy balance,
H
Q H m m
3H m
2H
1H
out in 3 2 1
steam table
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
Heat of solution H
~
298 diagram, Fig. 12.14
Solute 25 C
Solution 25 C
Liquid 25 C Q
As shown before, Q Hmix H
xH i i
Elements
Solute 25 C
Solution 25 C
Liquid 25 C Q
~
+ LiCl s 12H2O l LiCl12H2O H298 33,614J
~
LiCl s 12H2O l LiCl12H2O H298 33,614J
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
1m
Overall mass balance: m 2 m
3
1 xi,2m
Component i mass balance: xi,1m 2 xi,2m
3
H
Q m m
3H m
2H
1H
3 2 1
Where
H3 Enthalpywatervaporat132 C
Note: SSSF, Steady-state, steady flow mass balance Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Solution 2 (Cont.)
H
t So,
Q
H
t H
t H
t H
t ~ molesH2O 94.366 13.33
n
Q a b c d
molessolute 7.077
t : Unmixingprocess
H a
From Fig. 12.14
~
Mole entering Hmix 33800J/molsolute
0.3kg1000g/kg
7.077molLiCl
42.39g/mol s
H a
~
t 7.077 H
mix 239,250J/s
Mole entering
0.3kg1000g/kg
7.077molLiCl
42.39g/mol s
0.45kg1000g/kg
24.98molH2O
18.015g/mol s
~
t 7.077 H
H b
mix 164630J/s
t : Heatingthesolution Sensibleheat
H c
kg kJ
H
t m
c
C p T 0.75
2.72
132 25
C
s kg C
t 218.28kJ 218280J
H c
s s
t : Heatingliquidwateruntilitbecomessuperheate
H d water
d
Interpolation
Using steam table
kg kJ
H
t m
d
H m
Hout Hin 1.25
2740.3 104.8
s kg
t m
H d
H m
H
25100 C
Hn
H100132 C
Sensible heat
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Solution 2 (Cont.)
So,
H
Q t H
t H
t H
t
a b c d
3587300J
Q
Tutorial 6: