DISTILLATION SEPARATION FACTOR

STUDIES FOR IDEAL AND NON-IDEAL

SYSTEMS

Zawar Ahmad Khan

Supervisor
Dr. K. M. Bukhari

Co-Supervisor
Dr. Muhammad Aslam

Center for Nuclear Studies

Quaid-i-Azam University, Islamabad, Pakistan

OBJECTIVE

To study the Distillation Separation Factor.

For theoretical study H2O-HDO-D2O system (ideal system) was selected, because
experimental study of this system requires sophisticated and costly equipment, like
mass spectrometer etc.
For experimental study H2O-C2H5OH system (non-ideal system) was selected as
theoretical study of this system is quite complicated.

Theoretical Analysis
3.1

DERIVATION OF RELATIONSHIP (K = Ae-B/T)

This relationship is derived for exchange reaction H2O + D2O 2HDO in vapor phase .
For a typical reaction:

A + B C + D

(3.1)

the equilibrium constant K can be determined from the expression

K = [C] . [D] / [A] . [B]
and

RT lnK = -G

(3.2)
(3.3)

In the case of isotopic reaction, the G quantities are very small and it is not possible to calculate them from Eqn. (3.3),
since the uncertainties with which the molar free energies of the various isotopic species are known, are generally greater
than G. Furthermore, in statistical thermodynamics one can demonstrate that, for one mole of perfect gas
G = -RT ln(Z/N)

(3.9)

Where Z is the partition function for the system under consideration.

Comparing Eqn. (3.9) with Eqn. (3.3) we have
K = ZC.ZD/ ZA.ZB

(3.10)

Statistical mechanics thus permits the calculation of equilibrium constants

through the partition function Z, relevant to the reaction of various molecular
species. Since the total energy for each level can be broken down into the
terms relating to the different degrees of freedom, we find that
Z = Ztrans . Zrot . Zvibr . Zel . Znucl . e-Eo/kT

(3.11)

In which the first five factors refer in order to translational, rotational,

vibrational, electronic and nuclear degrees of freedom, and the final term

expresses the zero-point energy Eo.

For isotopic exchange reactions of the general type:

aAXb + bB*Xa aA*Xb + bBXa
(3.12)
In which X and *X are two isotopes of the same element and a and b are the number of moles
of different species
The equilibrium constant is
K = (*Z/Z)a AXb / (*Z/Z)b BXa
(3.13)
Introducing the notation u = h/kT we can write the *Z/Z ratio that appears in Eqn. (3.13) as
*Z/Z = (*Z/Z)trans.(*Z/Z)rot.(*Z/Z)vibr e()(*u-u)
(3.15)
Where Ztrans = const(M3/2 . T5/2)/P
(3.16)
And Zrot = const. IT/s
(3.17)
For diatomic or linear polyatomic molecules (where M is the molecular weight, P is the
pressure, I is the moment of inertia and `s` is the molecule's symmetry number), or
Zrot = const.(Ix Iy Iz)1/2.T/s
(3.18)
For non linear polyatomic molecules Ix, Iy and Iz are the principal moments of inertia. The
partition function for the vibrational degree of freedom is given by :
Zvibr = [1/(1-e-u)]
(3.19)
In which the product is extended to all the fundamental frequencies of the molecule. For
diatomic molecules, with only a single fundamental frequency, we obtain from Eqns. (3.16),
(3.17) and (3.19).

*Z/Z = s/*s(*M/M)3/2.(*I/I).[e-*u/2/(1-e-*u ) ].[(1-e-u)/e-u/2] (3.20)

Where as for nonlinear polyatomic molecules, we obtain from Eqns. (3.16),
(3.18) and (3.19)
*Z/Z = [(s/*s)(*M/M)3/2.(*Ix*Iy*Iz /IxIyIz)1/2]
{[e-*u/2/(1-e-*u )].[(1-e-u)/e-u/2]}
(3.21)
For polyatomic molecules the difficulties can be overcome in many cases by
making use of the rule of the product of frequencies, stated by O. Redlich
[86], which gives
(*M/M)3/2.(*Ix*Iy*Iz /IxIyIz)1/2 = (*u/u)
(3.22)
Eqn. (3.21) then becomes
*Z/Z = (s/*s) {(*u/u).[e-*u/2/(1-e-*u )].[(1-e-u)/e-u/2]}
(3.23)
This equation is also applicable to diatomic molecules, yielding results very
close to those obtained with Eqn.(3.21). Eqn. (3.23), developed in powers
series of of u = *u-u and approximated except for terms of a higher order
than the first, becomes:
*Z/Z = (s/*s)eG(u).u
(3.24)
With G(u) = 1/2 - (1/u) + 1/(eu-1).
Tabulation of the G(u) function [35], which varies from 0 to 1/2 for u
variable between 0 and , makes it far simpler to calculate the equilibrium
constants [87].

APPLICATION TO EXCHANGE REACTION

H2O + D2O 2HDO
H2O + D2O 2HDO
or
OHH + ODD OHD + ODH
Let a = b = 1; A= OH, B = OD, X = H and *X = D Using Eqs.3.12 and 3.25,
Eqn 3.13 becomes
Kvap =(*Z/Z)H O / (*Z/Z) HDO = (*Z)H O. ( Z ) HDO /{(Z ) H 2O.(*Z ) HDO}
2

Kvap = (Z)2HDO/{(Z)H O .(Z) D O}

Specifying the quantities of Eqn. (3.28) we have
2

(3.25)

(3.26)

(3.28)

Kvap=(Z)HDO.(Z)HDO /{(Z)H O .(Z) D O.}= ( SH O.SD O . /sHDO.sHDO)

(uHDO.uHDO/ u H O.u D O ){exp[-(uHDO + uHDO - uH2O - uD2O)]}f(u)
(3.29)
where
f(u) = [1-exp(-uD O )] [1-exp(- uH2O )]/[1-exp(-uHDO)]2
0
or neglecting the factor f(u) which at 1000 K differ from unity by less than 4%
we have:
Kvap = (SH O . .SD O / s2HDO )(u2HDO/ uH.O uD O).{exp[-(2uHDO - uH O uD O )]}
(3.30)
2

Sample Calculations
Consider the exchange reaction:
(H2O)vap + (D2O) vap (2HDO) vap
For the calculation of its equilibrium constant Table 3.1 below shows
the numerical values of the quantities required for the calculations.
These calculations are made by neglecting anharmonocity corrections
and by using Eqn. (3.30).
Table 3.1. Molecular constants of H2O, D2O and HDO [20].
Constant

H2O

D2O

HDO

M(a.m.u)

18

20

19

(o/c)(cm-1)

4671

3430

4077

uT (K)

6785

4938

5871

Plugging in the values of s's and u's in Eqn. (3.30) from Table 3.1, we have
Kvap = [2x2/(1)2]x[(5871)2]/[6785x4938)]x{exp[-(1/2T)(2x5871-6785-4938)]}
Kvap = 4.115 exp(-10/T)
Kvap (at 273 K) = 3.967
Kvap (at 298 K) = 3.979
Kvap (at 348 K) = 3.998
Relationship for Kvap is also determined by using Eqn. (3.23) and using the three
fundamental frequencies for every three isotopic molecules of water and the
relationship found is:
Kvap = 4 (0.753) (1..043) (1.3248) Exp (-19/T)
Kvap = 4.1732 Exp (-19/T)
Kvap (at 273 K) = 3.893
Kvap (at 298 K) = 3.915
Kvap (at 348 K) = 3.951
The corresponding error found for the three temperature are 2.0%, 1.53%, and 1.27%.

Table 3.25. Review of liquid and vapor phase equilibrium

constant data for the exchange reaction H2O + D2O
2HDO as a function of temperature by different workers.
Referenc
es
Temperat
ure C

Urey
1947
(data of
Libby and
Herzberg
1943)
K(HM)

[28]
Kirshenb
aum
1951

[35]
Bigelesi
n 1955
(Theo.)

[36]*
Pyper R. S
Newbury
and G. W.
Barton Jr
(1967) Kl
(Exptl.)

[37] A. J.
Kresgi
Chiang
(Substrate
Method)
1968 Kl
(Exptl.)

[38] J.
R.
Holston
(Calc.)
1969

[39] Wayne
C. Duer
and Gray L.
Bertand
(1970) K
(Exptl.)

[41] J. W.
Pyper, R.
J.Dupzyk, R. D.
Friesen, S. L.
Bernasek et.el
(1977) Kv

This
wor
k
199
8

3. 94

3.76

3.69

3.74 0.07

3.96
7

25

3.96

3.80

3.96

3.75 0.07

3.85 0.03

3.72

3.76 0.02

3.81 0.09

3.97
9

75

3.98

3.85

3.78

3.99
8

Conclusions
1.

2.
3.
4.
5.

Theoretical values of gas- phase equilibrium constant are calculated for

different spectroscopic data reported by different authors, from 1933 to 1997
using Eqn.(3.30).
Generally theoretical calculations of liquid-phase equilibrium constant are
quite difficult due to the involvement of intermolecular forces. But this is not
true in case of isotopic species as intermolecular forces are isotope
independent and cancel out in ratios. Also the required data is not frequently
available.
Harmonic data gives values more close to the classical value of 4.0 i.e. as
high as 3.98.
Anharmonic data gives values quite smaller than the classical value of 4.0 i.e.
as low as 3.20.
Semi empirical values of Kv and Kl show that at low temperatures i.e., up to
298 oK, Kv Kl, but at higher temperatures Kl Kv .
Values of K increases with the increase in temperature for this exchange
reaction.

SEPARATION FACTOR FOR H2O-HDO-D2O

SYSTEM
DEVELOPMENT OF SEMIEMPIRICAL RELATIONSHIP FOR
DISTILLATION SEPARATION FACTOR OF H2O-HDO-D2O SYSTEM
A theoretical approach is applied to develop a relationship between
the separation factor () for nearly ideal System i.e., H2O - HDO - D2O,

and the equilibrium constant for the exchange reaction H2O + D2O HDO
in liquid and vapor phase.
The resulting equation is of the type (distillation) = f(Kl, Kv) where Kl and
Kv are equilibrium constants in liquid and vapor, where K = Ae-B/T

DERIVATION OF RELATIONSHIP
[ (distillation) = f(Kl, Kv)]
Considering the exchange reaction in liquid phase:
H2O (liq) + D2O (liq) 2HDO (liq)
The equilibrium constant for the reaction (4.18) is
Kl = [HDO]2liq /[H2O]liq [D2O]liq

( 4.18)
( 4.19)

Applying Daltons Law of partial pressure and Roaults Law of ideal solution of mixtures
0

We arrive at
Kl / Kv = PH O PD O /( PHDO )
As HDO cannot exist in the absence of H2O and D2O its vapor pressure cannot be determined
directly and we have to make certain assumptions.

(4.23)

Assumption-I
0

PHDO is the geometric mean of PH02 Oand PD0 O i.e.,

0
PHDO
( PH0 O PD0 O )
2

(4.24)

Therefore Eqn. (4.23) gives

Kl / Kv = 1 or Kl = Kv

For separation to be possible Kl Kv, therefore this assumption is not valid [91].

(4.25)

Assumption-II

PH0 O

0
is the arithmetic mean of
PHDO

PH0 O + PD0 O

0
=(
PHDO

PD02 O

and

i.e.,

)/2

(4.26)

Subsituting Eqn. (4.26) in Eqn. (4.23) we get

Kl / Kv = 4
Kl / Kv =

0
PH0 O PD O
2

/(

PH0 O
2

+ P 0 )2
D 2O

(4.27)

(P 0 /PD0 O ) + ( PD0 O / P 0 ) +
H 2O

H 2O

/ PD0 O 2, from Eqn. (2.16); is used as it is assumed that GM rule is not

exactly obyed.
Therefore Kv / Kl (2/4) + (1/42) + (1/2)
(4.28)
The operational range of is 1.07 at 298K and 1.02 at 373K.
Let = 1.07 then Eqn. (4.28) gives Kv / Kl 1.0046
Therefore Kv 1.0046Kl , i.e., Kv > Kl
Also for = 1.02; Kv 1.0004 Kl or Kv > Kl
This result is contradicting the experimental data in this temperature range
[28]. Hence this possibility is also not valid.
But

PH0 O
2

Assumption-III
0
is the harmonic mean of
PHDO
0 =2
PHDO

PD02 O

PH0 O

PD02 O

0
D 2O

and

PH0 O
2

/( P
+ P
)
Subsituting Eqn. (4.29) in Eqn. (4.23) we get
2

H 2O

K l / Kv = ( P
+ P )2/4 P P
Kl / Kv (2/4) + (1/42) + (1/2)
When = 1.07 Kl 1.0046Kv, i.e., Kl > Kv
When = 1.02 Kl 1.0004 Kv, i.e., Kl > Kv
0
D 2O

H 2O

H 2O

i.e.,
(4.29)

0
D 2O

(4.30)

This result is in good agreement with experimental values given by Alferd

Narten in this temperature range [30]. Therefore this assumption is quite
valid. Therefore Eqn. (4.30) can be written as:
Kl / Kv (/2)2 + (1/2)2 + 2(/2)( 1/2)

We get
Kl / Kv - 1 {(-1) (+1)/2}2
(4.31)

We can assume: (i) when is slightly greater than 1 then log = (-1) and
(ii) (+1)/2 1
Therefore Eqn. (4.31) becomes
Exp((Kl / Kv - 1))

(4.32)

If C is the correction factor, then above Eqn. (4.32) becomes

= C Exp((Kl / Kv - 1))

(4.33)
As decreases and the ratio Kl / Kv increases with the increase in
temperature as shown in Table 4.16 the negative sign of exponential
power will lead to correct solution.
EXPANSION OF RELATIONSHIP
If K l A l e Bl /T , K v A v e Bv /T and C C avg , then Eqn. (4.33) becomes:
-

Al
e
Av

B v Bl
T

= C avg e
Taking log of both sides of above Eqn. and approximating:
Exp{(Bv-Bl) /T} = 1+(Bv - Bl)/T, we get:
log = log Cavg - [ (Al/Av) { 1 + (Bv - Bl)/T }- 1 ]1/2

(4.34)

CALCULATION OF CORRECTION
FACTOR (C)

Firstly (Kl, Kv) data quoted in [30] is used for the

calculation of factor
Exp( (Kl / Kv - 1) ).
Secondly is calculated using empirical Eqn. quoted
in [63 ] i.e;

log = log ( P / PHDO

) = (019645.4/T ) -(48.5026/T) +
0.013615
Then expression = C Exp( (Kl / Kv - 1) ) is used for
the calculation of correction factor C.
Values of these factors are reported in Table 4.16.
1

H2O

Table 4.16. Calculated values of C and data used in its calculations

Temp. K

Kl [28]

Kv [28]

Kl / Kv

Exp (-(Kl / Kv - 1))

270

3.42

3.448

0.99188

280

3.46

3.475

0.99570

290

3.50

3.497

1.00086

0.9711

1.083

1.11523

300

3.53

3.517

1.00370

0.9410

1.073

1.14030

310

3.55

3.533

1.00481

0.9331

1.064

1.14029

320

3.57

3.551

1.00540

0.9292

1.0554

1.13582

330

3.59

3.568

1.00620

0.9243

1.048

1.13383

340

3.61

3.583

1.00754

0.9170

1.042

1.13650

350

3.63

3.598

1.00890

0.9100

1.036

1.13864

360

3.64

3.621

1.00780

0.9155

1.031

1.12620

370

3.66

3.625

1.00970

0.9062

1.026

1.13220

380

3.67

3.638

1.00880

0.9105

1.0223

1.12280

Table 4.17 Data for the development of empirical equations and

evaluation of constants Al, Av, and Bl, Bv.
Temp.
K
270

X-axis
(1000/T)
3.704

Y-axis
(ln Kl)
1.22964

Y-axis
(ln Kv)
1.2378

280

3.571

1.24130

1.2456

290

3.448

1.25280

1.2519

300

3.333

1.26130

1.2576

310

3.226

1.26700

1.2622

320

3.125

1.27260

1.2672

330

3.030

1.27820

1.2720

340

2.941

1.28370

1.2762

350

2.857

1.28920

1.2804

360

2.778

1.29200

1.2843

370

2.703

1.29750

1.2879

380

2.632

1.30020

1.2914

121

120

1.29
1.30

1.29

1.28

1.29

Log K [Vapor]

Log K [Liquid]

1.28

1.28

1.28

1.27

1.27

1.27

1.26

1.27

1.26

1.26
2.80

2.70

3.00

2.90

3.20

3.10

2.80

3.30

1000/T

Figure 4.1. Fitted curve for the determination of empirical constants for K (l).

2.70

3.00

2.90

3.20

3.10

3.30

1000/T
Figure 4.2. Fitted curve for the determination of empirical constants for K (v).

RESULTS
Two curves are are plotted in Figures 4.1 and 4.2 using data given in
Table 4.17. Empirical equations and values of constants evaluated are
given below
4.2.4.1 Statistics and fitted empirical equation for Kl
(i) Statistics:
log Kl = -57.91/T + 1.4536
Regression sum of squares = 0.00226535
Residual sum of squares = 4.77678 E-006
Co-efficient of determination R2 = 0.997896
Residual mean squares = 5.97097 E-007
(ii) Empirical equation developed is of the type:
Kl = 4.2785 e-57.91/ T
4.2.1.1 Statistics and fitted empirical equation for Kv
(i) Statistics:
log Kv = - 48.463/ T + 1.41885
Regression sum of squares = 0.00158652
Residual sum of squares = 2.6971 E-007
Co-efficient of determination R2 = 0.99983
Residual mean squares = 3.3713-008
(ii) Empirical equation developed is of the type:
Kv = 4.132 e-48.463/T

(4.35)

(4.37)

SAMPLE CALCULATIONS
Empirical equations obtained are given below:
Kl = 4.2785 e - 57.91/T and Kv = 4.132 e - 48.463/T
The values of empirical constants obtained from these equations and
Table 4.16 are listed below:
log Cavg = 0.124155; Al = 4.2785, Bl = 57.91; Av = 4.132, Bv = 48.463
Plugging these values in Eqn. (4.34); we get
log = 0.124155 - [0.0355 - (9.782/T)]1/2
(4.39)
This equation is valid for the temperature range of 283 K to 370 K.
(i) Now at 300 K, log = 0.124155 - 0.0538 = 0.0704,
therefore = 1.073
(ii) And at 373 K, log = 0.124155 - 0.096306 = 0.02785,
therefore = 1.028

COMPARISON OF RESULTS
Table 4.18. Comparison of results of separation factor for H2O-HDO-D2O system of various workers as a function of temperature.
Re
f.N
o.

Temp. K

[6
3]

Lewis and
McDonald
1933(Calc;)

[2
1]

B. Topely
H. Eyring
1933
(Theoretical)

[5
6]

Riesenfeld
and Chang
1936 (Calc;)

1.082
2

[5
5]

Miles and
Menzies
1936
(Empirical)

1.093
6

[2
8]

Kirshenbau
m
1951
(Calculated)
Combs
Googin and
Smith 1954
(Calculated)

[6
1]

[6
1]

273

E. Whalley
1957
(Empirical)

[6
4]

W. M. Jones
1968(Calc.)

293

298

303

313

323

333

343

1.069
3

1.060
8

1.05
33

1.04
7

1.0406

1.067

1.060

1.05
3

1.071
4

1.062
9

1.056

1.04
94

1.04
37

1.0386

1.035

1.0298

1.02
58

1.079
5

1.069
8

1.061
3

1.05
34

1.04
65

1.0404

1.0348

1.030

1.02
58

1.066

1.059

1.05
2

1.071
4

1.063

1.05
45

1.075

1.063

1.05
1

1.079

1.092

1.12

Combs
Googin and
Smith 1954
(Exptl.)

[5
9]

283

1.083

1.07
1

1.087

1.07

1.093
6

1.082
2

1.100
3

1.087
3

1.109

1.08
2

1.07
2

1.088
2

1.078

1.060

1.05
3

353

363

373

1.0353

1.031

1.02
67

1.03
8

1.02
5

1.02
6

1.05
0

1.068
2

348

1.03
5

1.04
62

1.0403

1.02
5

1.0351

1.0304

1.02
61

Table 4.18 continued........

Ref.
No.

Temp. K

273

[65]

W. Alexander
Van Hook
1968
(Empirical)

1.105

[66]

Jovan Pupezine
et. al 1972
(Empirical)

1.1076

1.0932

1.081

1.0703

1.0612

1.0533

1.0464

1.0404

1.0352

1.0306

1.0267

[66]

From salt
solution
data (+0.3)
(Empirical)

1.1074

1.093

1.0807

1.0701

1.061

1.0531

1.0462

1.0403

1.0352

1.031

1.027

[38]

J. H. Rolston
1976 (Empirical)

1.113

1.098

1.080

1.074

1.065

1.056

1.040

[69]

Gy Jakli and
G. Jancso` 1980
(Empirical)

1.107

1.093

1.076

1.071

1.062

1.054

1.038

[72]

Rong Sen Zhang

1988 (Empirical)

1.108

1.0932

1.081

1.075

1.070

1.061

1.053

1.0463

1.0404

1.038

1.0353

1.031

1.027

1.098

1.0813

1.0751

1.070

1.061

1.0533

1.047

1.0414

1.039

1.03654

1.032

1.0282

This work 1998

(S. Empirical)
Eqn. (4.39).

283

293

298

303

313

1.075

323

333

343

1.054

348

353

363

1.038

373

1.028

1.027

Discussion
Previously it was thought that H2O-HDO-D2O system is a perfectly
ideal mixture, and it was also assumed that vapor pressure of HDO is
the geometric mean (GM) of the vapor pressure of H2O and D2O, as
HDO exists only in the presence of H2O and D2O, and cannot be
isolated [21, 52, 53, 35]. But later on several workers have reported
that this system deviates from perfect ideality and GM rule is not
exactly valid [30, 65, 66, 67, 69, 90]. The main problem in water is to
be able to distinguish between the contributions arising from deviation
of the
(i) GM rule for the vapor pressure of HDO (ii) that arising from the
non-ideality of liquid mixture (iii) and non ideality of the vapor, in the
sense of deviation from perfect gas equation. We have attributed the all
effect to non-validity of GM rule.
Our semi-empirical model is based on the assumption that vapor
pressure of HDO is the harmonic mean (HM) of vapor pressure of H2O
and D2O, and a comparison of our results with those of other workers
is given in Table 4.18 and Figure 4.3.

122

Separation Factor
vs Temperature Plots
of different Workers
Ref. 61

1.12

Ref. 19

1.11

Ref. 54
Ref. 53
Ref. 26

1.10

Ref. 59[Calc;]
Ref. 59[Exptl;]
Ref. 57

Separation Factor

1.09

Ref. 62
Ref. 63
Ref. 64[Empirical]

1.08

Ref. 64[salt solu; data]

Ref. 36
Ref. 67

1.06

Ref. 70

1.05

This work 1998

1.04

1.03

1.02
283.00

273.00

303.00

293.00

323.00

313.00

343.00

333.00

363.00

353.00

373.00

Temperature [K]
Figure 4.3. Separation Factor vs Temperature curves representing data of different
workers.

CONCLUSIONS

It is clear from Lewis and R.E. Cornish paper that if ideality of H2O - HDO - D2O
system is assumed then
=( P
/ P )1/2
In [21] B. Topley and H. Eyring (1934) have reported the theoretical expression
for = 0.861Exp (65/T).
In [50] it is reported by T. Tucholski that the action of slow evaporation is more
efficient than the action of boiling for the separation of D from H.
In [52] it is reported by Wynne Jones that (Exptl) differs from (Empirical)
and (Theoretical) due to the following assumptions
(i) ( P )GM = ( P P )1/2 or (ii) slight deviation from ideal behavior.
From [53] data it is concluded that the data of Milton H. Wahl and H. C. Urey
that ( P )HM is more close to ( P )Exptl than ( P )AM and (P )GM.
0

0
D 2O

H 2O

HDO

HDO

H 2O

0
D 2O

HDO

HDO

HDO

In Tables 4.4 to 4.6 it is concluded by Robert L. Combs et all that:

(i) (HM) is more close to (Exptl) (reported by Kirshenbaum).
(ii) From Table 4.6 it is again concluded that ( P )HM assumption
is more suitable.

HDO

 In [63] it is stated by Lewis and R. T. McDonald that [H(HDO)]liq

[H(HDO)]vap due to intermolecular forces in liquid phase.
It is also well known that [S(HDO)]liq [S(HDO)]vap, and as
G = H - S. Therefore [G(HDO)]liq [G(HDO)]vap.
Also it is known fact that
- G = RT ln K or K = Exp (- G/RT ) from where it is evident that Kv
Kl, which proves that HM rule is applicable instead of GM or AM

rule for PHDO

In [30] it is proved by Alfred Narten that geometric mean rule is not
obyed.
In [65] the non-ideality of H2O-HDO-D2O system is proved by
Alexander Van Hook.
In [67] the deviation from geometric mean rule is shown to be from
0.02 to 0.08 by Alexander Van Hook.

 In [68] and [69] Gy. J. Akli et. al also show the deviation from ideality
of H2O - HDO - D2O system and we have proved the validity of HM
assumption from their data and
Kl Kv indicates that separation is possible.
Kl - Kv ) decreases with increase in temperature which explains the fact
that decreases with increase in temperature.
Values of calculated from our semiempirical model match well with
the theoretical and empirical values of many other workers. The
values found by us are also in good agreement with the experimental
values quoted in litrature and it is safer to use our relationship in the
temperature range 295 K to 345 K.

EXPERIMENTAL STUDY OF H2O-C2H5OH

SYSTEM

EVAPORATION OF ETHANOL-WATER MIXTURE-I

Experiments were performed to determine the rates of evaporation in ethanol-water
mixtures under different conditions. The objectives of these experiments are to study
the separation of water from ethanol by using evaporation with forced circulation of air
at ambient temperature.
APPARATUS
The major apparatus used along with their functions are given below :
i)
Solution density measurement apparatus DMA-48 of Anton Parr was used to
determine the Vol% Ethanol in Ethanol-Water mixture.
ii)
Air Drying unit (AD) which contains CaCl2. Air is sucked through this unit to
make it as dry as possible.
iii)
Air flow rotameter (AFM) to measure the flow rate of air (range 0-3000 lt/hr).
iv)
Liquid flow rotameter (LFM) to measure flow rate of liquid feed mixture
(range 0-60 lt/hr).
v)

Thermometer (T) of thermovalve type to record the temperature of the process.

vi) Vacuum gauge (VG) with range 760 to 0 mm of Hg.

vii) Peri-Staltic type variable flow liquid pump (LP) having range up to 100 lt/hr.
viii) Oil diffusion vacuum pump (VP). A vacuum of 650 mm of Hg can be
attained in the apparatus.

Diameter of column
Packing nominal diameter
Packed height

80 mm (3 in)
8 mm (0.375 in)
1.5 m (5 ft)

EXPERIMENTAL DETAIL
The experiments were performed in Apparatus shown in Figure 5.1

PROCEDURE
1.
2.

3.

4.

5.
6
7

A calibration curve was plotted between LFM readings and liquid flow rate (lt/hr),as
shown in Figure 5.2.
Air Flow meter was calibrated using a pre-calibrated flow-meter and confirmed by
the collection of air in a polyethylene bag for a fixed time. A calibration curve was
drawn between air-flow rate and vacuum gauge readings, as shown in Figure 5.3.
To measure liquid mixture composition a calibration curve was drawn between liquid
mixture density (gm/cc) and Vol% Ethanol using Anton Parr DMA-48 fluid density
measurement apparatus, as shown in Figure 5.4.
1200 ml of mixture of a fixed composition, say 42% Ethanol by volume was taken in
each experiment with different air flow rates (420 lt/hr to 1220 lt/hr).
In each experiment the plant was operated for one hour with liquid flow rate of 6
lt/hr.
The experiments were repeated for 30.5, 26.5, 20.5, and 16.5 Vol% Ethanol in
mixtures.
In each experiment the column was first dried by passing dry air for 1/2 hr. The feed
liquid was then run through the column for 15 min. Then liquid is allowed to
accumulate in the calibrated liquid leg for 5 min and the liquid level is recorded and
its composition is measured by taking a small sample.
The change in liquid level giving the volume evaporated of liquid mixture and
change in composition was recorded after 1hr operation.

27.50

1200.00

25.00

1000.00

AIR FLOW RATE (lt/hr)

LIQUID FLOW RATE (lt/hr)

22.50

20.00

17.50

15.00

800.00

600.00

12.50

10.00

400.00

7.50

200.00

5.00

50.00

30.00

25.00

40.00

35.00

50.00

45.00

60.00

55.00

FLOW METER READINGS

Figure 5.2. Calibration curve for liquid flow meter.

0.00

150.00

100.00

250.00

200.00

350.00

300.00

400.00

VACUUM (mm Hg)

Figure 5.3. Calibration curve for air flow meter.

1.00

0.98

0.96

DENSITY (gm/cc)

0.94

0.92

0.90

0.88

0.86

0.84

0.82

0.80
10.00

0.00

30.00

20.00

50.00

40.00

70.00

60.00

90.00

80.00

100.00

VOL% ETHANOL

Figure 5.4. Density of ethanol-water mixture vs Vol% ethanol in mixture.

Table 5.1. Data for the evaporation of mixture of commercial ethanol and water
Air Flow Rate
(lt/hr)

Volume
of Mixture
Evaporated(ml/hr)

Vol% Ethanol
Initial

Vol% Ethanol
after 60 min

Vol% of Mixture
after 60 min

Process Temperature
oC

420

84

42.0

36.0

6.0

27.5

680

105

42.0

35.5

6.5

27.0

940

120

42.0

35.0

7.0

29.0

1220

140

42.0

34.0

8.0

27.5

420

65

30.5

27.0

3.5

27.0

680

85

30.5

25.5

5.0

28.5

940

90

30.5

25.5

5.0

27.0

1220

100

30.5

25.0

5.5

27.0

420

60

26.5

23.5

3.0

28.0

680

70

26.5

23.0

3.5

27.0

940

90

26.5

22.5

4.0

29.0

1220

90

26.5

21.5

5.0

27.5

420

55

20.5

18.5

2.0

29.0

680

65

20.5

17.0

3.5

27.5

940

80

20.5

17.0

3.5

27.0

1220

85

20.5

15.0

5.5

28.0

420

50

16.5

14.7

1.8

27.0

680

55

16.5

14.5

2.0

26.0

940

60

16.5

14.5

2.0

24.0

1220

60

16.5

14.0

2.5

24.0

MATHEMATICAL MODELING ( An Analytical Approach)

To develop different mathematical models a kinetic approach is
applied to the rate of evaporation of volatile liquids [73]. Due to
universal nature of the Arrhenius Law as it is applied to biological and
medical fields we have used it to study the rate of evaporation and
separation of mixture of volatile liquids. Different models have been
made by using different sets of assumptions. In each model a
mathematical equation is made that contains a parameter K (same
symbol K and k are used for different models, they should be
considered as different for every model). The value of this parameter is
then found by testing it against the experimental data. If the parameter
has the same value for each data, then we say that the fit is good, and
the particular model is also good. However, if different experimental
results give different values of K, then the model is not considered to
be good.

KINETIC MODEL -IA

This model is made with the following assumptions [74]:
i) Due to the lower volatility of water as compared to ethanol,
evaporation of water is neglected .
ii) Rate of evaporation of ethanol is proportional to its
concentration, i.e. exponential decrease in concentration
of ethanol as a function of time.
This results in the equation : C(t) = C(0)
velocity constant.

or

1
C ( 0)
K log
t
C(t )

Kt

, where K [1/hr] is the

(5.1a)

Values of 'K' are calculated for different air flow rates and feed
concentrations and as there is variation in the values of 'K',
therefore an average value is reported for different air flow rates
in Table 5.2 for ethanol water mixture. The values of Kavg
increases from 0.122 to 0.219 for air flow rate 420 to 1220 lt/hr
for Model-IA. Experimental and calculated values of vol%
ethanol in product are reported in Table 5.3.

Table 5.2. Values of average rate constants Kavg for different air flow rates and vol%
ethanol in feed for Model-IA.

420

680

940

1220

0.122

0.161

0.168

0.219

Air flow rate

(lt/hr)
Kavg

Table 5.3. Experimental and calculated values of vol% ethanol in product(Model-IA).

Vol% Ethanol
in feed C(0)

Vol% Ethanol
after 60 min
C(t)expt

Vol% Ethanol
after 60 min
C(t)cal

% error

420

42.0

36.0

37.176

-3.270

680

42.0

35.5

35.754

-0.716

940

42.0

35.0

35.505

-1.443

1220

42.0

34.0

33.740

+0.765

420

30.5

27.0

26.997

+0.011

680

30.5

25.5

25.964

-1.820

940

30.5

25.5

25.783

-1.110

1220

30.5

25.0

24.501

+1.996

420

26.5

23.5

23.456

+0.187

Air Flow Rate

(lit/hr)

Table 5.3 continued

680

26.5

23.0

22.559

+1.917

940

26.5

22.5

22.402

+0.436

1220

26.5

21.5

21.288

+0.986

420

20.5

18.5

18.146

+1.914

680

20.5

17.0

17.452

-2.659

940

20.5

17.0

17.330

-1.941

1220

20.5

15.0

16.468

-9.787

420

16.5

14.75

14.620

+0.881

680

16.5

14.5

14.050

+3.103

940

16.5

14.5

13.950

+3.793

1220

16.5

14.0

13.250

+5.357

Maximum error in this model is 9.787% which is much below the allowable value of 25%
[76]. Graphical represention of experimental and calculated vol% ethanol in product as a
function of vol% ethanol in feed and air flow rate are shown in Figures 5.5 and 5.6.

141

140

38.00

38.00

35.50

33.00

Air flow rate (lt/hr)

1220 lt/hr
1220 lt/hr
940 lt/hr
940 lt/hr
680 lt/hr
680 lt/hr
420 lt/hr
420 lt/hr

35.50

33.00

30.50

Vol% Ethanol in Product

Vol% Ethanol in Product

30.50

28.00

25.50

23.00

Vol% ethanol in feed

42%
42%
30.5%
26.5%
26.5% Markers represent Exptl. data.
20.5% Curves represent Calc. values.
20.5%
16.5%
16.5%

28.00

25.50

23.00

20.50

20.50

Markers represent Exptl. data.

Curves represent calc. values.

18.00

18.00

15.50

15.50

13.00

13.00
21.00

16.00

31.00

26.00

500.00

41.00

36.00

Vol% Ethanol in Feed

Figure 5.5. Experimental and calculated values of Vol% ethanol in product vs Vol%
ethanol in feed for Model-IA.

400.00

700.00

600.00

900.00

800.00

1100.00

1000.00

Air Flow Rate (lt/hr)

Figure 5.6. Experimental and calculated values of Vol% ethanol in product
vs Air flow rate for Model-IA.

1200.00

KINETIC MODEL-IB
i)
Due to the lower volatility of water as compared to ethanol,
evaporation of water is neglected.
ii) Linear decrease in concentration of ethanol as a function of time
is assumed i.e.,
C(t) = C(0) - K t
C(0) C(t)
or
(5.1b)
K
t

where K [hr-1] is a velocity constant. Values of 'K' are calculated for

different air flow rates and feed concentration and average values of
'K' are calculated for every air flow rate.
The values of Kavg increases from 3.25 to 5.3 when air flow rate
increases from 420 to 1220 lt/hr for Model-IB.
Maximum error in this model is 20% which is below the allowable
value of 25%

KINETIC MODEL-II
The following four assumptions are used :
i)
Due to the lower volatility of water as compared to ethanol
evaporation of water is negligible i.e., Vw(t) = Vw(0) = Vw =
constant, where Vw is the volume of water in mixture.
ii) Volume of ethanol in mixture is a function of time, i.e. Va(t).
Va ( t )
Ca ( t )
iii) Volume fraction of ethanol
(5.2)
Vw Va ( t )
iv) From Arrhenius Law, rate of decrease in volume of mixture is
proportional to ethanol concentration.
Therefore:

dVa t
Va t
KC a t K
dt
Vw Va t

V (loss) Vw (0)
K a

log
t
t

Va (loss)
1

Va (0)

(5.3)

(5.10)

Again values of 'K' are calculated for different air flow rates and feed
concentration, and as there is variations in the values of 'K' an average
value is calculated for every air flow rate, as reported in Table 5.6. The
value of Kavg increase from 264 to 405 for the Model-II when air flow
rate increases from 420 to 1220 lt/hr.
Maximum error in this model is 17.65% which is below the allowable
value of 25% [76]. A large positive error due to the reason that a
constant volume of water (VW) is assumed.

KINETIC MODEL -III

This model is based on the following two assumptions.
i)

Due to the lower volatility of water as compared to ethanol evaporation of

water is neglected.

ii)
dV/dt = -k [C(t)] n is assumed, where dV/dt = volumetric rate of
evaporation of mixture, C(t) = C(0) - Kt, where K [1/hr] is rate constant, n is order of
reaction and k = proportionality constant which is a function of air flow rate,
temperature, liquid flow rate, interfacial area and nature of the liquid.
Therefore

dV
k[ C(t)]n k [C(0) - Kt]n
dt
VI KJ FI n1 PI n1

VJ KI FJ n1 PJ n1

(5.11)
(5.16)

Where postscript I and J represents two different cases of volume evaporated (V),
vol% ethanol in feed (F), vol% ethanol in product (P) and rate constant (K).
The average values of ns varies from 0.41 to 0.87 for air flow rates from 420 to
1220 lt/hr.

MODELS IVA AND IVB

These models are based on the following assumptions :
i)
Due to the lower volatility of water as compared to ethanol evaporation of water
is neglected. dV
k[C( t )]n k [C(0) e-Kt ]n
ii)
(5.17)
dt
where, dV/dt is volumetric rate of evaporation, and n is order of reaction.
C(t) = C(0) e Kt, K is rate or velocity constant, and k is proportionality constant
as defined in model - III.
To use computer for iterative calculations the above equation is written as under:
MODEL-IVA
VI [CI]n KJ [1 e nKI]
VJ

[CJ ]n

*
KI [1 e nKJ ]

Where postscript I and J represents two different cases of ethanol concentration in feed
(C), rate constant (K) and volume evaporated (V).
As nK 0
e-nK = 1-nK
Eqn. (5.20) gives:

k[C( 0)]n
V
[1 1 nK] k [C( 0)]n
nK

(5.21)
For iterative computer calculations the above equation is written as under:
VI
VJ

CI n
CJ n

MODEL-IVB

For different air flow rates anavg varies from 0.396 to 0.920 and bnavg varies from 0.404
to 0.829.

DISCUSSION

The maximum error for Model-IA is 9.8%, which is reasonable for such experimental
data.
The maximum error for Model-IB is 20.0% at low concentration of ethanol i.e., 16.5%.
It is clear from Figure 5.8, that this model gives good results from 42 to 20% ethanol in
feed.
The maximum error for Model-II is 17.65%. This negative error is due to the addition
of a constant quantity Vw in the denominator of Eqn. (5.2). This assumption have more
effect due to the more evaporation of water at higher air flow rates.
Therefore analytical Model-IA is more appropriate for this process conditions due to
lesser error as compared to other two models. Furthermore by looking at Tables 5.8, 5.9
and 5.10 it is clear that order of reaction i.e., values of ns increases with air flow rate in
Model-III, IVA and IVB show same behavior. The values of navg for these models
match each other with maximum error of 4%.
The mathematical models developed by analytical techniques do not give a constant
value of the parameter 'K' and n for different cases due to the following reasons.
i)
Error in the measurements of 'volume evaporated' due to large hold up
ii)

iii)

of column and small volume change.

There is also temperature variation (i.e., 24 to 29C) which is not taken into
account.
Error due to the Humidity of input air.

EVAPORATION OF ETHANOL-WATER
MIXTURE-II
INTRODUCTION

There are two general approaches for curve fittings that are distinguished
from each other on the basis of the amount of error associated with the data.
First, when the data exhibits a significant degree of error or 'noise' the
strategy is to derive a single curve that represents the general trend of the
data. Approach of this nature is called Least Square Regression.
Second, when the data is known to be very precise the basic approach is
to fit a curve or a series of curves that pass directly through each of the
points. This estimation of values between well-known discrete points is
called Interpolation.
MATHEMATICAL MODELING (An Empirical Approach)

As our data is of first kind, so it is preferred to apply least square regression

technique to see the variation of 'volume evaporated' first as a function of
normalized air flow rate; secondly air flow rate as function of feed
concentration; and thirdly changes in ethanol concentration as a function of
air flow rate. The details of these curves which are made by using computer
software and experimental data of Table 5.1 are given below.

153

154

2.80

2.80
Vol%
42%ethanol in feed
42%
30.5%
30.5%
26.5%
26.5%
20.5%
20.5%
16.5%
16.5%

Volume Evaporated (Normalized)

2.40

2.20

2.60

2.40

Volume Evaporated (Normalized)

2.60

Vol%
42%ethanol in feed
42%
30.5%
30.5%
26.5%
26.5%
20.5%
20.5%
16.5%
16.5%

Markers represent data points.

Curves represents straight line fit.

2.00

1.80

1.60

1.40

Markers represent Exptl.data.

Curves represent log regression fit.

2.20

2.00

1.80

1.60

1.40

1.20

1.20

1.00
1.00

0.80

1.40

1.20

1.80

1.60

2.20

2.00

2.60

2.40

1.00

3.00

2.80

Air Flow Rate (Normalized)

Figure 6.1. Shows Normalized (Volume of mixture evaporated vs Air flow rate)
using straight line fit for different initial concentration of ethanol.

3.20

1.00

0.80

1.40

1.20

1.80

1.60

2.20

2.00

2.60

2.40

3.00

2.80

3.20

Air Flow Rate (Normalized)

Figure 6.2. Shows Normalized (Volume of mixture evaporated vs Air flow rate) using
Log regression curve fitting for different initial concentration of ethanol.

158
140.00

Markers represent Expt.; data.

Air
Flow
420
lt/hrRates Curves represent Log regression fits.
420 lt/hr
680 lt/hr
680 lt/hr
940 lt/hr
940 lt/hr
1220 lt/hr
1220 lt/hr

130.00

Volume of mixture evaporated (ml/hr)

120.00

110.00

100.00

90.00

80.00

70.00

60.00

50.00
21.00

16.00

31.00

26.00

41.00

36.00

Vol% ethanol in feed

Figure 6.6. Shows Volume of mixture evaporated vs Vol% ethanol in feed using Log
regression curve fitting for ethanol-water mixture for different air flow rates.

EMPIRICAL EQUATIONS OF TYPE ( V = a + b Log F + e Log C )

From the above figures it is clear that 'volume evaporated' shows logarithmic relationship
with 'air flow rate' and 'feed concentration of mixture'. On this basis the following empirical
equation is derived.
V1 a / b Log F

(6.1)

where F is air flow rate, V1 volume evaporated, a' and b are constants.
V2 d e Log C
Similarly
(6.2)
Where C is the ethanol concentration , V2 is volume evaporated, d and e are empirical
constants.
Combining Eqns. (6.1) and (6.2) we get:
(6.3)
V V1 V2 (a / d) b Log F e Log C
Let
a' + d = a
V a b Log F + e Log C
Then
(6.4)
The values of 'a', 'b', and 'e' are determined by 'Multiple Linear Regression' technique,
for which computer program is attached at Appendix-4. The values determined for, a, b, e
and V are given as output. These results indicate that more than 90% of the original
uncertainty has been explained by this model i.e. R 2 0.90 [75].
For commercial ethanol empirical equations for volume evaporated of ethanol and
ethanol-water mixture as a function of 'air flow rate' and 'feed concentration' are given
below:
V(ethanol) = -361.431 + 26.7 Log F + 77.3 Log C
(6.5)
V(mixture) = -336.7 + 33.95 Log F + 59.23 Log C
(6.6)
The three dimensional graphical representation for Eqns. (6.5) and (6.6) are given in Figures
6.11 and 6.12 respectively.

 The maximum error is 16.67% which is below the allowable value of 25%
[76]. Graphical representation of experimental and calculated volume of
mixture evaporated (ml/hr) as a function of log of air flow rate and vol%

ethanol in feed arerepresented in Figures 6.13 and 6.14 respectively. Plot

of calculated vs experimental values of volume of mixture evaporated for
this model are shown in Figure 6.15, the fitted line have equation Y =
1.012*X with R2 = 0.995736 (which means more than 99.58% of
uncertainity has been explained by this model [75]).

ETHANOL VOLUME EVAPORATED (ml/hr).

Fig 6.11

AIR FLOW RATE (lt/hr).

VOL% ETHANOL IN FEED

Figure 6.11. Three dimensional graphical representation for Volume of ethanol evaporated as a function of

Air flow rate and Vol% ethanol in feed for empirical Model-I [Eqn. (6.5)].

MIXTURE VOLUME EVAPORATED (ml/hr)

Fig 6.12

AIR FLOW RATE (lt/hr)

Figure 6.12. Three dimensional graphical representation for Volume of mixture evaporated as a function of

Air flow rate and Vol% ethanol in feed for empirical Model-I [Eqn. (6.6)].

165

166
124.00

124.00

Vol%
42%ethanol in feed
42%
30.5%
30.5%
26.5%
26.5%
20.5%
20.5%
16.5%
16.5%

114.00

114.00

104.00

Volume of mixture evaporated (ml/hr)

Volume of mixture evaporated (ml/hr)

104.00

Air
flow
420
lt/hrrates
420 lt/hr
680 lt/hr
680 lt/hr
940 lt/hr
940 lt/hr
1220 lt/hr
1220 lt/hr

94.00

84.00

74.00

64.00

54.00
Markers represent Exptl. data.
Curves represent Calc. values
44.00

94.00

84.00

74.00

64.00

Markers represent Exptl. data.

Curves represent Calc. values.

54.00

44.00

34.00

34.00
6.20

6.00

6.60

6.40

7.00

6.80

7.20

Log of air flow rate (lt/hr)

Figure 6.13. Shows Experimental and calculated values of Volume of mixture evaporated
vs Log of air flow rate for straight line fits for different Vol% ethanol in feed
for empirical Model-I.

2.90

2.80

3.10

3.00

3.30

3.20

3.50

3.40

3.70

3.60

Log of vol% ethanol in feed

Figure 6.14. Experimental and calculated values of volume of mixture evaporated vs
Log of Vol% ethanol in feed for straight line fit for different Air flow
rates for empirical Model-I.

3.80

167

115.00

V(Calc.) = 1.012* V(Exptl.) and R**2= 0.995736

for empirical Model-I [Eqn. (6.6)].

Calculated volume of mixture evaporated (ml/hr)

105.00

95.00

85.00

75.00

65.00

Markers represent Exptl. data.

Curves represent Calc. values.

55.00

45.00
55.00

45.00

75.00

65.00

95.00

85.00

115.00

105.00

Experimental volume of mixture evaporated (ml/hr)

Figure 6.15. Calculated values of volume of mixture evaporated vs Experimental values
of volume of mixture evaporated for empirical Model-I [Eqn. (6.6)].

EMPIRICAL EQUATIONS OF TYPE (Y = a Xb Zc )

We have done some further analysis of data of Table 6.1 using another technique given in
referance [76]. We have used the computer software and following procedure to find the
empirical equations of the type Y = a Xb Zc.

(i)

Plotted experimental values of volume of mixture evaporated (VE) vs air flow rate (AF).

This will give us four curves one for each ethanol concentration in feed. Fitted the power
exponential equation: VE = a (AF)b and found the value of a and b for each concentration.
An average value of 0.42 is taken for b taken from Figure 6.16.

(ii)

VE / (AF)0.42 = c (CF) d again. The value of c = 0.681, d = 0.643, and

Plotted VE / (AF)0.42 vs initial concentration (CF). Fitted the power exponential equation:

R2 (coefficient of determination) = 0.92 was obtained. Which means more than 92% of
uncertainty has been explained by this model [75] taken from Figure 6.17.

(iii)

Plotted (VE / (CF)0.643) vs AF. Fitted the power equation: VE / (CF)0.643 = e (AF)f. Then

we obtained e = 0.572, f = 0.427, and R2 = 0.921, taken from Figure 6.18.

(iv)

The equation VC= 0.572 (AF)0.427 (CF)0.643 was obtained.

 In Table 6.2 are shown the initial concentrations of ethanol, and the
volume of mixture evaporated (experimental and calculated by ModelII) for different air flow rates. As a first approximation since the
temperature are all within five degree Celsius of each other, we assume
that the effect of temperature may be neglected. The volume
evaporated has been related to the air flow rates and initial
concentration, and it has been found that best fit for the data is made
by the equation:
VC = 0.572 (AF)0.427 (CF)0.643
Where VC = Total Volume Evaporated (ml)

AF = Air flow rate (lit/hr)

CF = Initial ethanol concentration in mixture (Vol %)

(6.7)

168

8.00

Solid lines represent equation.

Markers represent exptl. data.
Vol%
42%ethanol in feed
42%
30.5%
30.5%
26.5%
26.5%
20.5%
20.5%

145.00

7.50

135.00

Volume of mixture evaporated (ml/hr)

Solid lines represent equations.

Markers represents data.
Y=0.681*X**0.643
R**2 = 0.916673

Volume Evaporated /(Air Flow Rate)**0.42

155.00

169

125.00

115.00

105.00

95.00

7.00

6.50

6.00

5.50

5.00

85.00
4.50

75.00

4.00

65.00
520.00

420.00

720.00

620.00

920.00

820.00

22.50

1120.00

1020.00

1220.00

Air Flow Rate (lt/hr)

Figure 6.16. Experimental Volume of mixture evaporated vs Air flow rate for different
Vol% ethanol in feed using Power law fit for the development of empirical
Model-II.

20.00

27.50

25.00

32.50

30.00

37.50

35.00

40.00

Vol% ethanol in feed

Figure 6.17. Plotted Volume evaporated / (Air flow rate)**0.42 vs Vol% ethanol in feed,
using Power law fit for the development of empirical Model-II.

170
14.00

Solid lines represent equation.

Markers represernt Exptl. data.
Y=0.572*X**0.427
R**2=0.921

Volume Evaporated/(Vol% ethanol in feed)**0.641

13.00

12.00

11.00

10.00

9.00

8.00

7.00
520.00

420.00

720.00

620.00

920.00

820.00

1120.00

1020.00

1220.00

Air flow rate (lt/hr)

Figure 6.18. Plotted Volume of mixture evaporated / (Vol% ethanol in feed)**0.643 vs
Air flow rate using Power law fit for the development of empirical
Model-II.

 The calculated values of the volume evaporated (VC) are given in

Table 6.2 and is plotted against the experimentally observed value of
volume evaporated (VE) in Figure 6.19. The markers represent
experimental values and continuous curve represents calculated values
of V. For ideal data, all points should lie on the 0
45 line. As seen in
Figure 6.19, most of the data lies about this line, represented by
equation VC = 0.999583 VE with R2 = 0.99738. The percent error in the
calculation of VC is found by:
Percent error = 100*( VE - VC)/ VE

(6.8)

which is also given in Table 6.2. It can be seen that the error in ModelII is always less than about 8.3 %, which shows that the fit is quite
good.

171

132.00

Markers represent Exptl. data.

Solid line represents fitted line.

45 Line

Y=0.999583*X
R**2=0.99738

122.00

Calculated Volume Evaporated (ml/hr)

112.00

102.00

92.00

82.00

72.00

62.00

52.00
65.00

55.00

85.00

75.00

105.00

95.00

125.00

115.00

135.00

Experimental Volume Evaporated (ml/hr)

Figure 6.19. Calculated values of volume evaporated vs Experimental values of Volume
evaporated for empirical Model-II.

DISCUSSION

The error observed in calculated values of two models may be due to the following
reasons:
(i)

Error in the measurements of "Volume evaporated " is due to large hold up of

column and small volume change.

(ii) There is also temperature variation (i.e., 24 to 290 oC) which is not taken into
account.
(iii) Humidity of input air may also be contributing some error.

We feel that the rate of separation is quite small, which can be improved by increasing
the amount of reflux, which can be done by increasing air flow rate, and by having
temperature difference between the liquids and air for condensation. Also, the inlet air
should be bubbled through the product. Air flow rate can be increased manifold by
having co-current flow, but how this will affect the separation factor, remains to be

seen. As the maximum error in Model-II is 8.3%, while the error in Model-I is 16.67%.
Therefore empirical Model-II is better than the empirical Model-I.

SEPERATION FACTOR OF ETHONOL-WATER

MIXTURE
CALCULATION OF SEPERATION FACTOR (semi-empirical) FOR
ETHONOL-WATER SYSTEM

INTRODUCTION
In this chapter we have discussed the calculations of distillation separation factor of
ethanol-water mixture by analytical (thermodynamic), semi-empirical, and
empirical techniques.
Distillation is the combination of two operations evaporation and condensation. For
the calculation of separation factor, only the experimental data of evaporation is
sufficient. Different setups of apparatus Figure 7.3 to Figure 7.18 and process
conditions, such as degree of vacuum (VM), process temperature (PT), room
temperature (RT), column top temperature (CTT), air flow rate (AFR), density of
feed (DF), density of product (DP), volume of mixture evaporated (VW), volume of
product (VP), volume of feed (VF), calculations factors (A1 and A2) and separation
factor (SF) were recorded in Tables 7.3 to 7.18. To decide about the best setup,
separation factor were calculated for different setups and process conditions.

MATHEMATICAL
The simplest example of batch distillation is a single stage differential
distillation, starting with a still pot, initially full, heated at a constant rate. In this
process the vapor formed on boiling the liquid is removed at once from the
system. This vapor is richer in the more volatile component, with the result that
the composition of the liquid product progressively alters. Thus, whilst the
vapor formed over a short period is in equilibrium with the liquid, the total
vapor formed is not in equilibrium with the residual liquid. At the end of the
process the liquid which has not been vaporized is removed as the bottom
product. The analysis of this process was first proposed by Reyleigh [57].
Let M be the number of moles of material in the still and X be the mole
fraction of component A. Suppose an amount dM, containing a mole fraction Y
of A, be vaporized. Then a material balance on component A gives:
Y dM = d(MX) = MdX + XdM
If MP, MF are the number of moles and XP, XF are volume fraction of product
and feed, then after rearrangement and integration of above equation we get:

XP

log

MP
dX

MF XF Y X

(7.41)

The integral on the right-hand side can be solved graphically if the

equilibrium relationship between Y and X is available. In some cases a
direct integration is possible. Thus if over the range concerned the
equilibrium relationship is a straight line of the form Y= mX+C

where m is the slope of the straight line and C is the intercept,

then:
log {MP/MF} = [1/(m-1)] log {[(m-1)XP + C]/ [(m-1)XF + C]}

or

MP/MF = [(Y-X)/(YF-XF)] (m-1)

(7.42)

From this equation the amount of liquid to be distilled in order to

obtain a liquid of given concentration in the still may be calculated and
from this the average composition of the distillate can be found by a
mass balance.
Alternatively, if the relative volatility may be assumed constant
over the range concerned, then Y = X/[ 1 + (-1)X] can be
substituted in Eqn. (7.42). This leads to the solution:
log{MP/MF}=[1/(-1)]log{XP(1-XF)/XF(1 - XP)}+log {(1- XF)/(1 -XP)}

(7.43)

As this process consists of only a single stage, a complete

separation is impossible unless the relative volatility is infinite.
Application is restricted to conditions where a preliminary separation
is to be followed by a more rigorous distillation, where high purities
are not required, or where the mixture is very easily separated.

STEPS FOR THE CALCULATION OF SEPARATION FACTOR

Experimental and calculated data is used for the calculation of
separation factor by using computer program. Detail of the steps for
the calculation of separation factor are given as under.
STEP-I To carry out this exercise a curve was drawn between
experimental data of vol% ethanol and density of ethanol water
mixtures as shown in Figure 5.4, then a polynomial of the type Y =
C1X2 + C2X + C3 was fitted to this curve (Figure 7.19). The fitted
equation is given below:
V = -2.0504x103 D2 + 3.148x103D - 1.1x103
( 7.44)
Where V is vol% ethanol in mixture; D is the density of mixture in
gm/cc, or
X = -20.504 D2 + 31.48D - 11.0
( 7.45 )
Where X is the volume fraction of ethanol in mixture.
STEP-II If DF and DP are the densities of feed and product, then
substituting these values in Eqn. (7.45) we get:
XF = -20.504 * (DF)**2 + 31.48*(DF) - 11.0
( 7.46 )
and
XP = -20.504 * (DP)**2 + 31.48*(DP) - 11.0
( 7.47 )

 STEP-III In this step overall and component volume balance

equations were written.
If VF, VP and VW are the volume of feed, product, and waste
respectively, and
VF = 1200 ml ; then

( 7.48 )

VP = 1200 - VW

( 7.49 )

Now as XF, XP and XW are the volume fraction ethanol in feed,

product and waste respectively and MF, MP and MW are the moles of
ethanol in feed, product and waste, then we can write:
MF = VF * XF * 0.018333

( 7.50)

MP = VP * XP * 0.018333

( 7.51 )

and

STEP-IV Writing formula for single stage batch distillation i.e., differential
distillation [10] we get:
Log (MP/MF) = (1/A) Log {[XP(1 - XF)]/ [XF(1 - XP)]}
+ Log{(1 - XF)/(1 - XP)}
( 7.52 )
rearranging
A = 1+ Log {[XP(1 - XF)]/[XF(1 - XP)]}(Log(MP/MF)
- Log {(1 - XF)/(1 - XP)}
(7.53)
Where A is the separation factor:
Separation factor of ethanol-water system has been calculated for
different setups of apparatus. The input and output data are attached in Tables
7.3 to 7.18. The symbols used in Tables, are not properly defined above are
given as under:
VM = Vacuum (mm of Hg)
AFR = Air flow rate (lt/hr)
DD = DP - DF
PT = Process Temperature
RT = Room Temperature
CTT = Column Top Temperature
A1 = Log{ XP(1 - XF) / (XF(1 - XP))}
A2 = Log{ MP(1 - XP) / ( MF(1 - XF))}
A = 1 + ( A1/A2)
SF = A = Separation factor

195

100.00

80.00

Vol% ethanol

60.00

40.00
Markers represents Expt. data.
Curve represents fitted polynomial.
V= -2050.4 D**2 + 3148.0 D - 1100

20.00

0.00
0.80

0.84

0.88

0.92

Density of ethanol (gm/cc)

Figure 7.19. Vol% ethanol in ethanol-water mixture vs density of ethanol.

0.96

1.00

FIG7.3

Figure 7.3 Experimental setup for the separation factor study of ethanol-water mixture using packed column,
recycling of liquid feed and dried air flow from the liquid surface at room temperature.

FIG7.5

Figure 7.5 Experimental setup for the separation factor study of ethanol-water mixture using, slightly heated
(liquid feed and dried air flow) with air flow from the liquid surface.

TABLE 7.3 INPUT AND OUTPUT DATA SETUP OF

FIGURE 7.3
S.No VM AFR
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

300
200
100
0
300
200
100
0
300
200
100
0
300
200
100
0
300
200
100
0

420
680
940
1220
420
680
940
1220
420
680
940
1220
420
680
940
1220
420
680
940
1220

DF

DP

DD

0.9508
0.9508
0.9508
0.9508
0.9646
0.9646
0.9646
0.9646
0.9689
0.9689
0.9689
0.9689
0.9757
0.9757
0.9757
0.9757
0.9800
0.9800
0.9800
0.9800

0.9566
0.9576
0.9581
0.9596
0.9680
0.9695
0.9696
0.9703
0.9721
0.9725
0.9732
0.9742
0.9779
0.9789
0.9790
0.9817
0.9819
0.9824
0.9824
0.9827

0.0058
0.0068
0.0073
0.0088
0.0034
0.0049
0.0050
0.0057
0.0032
0.0036
0.0043
0.0053
0.0022
0.0032
0.0033
0.0060
0.0019
0.0024
0.0024
0.0027

VW PT RT CTT VP
84
105
120
140
65
85
90
100
60
70
90
90
55
65
80
85
50
55
60
60

27.5
27
29
27.5
27
28.5
27
27
28
27
29
27.5
29
27.5
27
28
27
24
26
24

30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30

28
28
28
28
28
28
28
28
28
28
28
28
28
28
28
28
28
28
28
28

1116
1095
1080
1060
1135
1115
1110
1100
1140
1130
1110
1110
1145
1135
1120
1115
1150
1145
1140
1140

XF

XP

MF

MP

A1

A2

SF

0.3951
0.3951
0.3951
0.3951
0.2876
0.2876
0.2876
0.2876
0.2525
0.2525
0.2525
0.2525
0.1954
0.1954
0.1954
0.1954
0.1584
0.1584
0.1584
0.1584

0.3509
0.3431
0.3392
0.3275
0.2599
0.2475
0.2467
0.2409
0.2259
0.2225
0.2166
0.2082
0.1766
0.1679
0.1670
0.1435
0.1417
0.1373
0.1373
0.1347

8.6930
8.6930
8.6930
8.6930
6.3270
6.3270
6.3270
6.3270
5.5547
5.5547
5.5547
5.5547
4.2992
4.2992
4.2992
4.2992
3.4838
3.4838
3.4838
3.4838

7.1792
6.8881
6.7166
6.3636
5.4080
5.0598
5.0203
4.8580
4.7206
4.6097
4.4082
4.2363
3.7061
3.4939
3.4299
2.9332
2.9883
2.8830
2.8704
2.8151

-0.1894
-0.2237
-0.2410
-0.2939
-0.1394
-0.2047
-0.2092
-0.2407
-0.1464
-0.1657
-0.2001
-0.2506
-0.1247
-0.1853
-0.1916
-0.3714
-0.1304
-0.1671
-0.1671
-0.1896

-0.1207
-0.1502
-0.1695
-0.2059
-0.1188
-0.1688
-0.1755
-0.2007
-0.1277
-0.1472
-0.1843
-0.2134
-0.1253
-0.1738
-0.1912
-0.3198
-0.1339
-0.1646
-0.1690
-0.1854

2.5685
2.4889
2.4217
2.4278
2.1733
2.2131
2.1918
2.1992
2.1463
2.1259
2.0856
2.1745
1.9956
2.0665
2.0017
2.1614
1.9742
2.0147
1.9884
2.0224

TABLE 7.5 Input and Output Data For Setup of Figure 7.5
S.No VM AFR
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25

400
350
300
200
100
350
300
250
200
150
350
300
250
200
150
350
300
250
200
150
350
300
250
200
150

145
270
420
680
940
270
420
540
680
810
270
420
540
680
810
270
420
540
680
810
270
420
540
680
810

DF

DP

0.9529
0.9529
0.9529
0.9529
0.9529
0.9605
0.9605
0.9605
0.9605
0.9605
0.9687
0.9687
0.9687
0.9687
0.9687
0.9746
0.9746
0.9746
0.9746
0.9746
0.9795
0.9795
0.9795
0.9795
0.9795

0.9552
0.9564
0.9576
0.9593
0.9614
0.9657
0.9662
0.9654
0.9664
0.9678
0.9723
0.9743
0.9745
0.9746
0.9743
0.9783
0.9792
0.9798
0.9790
0.9797
0.9832
0.9836
0.9840
0.9845
0.9850

DD VW PT RT CTT VP
0.0023 20
0.0035 60
0.0047 75
0.0064 95
0.0085 100
0.0052 55
0.0057 80
0.0049 70
0.0059 90
0.0073 100
0.0036 50
0.0056 90
0.0058 80
0.0059 85
0.0056 85
0.0037 60
0.0046 70
0.0052 70
0.0044 85
0.0051 95
0.0037 60
0.0041 65
0.0045 70
0.0050 75
0.0055 80

30
30
30
30
30
30
35
25
30
30
35
40
35
30
25
30
35
30
30
35
40
30
35
30
25

12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12

23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23

1180
1140
1125
1105
1100
1145
1120
1130
1110
1100
1150
1110
1120
1115
1115
1140
1130
1130
1115
1105
1140
1135
1130
1125
1120

XF

XP

MF

MP

A1

A2

SF

0.3793
0.3793
0.3793
0.3793
0.3793
0.3204
0.3204
0.3204
0.3204
0.3204
0.2541
0.2541
0.2541
0.2541
0.2541
0.2048
0.2048
0.2048
0.2048
0.2048
0.1627
0.1627
0.1627
0.1627
0.1627

0.3617
0.3524
0.3431
0.3298
0.3132
0.2787
0.2746
0.2811
0.2730
0.2615
0.2242
0.2073
0.2056
0.2048
0.2073
0.1731
0.1653
0.1601
0.1670
0.1610
0.1303
0.1267
0.1232
0.1188
0.1143

8.3441
8.3441
8.3441
8.3441
8.3441
7.0479
7.0479
7.0479
7.0479
7.0479
5.5910
5.5910
5.5910
5.5910
5.5910
4.5051
4.5051
4.5051
4.5051
4.5051
3.5795
3.5795
3.5795
3.5795
3.5795

7.8247
7.3659
7.0768
6.6816
6.3167
5.8500
5.6388
5.8238
5.5553
5.2743
4.7267
4.2190
4.2222
4.1860
4.2380
3.6178
3.4246
3.3167
3.4146
3.2609
2.7229
2.6373
2.5522
2.4493
2.3471

-0.0754
-0.1157
-0.1568
-0.2164
-0.2925
-0.1989
-0.2192
-0.1868
-0.2274
-0.2859
-0.1647
-0.2645
-0.2748
-0.2800
-0.2645
-0.2071
-0.2626
-0.3008
-0.2500
-0.2944
-0.2602
-0.2918
-0.3243
-0.3660
-0.4093

-0.0363
-0.0824
-0.1081
-0.1455
-0.1772
-0.1268
-0.1579
-0.1346
-0.1706
-0.2069
-0.1286
-0.2207
-0.2178
-0.2253
-0.2162
-0.1803
-0.2258
-0.2516
-0.2308
-0.2696
-0.2355
-0.2634
-0.2921
-0.3282
-0.3659

3.0746
2.4052
2.4504
2.4868
2.6502
2.5689
2.3880
2.3874
2.3329
2.3819
2.2813
2.1984
2.2618
2.2427
2.2233
2.1489
2.1629
2.1957
2.0835
2.0920
2.1048
2.1079
2.1099
2.1151
2.1186

DEVELOPMENT OF EMPIRICAL RELATIONSHIP FOR

SEPERATION FACTOR
DEVELOPMENT OF COMPUTER PROGRAM

Computers programs have been written in FORTRAN to use the data obtained in the
experimental results reported in Tables 7.3 to 7.18. Separation factors (empirical) are
calculated by using the models of Eqns. (7.54), (7.55), (7.56) and (7.57) by using
computer programs mod-5 and mod-6 (modified form of mod-4) developed in
section 6.2.1.

Mod-5 calculates the empirical constants of Eqns. (7.54), (7.55) and (7.56) with
two independent variables, where as mod-6 calculates the empirical constants of Eqn.
(7.57) with three independent variables.

Different combinations of last three columns of master input file are used taking
two at a time along with first two columns. For example column 3 and 4 are used for
Eqn. (7.54), column 3 and 5 for Eqn (7.55) and column 3 and 4 for ARF=0 for Eqn.
(7.56) for vacuum distillation. For Eqn. (7.57) all the three columns of input file are
used. The steps involved in this are given in the next slide.

STEP-I Input data from Tables 7.3 to 7.18 are merged to a single file and an
master input file is prepared for 371 points, each data point having been taken
after 1.5 hr of operation time.

STEP-II A computer code called MOD-5 has been developed to calculate the
values of constants of the following empirical equations:
SF = a + b Log (DF) + e Log (T)

(7.54)

SF = a + b Log (DF) + e Log (AFR)

(7.55)

SF(VD) = a + b Log (DF) + e Log (T)

(7.56)

Where AFR is the air flow rate in lt/hr, and T is the temperature in K. Eqn.
(7.56) is for vacuum distillation , in this case AFR = 0.

STEP-III A computer code called MOD-6 has been developed to

calculate the values of constants for empirical equation of the type:
SF = a + b Log (DF) + e Log (AFR) + d Log (T)

(7.57)

The computer programs, Input and Output files for these models are
attached at Appendix-5 and 6.

RESULTS
Resulting empirical equations for different cases are given below:

CASE-I

SF = f (DF, T)

SF = 0.539 - 10.403 Log (DF) + 0.236 Log (T)

(7.58)

DF(0.9492 gm/cc to 0.9969 gm/cc), T(294.5 K to 350 K)

CASE-II

SF = f (DF, AFR)

SF = 1.797 - 10.466 Log(DF) +0.014 Log (AFR)

(7.59)

DF(0.9492 gm/cc to 0.9969 gm/cc), AFR(25 lt/hr to 1220 lt/hr)

CASE-III

SF (VD) = f (DF, T)

SF = -12.746 - 20.494 Log (DF) + 2.506 Log (T)

(7.60)

DF(0.9810 gm/cc to 0.9944 gm/cc), T(314 K to 350 K)

CASE-IV

SF = f (DF, AFR, T)

SF = 3.008 - 10.258 Log (DF) + 0.016 Log (AFR) - 0.214 Log(T)

(7.61)

DF(0.9492 gm/cc to 0.9969 gm/cc), AFR(25 lt/hr to 1220 lt/hr), T(294 K to 335 K)

(i) Values of SF (Experimental) given in Tables 7.3 to 7.18 and SF (Calculated) by this program
are plotted in Figures 7.20 to 7.23. Fitted straight lines through origin have slopes almost equal to
1 i.e., 450 showing that the calculated values are in good agreement with the experimental values.

(ii) Surface plots of Eqns. (7.58), (7.59) and (7.60) are also shown in Figures 7.24, 7.25 and 7.26.

196
197

2.60

Markers represents Calculated (SF) vs Experimental (SF).

Straight line represents fitted straight line through origin.

2.60

Markers represents Calculated (SF] vs Experimental (SF).

Line represents fitted straight line through origin.

SF = f (DF, PT)

SF = f (DF, AFR)

Y = 0.9995*X

Y = 0.999999*X

R**2 = 0.9995

2.50

R**2 = 0.9995

2.40

Separation Factor (calculated)

Separation Factor (calculated)

2.40

2.20

2.30

2.20

2.10

2.00
2.00

1.90

1.80
1.90

1.80

2.10

2.00

2.30

2.20

1.80

2.50

2.40

Separation Factor (experimental)

Figure 7.20. Calculated vs Experimental separation factor as a function of density of feed
and process temperature.

2.60

1.90

1.80

2.10

2.00

2.30

2.20

2.50

2.40

2.60

Separation Factor (experimental)

Figure 7.21. Calculated vs Experimental separation factor as a function of density of feed
and air flow rate.

198
199

2.30

Markers represents Calculated vs Experimental Separation factor.

Straight line represents straight line fit through origin.

Markers represents Calculated (SF) vs Experimental (SF).

Line represents fitted straight line through origin.

SF(VD) = f (DF, PT)

SF = f (DF, AFR, PT)

Y = 0.999961*X

Number of data points = 293

R**2 = 0.999812

2.40

Y = 0.999552*X
R**2 = 0.999539

Separation Factor (calculated)

Separation Factor (calculated)

2.20

2.10

2.20

2.00

2.00

1.90

1.80

1.95

2.00

2.05

2.10

2.15

2.20

Separation Factor (experimental)

Figure 7.22. Calculated vs Experimental separation factor as a function of density of
feed and process temperature for vacuum distillation i.e. no air flow.

2.25

1.80

2.00

2.20

2.40

Separation Factor (experimental)

Figure 7.23. Calculated vs Experimental separation factor as a function of density of feed,
air flow rate and process temperature.

Separation Factor (calculated)

Fig 7.24

2.4
2.2

340

2
0.95

320

0.96

0.97
0.98
Density of Mixture (gm/cc)

Process Temperature ( K)

0.99

300

Figure 7.24. Surface plot of separation factor as a function of ethanol-water mixture feed density and
process temperature for empirical model MOD-5.

Separation Factor (calculated)

FIG 7.25

2.4
2.2

1000

2
0.95

750
500

0.96
0.97

250

0.98
Density of Mixture (gm/cc)

0.99

Air Flow Rate (lt/hr)

Figure 7.25. Surface plot of separation factor as a function of ethanol-water

mixture feed density and air flow rate for empirical model MOD-5.

Separation Factor (calculated)

FIG7.26

2.2

350

340

1.8

330
0.985
0.99

320 Process Temperature ( 0

K)

Density of Mixture (gm/cc)

Figure 7.26. Surface plot of separation factor (vacuum distillation) as a function of ethanol-water mixture
feed density and process temperature for empirical model MOD-5.

CONCLUSION AND SUGGESTION

CONCLUSIONS

Separation of ideal (isotopic) liquid mixture e.g. H2O-HDO-D2O is

possible only due to mass difference (which gives rise to zero point
energy difference) at low temperature, because the Van der Waals fields
are almost equal in these systems. As the zero point energy (vibrational
energy) of lighter molecule is more as compared to the heavier molecule,
therefore lighter molecule needs less energy for detaching it from other
liquid molecules and this proves that normal effect prevails at low
temperature. Now as the temperature is raised the infrared frequency of
lighter molecule is absorbed more strongly by heavier molecule and as a
result it needs lesser energy for evaporation and becomes more volatile,
therefore inverse effect prevails at higher temperature e.g.,
in case of H2O-HDO-D2O system this inversion temperature is 230C.

 The theoretical study which includes the review of literature from 1933
to 1998 regarding isotopic exchange reaction H2O + D2O 2HDO
reveals that theoretical calculations of equilibrium constant for this
reaction are easier in vapor phase than in liquid phase due to the
involvement of Van der Waals forces in liquid phase in general cases,
but cancel out in case of isotopes. We also note that:
(i)

Kl Kv at lower temperatures and Kl Kv at higher

temperatures.
(ii)

In the theoretical derivation of relationship between K and T it is

seen that if harmonic molecular spectroscopic data is used the value of

K is more near to the classical value of 4.0, and if anharmonic data is
used the values are much smaller than 4.0.

 Previously it was believed that H2O-HDO-D2O is a perfectly ideal

system and since HDO cannot exist independently in the absence of
H2O and D2O, we have to make certain assumptions regarding the
vapor pressure of HDO. So previously it was assumed that vapor
pressure of HDO is geometric mean of the vapor pressures of H2O and
D2O. But now it is revealed from the theoretical study of vapor
pressure data of H2O and D2O that H2O-HDO-D2O system is not
perfectly ideal but it slightly deviates from ideal behavior and due to

this deviation geometric mean rule is not exactly valid. In this work we
have tried harmonic mean assumption which is found to be more
suitable and gives results more near to the experimental values. In the
end we have successfully related distillation separation factor of this
system to Kl and Kv, and a semi-empirical relationship is developed.
When () is plotted against T, it gives a curve which passes right
through the thick of the curves of previous workers (Figure 4.3).

 As the theoretical study of separation factor of ethanol-water mixture

is very difficult due to non-ideality of this system therefore an
experimental study was conducted. Firstly the evaporation of ethanolwater mixture was studied. In the first step four mathematical
(analytical) models were developed to calculate volume evaporated
and their validity was checked by fitting experimental data. In case of
analytical Model-IA the maximum error in the calculated volume %
ethanol in product is approximately 10%, in analytical Model-IB the
maximum error in the calculated volume % ethanol in product is 20%
and in case of analytical Model-II the maximum error in calculated

volume evaporated is 17.65%. Although these errors are less than the
acceptable value of 25% [74], still we have tested two more empirical
models.

 Two empirical models were also developed and tested for this data, in
case of empirical Model-I the maximum error in calculated volume
evaporated is 16.67%, while in case of empirical Model-II the
maximum error is only 8.3%, which is lowest of all the tested models.
For the experimental separation factor studies of ethanol-water system,
sixteen different setups of apparatus and different process conditions
are used to collect the separation factor data. Approximately 370 data
points are collected. These data points values are firstly used in
Relayigh`s analytical equation for the calculation of separation factor
for each data point [55]. The separation factor values for ethanol-water
mixture for these process conditions are very much near to the
experimental value of 2.5.

Four different empirical relationships are also developed by using the above
separation factor (experimental) values and two and three different independent
variables. The first model SF = f (DF, T) has goodness of fit value = 0.864, the
second model SF = f (DF, AFR) has goodness of fit value = 0.875, the third

model for vacuum distillation SF (VD) = f (DF, T) has goodness of fit value =
0.883, the fourth model SF = f (DF, AFR, T) has goodness of fit value = 0.880.
Although the value of co-efficient of determination is slightly less in case of
fourth model as compared to third model, but the number of data points are much

more in case of 4th model, so the best model which has three independent
variables is the fourth model and this model is valid for the following ranges of
three different variables, DF (0.9492 gm/cc to 0.9969gm/cc), AFR (25 lt/hr to
1220 lt/hr), T (294 to 3350 K). When calculated vs experimental separation factor

values of this model are plotted we get a straight line with slope nearly equal to 1
with goodness of fit value = 0.99954.

SUGGESTIONS FOR FUTURE WORK

Reasons for the following experimental facts should be investigated.

(i) Why at low temperatures i.e. up to 25C, Kl Kv and at higher
temperatures i.e. 25C, Kl Kv.
(ii) Why K (HM) K (ANH).
(iii) As we also know that Kl Kv, does it indicate
any relevance between (i) and (ii).
(iv) Why heavy water distillation plants are not operated at higher
temperature to have more D2O in the vapor phase as at higher temperatures
inverse effect prevails. A study should be conducted for the separation of
heavy water at higher pressure and temperatures (more than 230C).
(v) As

PH 2 O

D2O

and (PH O PD O ) is maximum at 170C, a study should be

2

conducted at this temperature for the separation of heavy water from light
water.

Experimental results regarding ethanol-water separation can be improved by

taking the following measures.
(i)
Measurement of volume evaporated can be made more exact by
reducing the quantity of hold-up volume.
(ii) Process temperature variations should be made minimum.
(iii) Humidity control of evaporating air should be improved.
The rate of separation can be improved by increasing the amount of reflux,
which can be achieved by increasing temperature difference between the
process temperature and cooling water temperature also the inlet air should be
bubbled through the liquid. Air flow rate can be increased manifold by having
concurrent flow, but how this will affect the separation factor remains to be
seen.
A power law fit be done for four models by relating Log (SF) to Log (AFR),
Log (DF) and Log (T). Although the value of goodness of fit is maximum for
VD, but the air flow is zero in this case. The introduction of air is giving some
negative effect on the separation of mixture due to the formation of a thin layer
of air between vapor and liquid films. So this process can be used for the
liquid mixtures separation at low temperature if we have some way of
separating air-water mixture after helping the first evaporation of the liquid
mixture.