Physical Properties and Its Use For Selection of Separation Techniques

ChE-396 Senior Design
Physical Properties
Physical Properties, their

Prediction and Usage for Selection
of Separation Techniques
Senior Design ChE 396
Pooja Pathak
Shumaila Khan
Navin Katyal
Kaushik Shah
Physical Properties
Table of Contents
1. Introduction_________________________________________________________ 3
2. Estimation Method for Activity Coefficient ________________________________ 4
2.1 UNIFAC Method _________________________________________________ 4
2.2 Margules Method _______________________________________________ 11
2.3 Non Random Two Liquid Method (NRTL) ___________________________ 13
3. Systems with Acid Components ________________________________________ 16
4. Comparison of Activity Coefficient Models Used __________________________ 20
5. Estimation Methods for Heat Capacity __________________________________ 24
5.1 Benson Cruickshand Method for Gases ______________________________ 24
5.2 Johnson Huang Method __________________________________________ 26
6. Estimation Method for Heat of Vaporization _____________________________ 29
6.1 Klein Method ___________________________________________________ 29
7. Estimation Methods for Normal Boiling Point ____________________________ 33
7.1 Lydersen-Forman-Thodos Method __________________________________ 33
References ___________________________________________________________ 36
Nomenclature
37
Physical Properties
1. Introduction
The physical properties molecular weights, boiling points, vapor pressures, heat
capacities, heats of vaporization, heats of reaction, liquid densities, and fugacity
coefficients can be estimated by using different methods. The need for estimation
method arises when the data for a specific compound is not readily available. Activity
coefficient may be calculation and the vapor liquid equilibrium data can be known by
methods such as UNIFAC, Margules, and NRTL etc. Heat capacity can be estimated by
Benson Cruickshank or Johnson Huang method. Heat of vaporization may be estimated
by using Klein method. Lydersen-Forman-Thodos Method may be used to estimate the
normal boiling points.
Physical Properties
2. Estimation Methods for Activity Coefficient

The purpose of this section is to provide methods of estimating the activity coefficient of
components in solution. The discussion will be limited to binary systems although, in
principle, the methods are applicable to multicomponent equilibria. As applied to
solutions, an activity coefficient, ? , is a correction factor compensating for non-ideal
behavior.
Methods of Estimation
-
UNIFAC (UNIQUAC (Universal Quasi-Chemical) Function Group Activity

Coefficient)
Margules Equation
NRTL
2.1 UNIFAC Method

The UNIFAC method is a group contribution concept. The basic idea is that, whereas
there are thousands of organic compounds, the number of functional groups that
constitute these compounds is much smaller. The primary aim of the solution of groups
method is to utilize existing phase equilibrium data for predicting phase equilibria of
systems for which there are no experimental data.
The method entails suitable reduction of experimental data to obtain parameters can then
be used in other systems containing these groups. A group is defined as any convenient
structural fragment---CH3, CH2OH, COOH, CH2Cl, etc.
The primary feature of all solution-of-group methods is that the logarithm of the
activity coefficient is assumed to be the sum of two contributions a combinatorial part,
essentially due to difference in size and shape of the molecules in the mixture, and a
residual part, essentially due to energy interactions. Thus, for molecule i in any solution:
C
ln
i = ln
i
Combinatorial
R
ln
i
(1)
Residual
where combinatorial part of Eq. 1 is given for a binary mixture by
and
C
ln
1 = ln (1/x1) + (z/2) q1 ln (1/1) + l1 (1/x 1)(x1l1+x 2l2)
(2)
C
ln
2 = ln (2/x2) + (z/2) q2 ln (2/2) + l2 (2/x 2)(x1l1+x2l2)
(3)
where
1 = (r1x1)/( r1x1 + r2x2)
1 = (q1x1) / (q1x1 + q2x2)
(4a)
2 = (r2x2)/( r1x1 + r2x2)
2 = (q2x2) / (q1x1 + q2x2)
(4b)
Physical Properties
Note that 1+ 2 = 1 and 1 + 2 = 1.
l1 = (z/2) (r1 q1) (r1 - 1)
z = 10
(5a)
l2 = (z/2) (r2 q2) (r2 - 1)
z = 10
(5b)
rI = kvk(1)Rk
r2 = kvk(2)Rk
(6a)
q1 = kvk(1)Qk
q2 = kvk(2)Qk
(6b)
and where
x1 , x2
vk
Rk
Qk
k
= mole fraction of components 1 and 2

= 1, 2, N (number of groups in molecule 1 or 2)
= the van der Waals volume for group k
= the van der Waals surface area for group k
= group number (assigned) from Table 11-6
For a binary mixture, the residual part of Eq. 1 is given by:

R
(1)
(1)
ln
1 = k vk (ln k ln k )
(7a)
R
(2)
(2)
ln
2 = k vk (ln k ln k )
(7b)
where
ln k = Qk [1 - ln (m m mk) - m(m km/(nn nm))]
(8)
and m and n = 1,2, N (all groups)
m = QmXm / n Qn Xn
mn = exp (-amn/T)
(9)
j = 1, 2, M; n = 1, 2, , N
Similar relationships hold for ln k(1) and ln k(2). Note, however, that these refer to the
pure components.
Physical Properties
Case Study
Estimate the activity coefficients for the Acetone (1)-Acetic Acid (2) system at 300K, P =
1 atm and x1 = 0.80 (whence x2 = 0.20).
(1)
The Structure are:
Acetone
(CH3)2C=O
Acetic Acid
CH3COOH
(2)
Acetone contains one CH3C=O group and one CH3 groups.

Acetic Acid contains one CH3 and one COOH groups.
Table 11.6 in reference[1] lists the appropriate group parameters.
Group
CH3
CH3C=O
COOH
CH3
(3)
Main Group #
1
9
20
1
k
1
19
43
1
J
1
1
2
2
vk
Rk
Qk
1
1
1
1
0.9011
1.6724
1.3013
0.9011
0.848
1.488
1.224
0.848
From Equations
rI = kvk(i)Rk
qI = kvk(i)Qk
r1 = (1)(0.9011)+(1)(1.6724) = 2.5735, q1 = (1)(0.848)+(1) (1.4880)=2.3360

r2 = (1)(1.3013)+(1)(0.9011) = 2.2024, q2 = (1)(1.224)+(1) (0.8480)=2.0720
(4)
Calculate i and i from equations
I = (rIxI)/(j rj xj )
1 = (2.5735)(0.8)/[(2.5735)(0.8)+(2.2024)(0.2)] = 0.82376
2 = 1 - 1 = 0.17624
and from
I = (qIxI) / (j qj xj )
1 = (2.336)(0.8)/[(2.336)(0.8)+(2.2072)(0.2)] = 0.8185
2 = 1 - 1 = 0.1815
(5)
Calculate l1 and l2 from equation
li = (z/2) (rI qI) (rI - 1)
Where z = 10
l1 = (10/2)(2.5735 2.3360) (2.5735 1) = -0.3860

l2 = (10/2)(2.2024 2.0720) (2.2024 1) = -0.5504
(6)
C
C
Calculate ln
1 and ln
2 from equation
C
ln
i = ln (/xi ) + (z/2) qi ln (i /i ) + li (i /xi )j xj lj
Physical Properties
C
ln
1 = ln (0.82376 / 0.8) + (5) (2.3360) ln (0.8185 / 0.82376) + (-0.3860)
[(0.82376) / (0.8) (.03860)) + (0.2) (-0.5504))]
= -1.925*10-4
C
ln
2 = ln (0.17624/0.2) + (5) (2.0720) ln (0.1815/0.17624) + (-0.5504)
[(0.17624) / (0.2)(-0.41888)]
= -3.230*10-3
(7)
Calculate m and Xm for each group, using equations
m = QmXm / n Qn Xn
Xm = (j xj vmj) / (j xj mvmj)
For pure component

X1 = 1
X2 = 1 X1= 0
V 11 = 1
V 12 = 1
For pure Acetone
V191 = 1
V192 = 0
V431 = 0
V432 = 1
X11 = (X1* V11 + X2* V12) / [x1 (V11 + V191 + V431) + x2(V12 + V192 + V432)
= ( 1*1+1*0) / [1 (1+1+0) + 0(1+0+1)] = 0.5
X191 = (X1* V191 + X2* V192) / [x1 (V11 + V191 + V431) + x2(V12 + V192 + V432)
= ( 1*1+0*0) / [1 (1+1+0) + 0(1+0+1)] = 0.5
X431 = 1 - [x11 + x191]
= 1- [0.5 + 0.5 ] = 0
For mole Fraction x1 = 0.8, x2 = 0.2
x1 = (X1* V11 + X2* V12) / [x1 (V11 + V191 + V431) + x2(V12 + V192 + V432)
= ( 1*0.8+1*0.2) / [0.8 (1+1+0) + 0.2(1+0+1)] = 0.5
x19 = (X1* V191 + X2* V192) / [x1 (V11 + V191 + V431) + x2(V12 + V192 + V432)
= ( 1*0.8) + (0.2*0) = 0.4
x43 = 1 (x1 + x19)
= 1 (0.5 + .04) = 0.1
For pure Acetone
m = QmXm / n Qn Xn
11 = Q1X11 / ( Q1 X11 + Q19 X191 + Q43 X431)

7
Physical Properties
= (0.8480.5) / [
(0.8480.5) + (1.488 0.5) + (00)]= 0.3630
191 = Q19X191 / ( Q1 X11 + Q19 X191 + Q43 X431)
= (1.488 0.5) / [
(0.8480.5) + (1.488 0.5) + (00)]= 0.6370
431 = 1 [11 + 191] = 1 [
0.3630 + 0.6370]= 0
For pure Acetic Acid
1
m = QmXm / n Qn Xn
= Q1X12 / ( Q1 X12 + Q19 X192 + Q43 X432)

= (0.8480.5) / [
(0.8480.5) + (1.224 0.5) + (1.4880)]= 0.409 2
192 = Q19X192 / ( Q1 X12 + Q19 X192 + Q43 X432)

= (1.224 0.5) / [
(0.8480.5) + (1.224 0.5) + (1.4880)]= 0.59 07
432 = 1 [12 + 192] = 1 [
0.409 2 + 0.59 07]= 0
t x1 = 0.8
m = QmXm / n Qn Xn
1 = Q1X1 / ( Q1 X1 + Q19 X19 + Q43 X43)

= (0.8480.5) / [
(0.8480.5) + (1.488 0.4) + (1.2240.1)]= 0.3714
19 = Q19X19 / ( Q1 X1 + Q19 X19 + Q43 X43)
= (1.488 0.4) / [
(0.8480.5) + (1.488 0.4) + (1.2240.1)]= 0.5228
43 = 1 [1 + 19] = 1 [
0.3714 + 0.5228]= 0.1072
(8)
Calculate
mn
for each group using the value of amn in Table 11-7.
mn = exp (-amn/T)
From Table 11-7, the following parameters were obtained

Parameter
Temperature(K)
A1,1
0
A19,19
0
A43,43
0
A1,19
476.4
A19,1
26.76
A19,43
669.4
A43,19
-297.8
A43,1
315.3
A1,43
663.5
8
Physical Properties
Now find mn for the various parameters at T=300K

Value
mn = exp (-amn/T)
1
1,1
1
19,19
1
43,43
0.2043
1,19
0.9147
19,1
0.1073
19,43
2.6984
43,19
0.34958
43,1
0.1095
1,43
(9)
Calculate ln k and ln k
(j)
for each group

ln k = Qk [1 - ln (m m mk) - m(m km/(nn nm))]
For pure acetone:

ln 11 = Q1 [1 - ln [(11 1,1) + (19 1 19,1) + (431 43,1)]
-(11 1,1) / [(11 1,1) +(19 1 19,1) + (431 43,1)]
-(19 1 1,19) / [(11 1,19)+(19 1 19,19) + (431 43,19)]
-(431 1,43) / [(11 1,43)+(19 1 19,43) + (431 43,43)]
ln 11 = 0.848[1 ln [(0.3630*1)+(0.6370*0.91466)+(0.3496*0)]
- (0.3630*1) /[(0.3630*1) + (0.6370*0.9146)+ (0.3496*0)]
- (0.6370*0.2043) / [(0.363+0.2043) + (0.6370*1 ) +(0*2.6898)]
- (0)]
ln 11 = 0.414699
ln 191 = Q19 [1 - ln [(19 1 19,19) + (11 1,19) + (431 43,19)]
-(19 1 19,19) / [(19 1 19,19) +(11 1,19) + (431 43,19)]
-(11 19,1) / [(19 1 19,1)+(11 1,1) + (431 43,1)]
-(431 19,43) / [(19 1 19,43)+(11 1,43) + (431 43,43)]
After substituting the respective values
ln 191 = 0.236846
Now at x = 0.8
1 = 0.371409
19 = 0.531373
Physical Properties
43 = 0.107218
Solve for ln 1 and ln 19 as illustrated in the previous calculations except now substitute
the above values for 11 , 191, and 431
Solving for ln 1,
ln 1 = 0.848[1ln [(0.371409*1)+(0.52284*0.91466)+(0.10575*0.3496)]
- (0.371409*1) /[(0.371409*1) + (0.52284*0.9146)+ (0.3496 * 0.10575)]
- (0.52284*0.2043) / [(0.371409+0.2043) + (.52284*1 ) +(0.10575*2.6898)]
- (0.10575*0.10952)/[ 0.371409+0.10952) + (.52284*0.107385 )+(0.10575*1)]
ln 1 = 0.3538158
and solving for ln 19
ln 19 = 1.488[1ln [(0.52284*1)+(0.371409*0.2043)+(0.10575*2.6984)]
- (0.52284*1) /[(0.52284*1) + (0.371409*0.2043)+ (0.10575 * 2.6984)]
- (0.371409*0.91466) / [(0.52284+0.91466)+(0.3714085*1)+(0.10575*0.34958)]
- (0.10575*0.107385)/[0.52284+0.107385) + (0.371409*0.10952)+(0.10575*1)]
ln 19 = 0.1373489
(10)
Calculate ln
I by using
R
R
(i)
(i)
ln
I = k vk (ln k ln k )
R
1
1
19
1
ln
I = v1 (ln 1 ln 1 ) + v1 (ln 19 ln 19 )
R
ln
I = [1 (0.44378 0.414699) + [1 (0.13778 0.236846)]
R
ln
I = -0.06342
C
-4
Recall: ln
I = -1.9258*10
(11)
Calculate ln
i using
C
ln
1 = ln
1
combinatorial
R
ln
1
Residual
= (-0.06342 + -1.9258*10-4)
= -0.063617
Therefore
1 = 0.93836 for Acetone @ T= 300K and x1 = 0.8
The experimental value is 0.95401 for an error of -7.0%[1].
By following exactly the same procedure for acetic acid it is found that
2 = 0.8803 and
the experimental value is 0.88725 for an error of 8.0%[1].
10
Physical Properties
2.2 Margules Method

The activity coefficient for a liquid is related to the excess fluid properties such as Gibbs
energy. This relation is represented by equation (10).
E
ln
i = ((nG /RT)/ni ) P, T, nj
(10)
A simple mathematical relation can thus be derived by calculating GE/x1x2RT and

expressing this relation by equation (11).
GE/x1x2RT = A21x1 + A12x2
(11)
Equation (1) and (2) are then combined and ln

1 and ln
2 are solved for. Equations (12)
and (13) represent the equations for the activity coefficients in a binary system.
2
ln
1 = x2 [A12 + 2(A21 A12)x1]
(12)
2
ln
2 = x1 [A21 + 2(A12 A21)x2]
(13)
These are Margules equations, which represent a commonly used empirical model of
solution behavior. For the limiting conditions of infinite dilution, they show that when x1
= 0, ln
1 = A12 and when x2 = 0, ln
2 = A21. For the acetone-acetic acid system
considered here, the curves in Figure (1) show that. What this accomplished is the
reduction of a set of vapor liquid equilibrium data to a simple mathematical equation of
the dimensionless excess Gibbs energy.
Margules Sample Calculations
Properties that should be given or known are P, A12, A21, Aacetone, Bacetone, Cacetone, Aacid,
Bacid, Cacid, R, and xacetone. The calculation are done at xacetone = 0.10. Temperature is
calculated in our case by the equilibrium given in the tables of Gmehling and Onken[2],
but any temperature can be plugged in to find the equilibrium at a different temperature.
We know that: P = 760mmHg
A12 = -0.0508
A21 = 0.3481
Aacetone = 7.6313
Bacetone = 1566.69
Cacetone = 273.419
Aacid = 8.021
Bacid = 1936.01
Cacid = 258.451
R = 1.98721 cal / mol K
xacetone = 0.10
T = 103.56oC (376.71K)
11
Physical Properties
Determine the vapor pressures by using Antoine equations:

log (VPacetone) = Aacetone Bacetone/(T+Cacetone)
log (VPacetone) = 7.6313 1566.69/(103.56oC + 273.419)
VPacetone = 2988.32 mmHg
log (VPacid) = Aacid Bacid/(T+Cacid)
log (VPacid) = 8.021 1936.01/(103.56oC + 258.451)
VPacid = 471.10mmHg
Determine the activity coefficients for the acid and the acetone liquid using Margules
equations:
2
ln
acetone = xacid [A12 + 2(A21 A12)xacetone]
2
ln
acetone = (0.90 )[-0.0508 + 2(0.3481 -0.0508)0.10]
acetone = 1.02375
2
ln
acid = xacetone [A21 + 2(A12 A21)xacid]
2
ln
acid = (0.10 )[0.3481 + 2(-0.0508 0.3481)0.90]
acid = 0.996308
Now the vapor mole fractions can be determined due to equality in vapor and liquid
phase chemical potentials. They relate the pressure and mole fractions of species in the
gas phase.
yacetone =
acetone xacetone VPacetone / P
yacetone = 1.02375*0.10*2988.32 mmHg / 760mmHg
yacetone = 0.4025
yacid =
acid xacid VPacid / P
yacid = 0.996308*0.90*471.10mmHg / 760mmHg
yacid = 0.5558
2.3 Non-Random-Two-Liquid Method (NRTL)

Modern theoretical developments in the molecular thermodynamics of liquids solution
behavior are based on the concept of local composition. Within a liquid solution, local
compositions, different from the overall mixture composition, are presumed to account
for the short-range order and non-random molecular orientations that result from
differences in molecular size and inter-molecular forces. Many local composition models
currently exist, and one of which is the NRTL (Non-Random-Two-Liquid) equation [3].
12
Physical Properties
NRTL equation contains three parameters for a binary system and is written as in
equation (14).
GE/x1x2RT = G2121/(x1 + x2G21) + G1212/(x2 + x1G12)
(14)
Then equate this equation by plugging into equation (10). This leads to equations for the
activity coefficient.
2
2
2
ln
(15)
1 = x2 {21[G21/(x1 + x2G21)] + G1212/(x2 + x1G12) }
2
2
2
ln
2 = x1 {12[G12/(x2 + x1G12)] + G2121/(x1 + x2G21) }
(16)
Where, G12= exp (-12), G21=exp (-21), 12 = b12 / RT, and 21 = b21 / RT.
The graph as compared to the other methods is shown in Figure (2).
NRTL Sample Calculations:
Properties that should be given or known are P, A12, A21, , Aacetone, Bacetone, Cacetone, Aacid,
Bacid, Cacid, R, and xacetone. The calculation are done at xacetone = 0.10. Temperature is
calculated in our case by the equilibrium given in the tables of Gmehling and Onken, but
any temperature can be plugged in to find the equilibrium at a different temperature [2].
We know that: P = 760mmHg
b12 = 1920.7646
b21 = -1062.2181
= 0.2278
Aacetone = 7.6313
Bacetone = 1566.69
Cacetone = 273.419
Aacid = 8.021
Bacid = 1936.01
Cacid = 258.451
R = 1.98721 cal / mol K
xacetone = 0.10
T = 103.56oC (376.71K)
Determine the vapor pressures by using Antoines equations:
log (VPacetone) = Aacetone Bacetone/(T+Cacetone)
log (VPacetone) = 7.6313 1566.69/(103.56oC + 273.419)
VPacetone = 2988.32 mmHg
log (VPacid) = Aacid Bacid/(T+Cacid)
log (VPacid) = 8.021 1936.01/(103.56oC + 258.451)
VPacid = 471.10mmHg
13
Physical Properties
Determine the values of the constants 12, 21, G12, and G21.
12 = b12 / RT
12 = 1920.7646 / (1.98721 cal / mol K * 376.71K)
12 = 2.56578
21 = b21 / RT
21 = -1062.2181 / (1.98721 cal / mol K * 376.71K)
21 = -1.41892
G12= exp (-12)
G12= exp (-0.2278*2.56578)
G12= 0.55739
G21= exp (-21)
G21= exp (-0.2278*-1.41892)
G21= 1.38158
Determine the activity coefficients for the acetic acid and the acetone liquid using NRTL
equations:
2
2
2
ln
acetone = xacid {21[G21/(xacetone + xacid G21)] + G1212/( xacid + xacetoneG12) }
2
2
ln
acetone = 0.90 {-1.41892*[1.38158/(0.10 + 0.90*1.38158)] + 0.55739*2.56578/(0.90
+ 0.10*0.55739)2}
acetone = 1.05406
2
2
2
ln
acid = xacetone {12[G12/( xacid + xacetone G12)] + G2121/( xacetone + xacidG21) }
2
2
ln
acid = 0.10 {2.56578[0.55739/(0.90 + 0.10*0.55739)] + 1.38158*-1.41892/(0.10 +
2
0.90*1.38158) }
acid = 0.99787
Now the vapor mole fractions can be determined due to equality in vapor and liquid
phase chemical potentials. They relate the pressure and mole fractions of species in the
gas phase.
yacetone =
acetone xacetone VPacetone / P
yacetone = 1.05406*0.10*2988.32 mmHg / 760mmHg
yacetone = 0.41446
yacid =
acid xacid VPacid / P
yacid = 0.99787*0.90*471.10mmHg / 760mmHg
yacid = 0.5567
14
Physical Properties
3. Systems with Acid Components

For systems with components associating in the vapor phase, deviations from ideal gas
behavior must be accounted for even at low pressures. This can be done by regarding
vapor phase association as a chemical equilibrium reaction for which equilibrium
constants can be defined. The liquid phase is assumed to be composed only of the
original mixture. However the new species formed, the dimer in this case, must be
treated as an individual component of the vapor phase. Therefore when constructing the
vapor liquid equilibrium, these interactions in the vapor phase must be considered.
Derivations for a binary system consisting of acid is provided. The acid component is
taken as component1. Dimerization occurs as follows:
2M D
(17)
The dimerization can be accounted by the dimerization constant KD, where the
equilibrium relation in terms of partial pressure is:
KD =
PID
PIM2
(18)
The constant KD is dependent on the temperature and the acid component where the
relation is:
K D = AD +
BD
T
(19)
AD and BD are specific to the acid and may be looked up.
p 1 = p IM + p ID
(20)
Thus the total pressure is consists of the partial pressure of the acid and the second
component.
P = p 2 + p IM + p ID
(21)
where p2 is the partial pressure of the second component. The partial pressure of the
second component may be obtained from the equilibrium relation:
p 2 = x 22 p 2o
(22)
Where x2 is the liquid mole fraction, p2 is the partial pressure, p2o is the saturation
pressure of the non-acid component. The partial pressure of the monomer can similarly
be calculated using:
15
Physical Properties
o
p IM = x 1
1 p IM
(23)
Here pIM o is the hypothetical vapor pressure of the pure monomer of component 1. It is
related to the real vapor pressure of p1 o of pure component 1 by:
o
o
p 1o = p IM
+ K D p IM
(24)
This can be obtained by the following derivation at y1=1. When y1=1, x1=1 and the
partial pressure is equal to the saturation pressure.
Therefore p1 = p1o and pIM = pIM o
(25)
Plugging in these relations to equation (20) and substituting pID from equation (18) we
obtain
o
o
p 1 = p IM
+ K D p IM
o
(26)
Upon rearrangement equation (/24) is obtained.

Now the mole fraction of the vapor is defined as:
y1 =
mole _ acid
total _ moles
(27)
where the moles of the acid consists of the moles of the monomer plus the dimer. Each
mole of dimer contains two moles of the monomer therefore:
moles acid = moles monomer + 2* moles dimer
partial pressure acid = partial pressure of monomer + 2* partial pressure of dimer
total moles = moles acid + moles acetone
pressure = partial pressure of monomer + 2* partial pressure of dimer + partial pressure
acetone
From the above relations the vapor mole fraction of the acid is calculated as:
y1 =
p IM + 2 p ID
P + p ID
(28)
Partial pressure of the dimer is added to the top and bottom because we wish to calculate
the pressure of the acid, and each dimer consists of two monomers.
16
Physical Properties
Case Study
Now let us revisit the acetone-acetic acid equilibrium taking into account the acid
dissociation. The sample calculation is illustrated at 110oC where the liquid mole
fraction of the acid is 0.05.
K D = AD +
BD
T
where A=-10.42 and B=3166.

KD.007. Now the partial pressure of the acetone may be calculated from equilibrium
using equation (22)
p 2 = x 22 p 2o
p2 = (3623.76)(0.05)(0.99)
= 174.43 mm Hg
Using KD, as calculated and the saturation pressure of acetic acid, equation can be solved
for to obtain the saturation pressure of the monomer.
o
o
p 1o = p IM
+ K D p IM
0.007pIMo2+pIMo-606.51=0
pIMo=231.47 mm Hg
Similarly the partial pressure of the acetic acid may be calculated using equation:
o
p IM = x 1
1 p IM
pIM= (231.47)(0.95)(0.99)
= 217.67 mm Hg
The partial pressure of the dimer may be found from that of the monomer from equation:
pID= KD* pIM2
= 329.6 mm Hg
The total pressure by equation is:
P = p 2 + p IM + p ID
P= (217.67 + 174.43 + 329.6) mm Hg
17
Physical Properties
= 721.7 mm Hg
Finally the mole fraction of the acetic acid in the vapor phase is given by equation :
y1 =
p IM + 2 p ID
P + p ID
yi = {217.67+(2*329.6)}/(721.7+329.6)
= 0.834
Compared to the experimental value which is 0.84.
18
Physical Properties
4. Comparison of Activity Coefficient Models Used

Activity Coefficient using different methods
1.5
1.4
1.3
Activity Coefficient
Margules
1.2
1.1
1
0.9
0.8
UNIFAC
0.7
0.6
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
xacetone
Figure 1: The difference in activity coefficient for Margules and UNIFAC Methods.
Figure 1 illustrates the difference in the calculated activity coefficient for the different
methods used.
19
Physical Properties
Equilibrium Data For Acetone and Acetic Acid

1.1
NRTL
1
0.9
Margules
0.8
Experimental
Yacetone
0.7
UNIFAC
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Xacetone
Figure 2: Plot of vapor liquid equilibrium data obtained from using different methods.
Figure 1 graphically shows all of the different methods of calculation of the equilibrium
curve and the vapor liquid equilibrium data. It is obvious from this graph that these
estimation methods are inaccurate. This is explained as a result of acid dissociation.
20
Physical Properties
Equilibrium Data For Acetone and Acetic Acid

1.1
1
0.9
Margules
Margules with dimerization
0.8
Experimental
Yacetone
0.7
UNIFAC
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Xacetone
Figure 3: Calculation of Margules with the dimerization.

The equilibrium line has been calculated using the dimerization and adjusting the
Margules equation. The accuracy of this method is within 1-2% of the experimental data.
21
Physical Properties
Equilibrium at 40oC
1
0.9
Margules
0.8
0.7
UNIFAC
Yacetone
0.6
0.5
0.4
Experimental
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Xacetone
Figure 4: Equilibrium at 40oC using UNIFAC and Margules Method.

The absorption column in our design process operates at a low temperature and high
pressure. These conditions are out of range of the normal equilibrium data. Therefore a
method which is more applicable to such conditions must be considered. The graph
above is the vapor liquid equilibrium calculated at 40 0C temperature using UNIFAC as
well as NRTL.
Figure 4 shows that the UNIFAC method would be a better method to be used to transfer
the activity to a lower temperature. Therefore it is suggested by the team that UNIFAC
method be used for the absorber in the acetic anhydride plant.
22
Physical Properties
5. Estimation Methods for Heat Capacity

Theory
Heat capacity is defined as the ratio of the heat absorbed by a system to a specific
resulting temperature. Heat capacities are often required for heat balance calculations
and other engineering parameters. Values can be obtained from tabulated reference data,
experimental data, or from empirical estimation methods. Estimation methods are
generally based on structural considerations, such as the contribution of component bonds
or functional groups to the total heat capacity.
5.1 Benson Cruickshank Method for Gases

The Benson Cruickshank method allows the estimation of heat capacities at constant
pressure for gases. This method assigns a value to each divalent or polyvalent atom
based on the number and type of bonds to neighboring groups or other atoms. The
contributions of each atom are then combined to give the total Cpg .
Applicability and Limitations

This method is applicable only to gases at 300 K. Values of contribution have been
compiled for most groups which are like to be encountered. The method is considered to
be accurate to 1% of observed values, however, it maybe considerably complex for large
molecules.
In comparison with other methods, the Benson Cruickshank method seems to provide a
good compromise between ease of use and accuracy. An alternative estimation method is
one proposed by Rihani and Doraiswamy which may be applied to gases within a larger
temperature range. However, at 300K, the Benson Cruickshank method provides greater
accuracy. Contributions are listed for a wide range of groups for Benson Cruickshank
while group contribution tabulations are limited for the other method. Use of both
methods requires knowledge of the molecular structure of the compound.
Basic Steps
1. Draw the structure of the compound.
2. Find the individual group contributions to Cpg and add them in proportion to the
number of groups in the molecule.
3. Add or subtract any corrections for next nearest neighbors and ring structures.
4. The resulting value is in units of cal / mol o C. To convert to units of cal/g oC, divide
by molecular weight of compound.
23
Physical Properties
Example 1
Calculate the Cpg of a) acetone and b) acetic acid
a) Cpg of acetone
Groups
CH3-C
CO-(C)2
Contributions (cal/mol oC)

2 x 6.196
5.596
Thus, adding all contribution values, we obtain a value of 17.97 cal/mol oC at 300K.
4. The resulting value is in units of cal/mole oC. To convert to units of cal/goC, divide by
the molecular weight.
Cpg = 17.97 (cal/mol oC )/ 58 (g/mole)= 0.3098 cal/g oC
Experimental Value = 23.0 cal/mol 0C [8]
Comparison of values gives 16 % error.
b) Cpg of acetic acid
24
Groups
CH3-C
C-(O)2CH
Physical Properties
6.196
5.066
Cpg = 11.27 (cal/mol oC) / 60 (g/mole) = 0.186 cal/goC
5.2 Johnson Huang Method

Like gases, liquid heat capacities are estimated from the total contribution of bonds or
groups. The Johnson Huang method allows the estimation of heat capacities at constant
pressure for liquids. This method is based on the molecular structure of a molecule and
requires the identification of various molecular groups. The contributions by each groups
are summed and equal the overall value of Cpl .

This method is applicable only to liquids. Liquid heat capacity usually increases with
temperature, however, its a very weak function of temperature except in the region just
below the critical temperature. Values of contribution have been compiled for most
groups which are like to be encountered. The method is considered to be accurate to 10%
of observed values.
The Johnson Huang method is simplified in comparison to another more complex method
proposed by Chueh and Swanson. Chueh and Swanson is based on aggregate group
contributions while Johnson Huang is based on individual contributions. Individual
groups are easier to discern in a molecule which makes Johnson Huang easier to use.
Chueh and Swanson is slightly more accurate, however. Use of both methods requires
knowledge of the molecular structure of the compound.
Basic Steps
2. Find the individual group contributions to Cpl and add them in proportion to the
25
Physical Properties
3. The resulting value is in units of (cal / mol o C). To convert to units of (cal/g oC),
divide by molecular weight of compound.
Example 2
Calculate the Cpl of a) acetone and b) acetic acid
a) Cpl of acetone
Groups
CH3
CO

2 x 9.910
14.710
Cpl = 34.5 cal/mol oC / 58 = 0.595 cal/goC
Experimental value = 30.26 cal/moloC [8]
Thus, comparison of values gives experimental error of 11%
b) Cpl of acetic acid
26
Physical Properties
Groups
CH3
COOH

9.910
19.110
Cpg = 29.0 (cal/mol oC )/ 60 (g/mole)= 0.483 cal/goC
Experimental value = 29.42 cal/moloC [8]
Thus, comparison of values gives experimental error of 1.41%
27
Physical Properties
6. Estimation Methods for Heat of Vaporization

Theory
The heat of vaporization, Hv, is defined as the quantity of heat required to convert a unit
mass of liquid into a vapor without a rise in temperature. Heat of vaporization values are
often obtained from tabulated reference data, experimental data, or from empirical
estimation methods. The estimation methods are generally based on the Clapeyron
equation, which is modified and fit to experimental data.
The Clapeyron equation,
dP
Hv
dT
where
(29)
T (Vg - Vl)
dP/dT = derivative of the vapor pressure with respect to temperature

Hv = heat of vaporization at temperature T
Vg = saturated molal volume of the vapor phase
Vl = saturated molal volume of the liquid phase
The quantity Vg - Vl can be obtained from the compressibility factor equation of state:
Vg - Vl = RT/P (Zg - Zl ) where
(30)
R is the universal gas constant and Zg and Zl are the compressibility factors for
vapor and liquid phases .
Substitution into the Clapeyron equation and rearrangement leads to :
d (ln P)
d (1/T)
- Hv
(31)
R (Zg - Zl)
This equation is the starting point for methods of estimating the heat of vaporization of a
material.
6.1 Klein Method

The Klein method uses physical properties such as boiling point, Tb, critical temperature,
Tc, and critical pressure, Pc to estimate heats of vaporization. Starting with equation (31),
and assuming the right side of the equation is constant, the Klein equation is obtaining by
28
Physical Properties
the integration of (3). A correction factor, Kkl, was introduced when it was found that
the original Klein method often underestimated Hv . The resulting is equation is as
follows:
(32)
where R is 1.9872 cal/K-mol , Kkl = 1.045, Hvb is in units of cal/mol, Pc is in

atmospheres, and Tb and Tc are in K.
The critical pressure, Pc, may be obtained from literature or estimated by methods such
as a relation proposed by Lydersen:
Pc =
M
(.34 + P)2
(33)
where M is molecular weight and P are contribution values obtained from literature.

This method can be applied to all compounds when boiling point, critical pressure, and
critical temperature are known or can be estimated. Estimated values are within 4 to 8 %
accurate and combining the Klein method with other methods may attain more reliable
estimates.
The Klein method should be used when boiling point and critical temperature and
pressures are known or can be readily estimated. If Pc or Tc are unavailable, another
methods proposed by Haggenmacher may be useful which is calculated from vapor
pressure data and Antoines relationship.
Basic Steps
1. Obtain Tb and Tc from tabulated data in literature.
2. Obtain Pc from literature or using estimation method by Lydersen.
3. Find Hvb using modified Klein equation (4).
29
Physical Properties
Example 3
Calculate Hvb for (a) acetone and (b) acetic acid

(a) Hvb for acetone
1. Obtain Tb and Tc from tabulated data in literature9.
Tc = 508 K Tb = 329K
Groups
Contributions (atm)
CH3
2 x .2278
CO
0.28
Thus, adding all contribution values, for P we obtain a value of 0.654 atm
Pc = 58g / (.34 +.654)2 = 58.70 atm
Hvb = 7604 cal/mol = 546.45 kJ/kg

Experimental Value = 6960 cal/mol [8]
(b) Hvb for acetic acid
1.
Obtain Tb and Tc from tabulated data in literature8.
Tc = 594.6 K Tb = 391K
Groups
Contributions (atm)
CH3
2 x .2279
COOH
0.49
Thus, adding all contribution values, for P we obtain a value of 0.854 atm
Pc = 60g / (.34 +.854)2 = 42.086 atm
30
Physical Properties

Hvb = 8489.3cal/mol = 592.38 kJ/kg
7. Estimation Methods for Normal Boiling Point

Theory
The boiling point is defined as the temperature at which the vapor pressure of a liquid is
equal to the pressure of the atmosphere on the liquid. The normal boiling point is the
boiling point at one standard atmosphere of pressure. Boiling points are indicators of
physical states of compounds and provide an indication of volatility. Once known, they
can help predict other physical properties such as critical temperature and enthalpy of
vaporization.
7.1 Lydersen-Forman-Thodos Method

This method estimates normal boiling points from the critical temperature and the ratio
between the boiling point and the critical temperature. It is actually a combination of two
methods. Forman and Thodos conducted investigations into the estimation of critical
temperature while the parameter
= Tb/Tc
(34)
was developed independently. This ratio is relatively constant for most organic
compounds.
Lydersen developed a convenient way to determine . Various T increments relating to
atomic and structural features are summed. This summation is then substituted into the
following equation:
= 0.567 + T - (T)2
(35)
The estimation of Tc by Forman and Thodos is based on the correlation with van der
Waal's constants:
31
Physical Properties
Tc =
8a
= 0.2963a
27bR
bR
(36)
where Tc is the critical temperature in K, a and b are Van der Waal's constants, and R is
the universal gas constant expressed as 82.05 (atm-cm3/mol K).
Each molecule is considered to be a sum of various types of carbon atoms and functional
groups. Each group's contribution to a2/3 and b3/4 are obtained from literature and are
summed for each carbon type present and then substituted into equation (36).
Final contributions to a2/3 and b3/4 are due to functional groups present. The
contributions depend on the particular group involved and the number of carbon atoms
present. Values for a2/3 and b3/4 contributions are obtained by using tabulated values
in literature and the following equations:
a2/3 = K1/n + K2
(37)
b3/4 = K3/n +K4
(38)
where K values are obtained from literature and n is the number of carbon atoms plus
functional groups.

This method is applicable to organic compounds containing C, H, N, O and halides. Its
accuracy is generally expected to be within in 5 to 10 degrees Kelvin of the measure
value.
Basic Steps
1.
2.
3.
4.
5.
6.
Sketch the molecule, showing the locating of atoms, rings, and double bonds.
Compute T by summing the atom contributions.
Compute the value for .
Compute contributions for any functional groups.
Obtain values for a and b by using the calculating ( a 2/3)3/2 and ( b3/4)4/3
Compute Tb and Tc .
Example 4
Calculate Tb and Tc for a) acetone and b) acetic acid
a) Tb and Tc for acetone
1. Sketch the molecule, showing the locating of atoms, rings, and double bonds.
32
Physical Properties
2. Compute T by summing the atom contributions.

Groups
CH3
CO
Contributions (T)
2 x .0201
0.81
Thus, T = 0.84
3. Compute the value for
= 0.567 + 0.84 - (.84)2 = 0.6406
4. Compute contributions for any functional groups.
Groups
CH3
CO
Type
1
Organic
a2/3
15, 0351
32,4001
b3/4
11.4531
11.351
For the functional group, C=O, values for a2/3 and b3/4 contributions are calculated by
using tabulated K values and applying equation (37) a2/3 = K1/n + K2 and equation (38)
b3/4 = K3/n +K4. In this case n = 4 because acetone contains 3 carbon atoms plus one
functional group (C=O).
5. Obtain values for a and b by using the calculating ( a 2/3)3/2 and ( b3/4)4/3
a = (47,435)3/2 = 1.033 x 107
b= (22.803)4/3 = 64.66
6. Compute Tb and Tc .
Substituting values into equations (34) and (36):
Tc =(0.2963) x (1.033 x 107) / (64.66) x (82.05) = 514.6 K
33
Physical Properties
Tb = (0.6406) x (514.6) = 330.56 K

Experimental value = 329.35 K [8]
b) Tb and Tc for acetic acid
1. Sketch the molecule, showing the locating of atoms, rings, and double bonds.
2. Compute T by summing the atom contributions.
Groups
CH3
CO
Contributions (T)
.0201
0.851
Thus, T = 0.105
3. Compute the value for
= 0.567 + 0.105 - (.105)2 = 0.661
4. Compute contributions for any functional groups.
Groups
CH3
COOH
Type
1
Organic
a2/3
150351
64286.671
b3/4
11.4531
27.3661
For the functional group, COOH, values for a2/3 and b3/4 contributions are calculated
by using tabulated K values and applying equation (37) a2/3 = K1/n + K2 and equation
(38) b3/4 = K3/n +K4. In this case n = 3 because acetic acid contains 2 carbon atoms plus
one functional group (COOH).
5. Obtain values for a and b by using the calculating ( a 2/3)3/2 and ( b3/4)4/3
34
Physical Properties
a = (79231)3/2 = 2.10 x 107

b= (38.819)4/3 = 101.08
6. Compute Tb and Tc .
Substituting values into equations (34) and (36):
Tc =(0.2963) x (2.23 x 107) / (101.08) x (82.05) = 612.73 K
Tb = (0.6406) x (514.6) = 392.51 K.
Experimental value = 391.02 K [8]
References
[1] Lyman, Warren. Handbook of Chemical Property Estimation Methods. American
Chemical Society. Washington, D.C., 1982.
[2] J Gmehling and Onken. Vapor-liquid equilibrium data collection, Chemistry data
series, Dechema, 1982.
[3] Smith, Van Ness, Abbott. Introduction to Chemical Engineering Thermodynamics,
fifth Edition. McGraw-Hill. New York, 1996.
[4] Perry, William. Perry's Chemical Engineers' Handbook. Seventh Edition. McGraw
Hill, New York. 1997.
[5] King, C. Judson. Separation Processes. McGraw Hill. New York. 1980.
[6] Reid, Prausnitz, and Sherwood. The Properties of Gases and Liquids. McGraw Hill.
New York. 1977.
[7] Fredenslund. Vapor-liquid equilibria using UNIFAC. Elsevier. New York. 1977.
[8] Vargaftik, N.B. Handbook of Physical Properties of Liquids and Gases. Begell
House, Inc. 1996
[9] Manual for Predicting Chemical Process Design Data, New York, 1983.
[10] Johnson and Huang, Estimation of the Heat Capacities at Constant Pressure as a
Function Temperature, New York, 1997.
35
Physical Properties
Nomenclature
J
M
n
N
m
Xm
Xj
Vm(j)
nm
T
= component number (1 or 2 for a binary mixture)

= total number of components (=2 for a binary mixture)
= group number
= total groups
= group surface area function
= group fraction
= mole fraction of molecule j in the mixture
= number of groups of type m in molecule j
= exp (-anm / T)
= temperature (K)
36

Physical Properties and Its Use For Selection of Separation Techniques

Enviado por

Dados do documento

Título original

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

Physical Properties and Its Use For Selection of Separation Techniques

Enviado por

Direitos autorais:

Formatos disponíveis

ChE-396 Senior Design

Physical Properties, their

Senior Design ChE 396

ChE-396 Senior Design

ChE-396 Senior Design

ChE-396 Senior Design

2. Estimation Methods for Activity Coefficient

UNIFAC (UNIQUAC (Universal Quasi-Chemical) Function Group Activity

2.1 UNIFAC Method

where combinatorial part of Eq. 1 is given for a binary mixture by

1 = (r1x1)/( r1x1 + r2x2)

1 = (q1x1) / (q1x1 + q2x2)

2 = (r2x2)/( r1x1 + r2x2)

2 = (q2x2) / (q1x1 + q2x2)

ChE-396 Senior Design

Note that 1+ 2 = 1 and 1 + 2 = 1.

l1 = (z/2) (r1 q1) (r1 - 1)

l2 = (z/2) (r2 q2) (r2 - 1)

= mole fraction of components 1 and 2

For a binary mixture, the residual part of Eq. 1 is given by:

ln k = Qk [1 - ln (m m mk) - m(m km/(nn nm))]

and m and n = 1,2, N (all groups)

ChE-396 Senior Design

Acetone contains one CH3C=O group and one CH3 groups.

r1 = (1)(0.9011)+(1)(1.6724) = 2.5735, q1 = (1)(0.848)+(1) (1.4880)=2.3360

Calculate i and i from equations

Calculate l1 and l2 from equation

li = (z/2) (rI qI) (rI - 1)

l1 = (10/2)(2.5735 2.3360) (2.5735 1) = -0.3860

ChE-396 Senior Design

Calculate m and Xm for each group, using equations

For pure component

11 = Q1X11 / ( Q1 X11 + Q19 X191 + Q43 X431)

ChE-396 Senior Design

= Q1X12 / ( Q1 X12 + Q19 X192 + Q43 X432)

192 = Q19X192 / ( Q1 X12 + Q19 X192 + Q43 X432)

1 = Q1X1 / ( Q1 X1 + Q19 X19 + Q43 X43)

for each group using the value of amn in Table 11-7.

From Table 11-7, the following parameters were obtained

ChE-396 Senior Design

Now find mn for the various parameters at T=300K

for each group

For pure acetone:

ChE-396 Senior Design

ChE-396 Senior Design

2.2 Margules Method

A simple mathematical relation can thus be derived by calculating GE/x1x2RT and

Equation (1) and (2) are then combined and ln

ChE-396 Senior Design

Determine the vapor pressures by using Antoine equations:

2.3 Non-Random-Two-Liquid Method (NRTL)

ChE-396 Senior Design

ChE-396 Senior Design

ChE-396 Senior Design

3. Systems with Acid Components

AD and BD are specific to the acid and may be looked up.

ChE-396 Senior Design

Upon rearrangement equation (/24) is obtained.

ChE-396 Senior Design

where A=-10.42 and B=3166.

ChE-396 Senior Design

ChE-396 Senior Design

4. Comparison of Activity Coefficient Models Used