Verslag behorende

bij het fabrieksvo~rontwerp

van

'
JOSEF
....................... ...... ............................. FRENKEL .
.,. ................................................ ............ _......... '

. onderwerp:

............................................................................ -<""~ ..... ..... .. _ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..

)' .1i - ,. ' , :..

DISTILLATION OF TRIMETmAMINE' FROM A MIXTURE OF ', ..

• "f),. ~ J 'J

..WA::J;1~;2..s.,M.9.~Qi~.~X::-...~.. ::ç~~r.~~~.~ ...... .':.... .

adres: Koornmarkt 9 opdrachtdatum : Ju1y 1973

Delft verslagdatum: June 1974

 [
[
[
[
[
An Initial Study of the Calculation of the
Extractive Distillation of Trimethyl@nine
[ from a Mixture of Water, Mono-, Di- and
r ' Trimethylamine .
l.
r '

l.
r'
I I

I
L •

~
.I

rl
~J

June, 1974 Process-Design Project

Josef F'renkel

n Koornmarkt 9
Delft

n
n
r
u

l _

l.

"

. ,I

.j

l
l To strive, to seek, to find

l and not to yield.

Front "Ulysses"
by Alfred Lord Tennyson
l
n
l •
J -1-

List of contents

Topic

I. Summary 2
11. Conclusions and Recommendations 3
III. Introduc tion 4
IV. Theory and literature research 6
V. Calculational procedure 10

VI. Results and discussion 22

VII. Figures 37
VIII. Nomenclature 45
L. IX. Literature cited 47
X. Appendices 49
l,

, ,

n
n
 -2--

L
I. Summary
----------

The core of the problem was to describe the vapor-liquid equilibria

l of the multicomponent system, composed of:
(a) Monomethylamine (r-1MA);
[ (b) Dimethylamine (DMA);
(c) Trimethylamine (TMA);
(d) Hater (H).
Based on this description a distillation column was supposed to be
designed "hich would separate TMA from the system by means of extractive
distillation.

r
l _ The problem was attacked by selecting, aftel' an extensive literature
study, the Wilson equation which seemed to be the most applicable
,, ~

equation to this type of syst em composed of highly polar nonideal

components. The Hilson constants of the binary system DMA-H were regular
in their trend; while those of the binaries: (a) I1MA-H , (b) TMA-H
exhibited some anomalous results. An atternpt ,-laS made to clarify these
phenomena.

The attempts to design the distiIIation column were not successful.

, '
The program was run many times with different reflux ratios and rates
of extracti ve '-later. Unfortunately, no optimal solution was found. It
lS very weIl possible that the Vlilson equation cannot be applied to the
l J system under discussion because of incomplete miscibility . It is
suggested to check this point experiffientally , and in any case, to try
to appIy the Renon equation.

~l
In order to check the whole calculational procedure of the Wilson constants
and the incorporation of the latter in a design of a distillation column,
it is suggested to apply it to a system for which the Vlilson constants
J are known in the literature.

1
n

n
u -3-

[ 11. Conclusions and Recommendations

1. The Wilson constants for the binary system (a) DMA-water exhib ited
regular behaviour, while those for thc binary systems (b) },flvlA.-water
and(c) TMA-water exhibited some anomalies. The cause(s) of this
irregular behaviour may lie in one or more of the following factors:
(a) tbe occurrence of immiscibility;
(b) data over an insufficiently wide range;
(c) inaccuracies in the data.

2. It is suggested to determine experimentally whether the binary

r mixtures of water and the respective amines and the multiconrponent
I

system under discussion are completely miscible.

l, 3. It is recommended to try to apply Renon's equation to the system

under discussion for the description of its vapor-liquid equilibria.
I '

l .
4. It is suggested to check the calculational procedure concerning the
r , Wilson ccnstants and the distillation column for a system, whose
L • Wilson parameters and distillation' s design are knovn from literature.

r '
5. It is suggested to develop a more efficient computer program for the
design of a distillation column for nonideal systems.
r 1

l
l
l

n
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 -4-

111. Introduction

1. General

t1ono-, di- and trimethylamines , CH NH 2 , (CH ) 2NH anel (CH ) 3N

3 3 3
are manufactured in a continuous process (the Leonard process) from
technical grade anhydrous ammonia and methanol (1). The flow sh eet
is described in Fig. 1. Accordingly, e.rnmonia, methanol and r e cycle

,- - liquid are fed continuously at controlled rates through a vapor1zer,

heat exchanger and superheater into an amination catalyst packed
converter. Part of the exothermic reaction heat 1S used in the feed
preheater. The crude product is fed to a series of fOUT distillation
columns. The first column separates excess ammon1a and part of the
TMA-ammonia azeotrope which is recycled. Bottoms go to the TMP. column,
where T~ffi is separated by means of extractive distillation and goes
over-head. Bottoms are fed to the MMA column where pure NMA goes over-
head to storage or recycle. MMA-column bottoms go to the DMA-column
where pure DMA goes over-he ad to product storage or recycle with water
drained from the bottom to waste. The reaction system is in perfect
equilibrium and any amount of tri-, mono-,or dimethylamine can be
r '
taken off as product with any amount of unwanted product recycled
L i

which suppresses formation of an equivalent amount of that material.

All the products-are 99% pure.

The overall yield of both ammon1a and methanol is above 95%.

Raw materials used per 100 Ibs. of anhydrous product are as follows:

MMA DMA TMA

Methanol 108.7 149.7 171.3

Ammonia, anhydrous 57.7 39.8 30.3
.1 Utility consumptions per 100 Ibs. of anhydrous product are as follows:

Stearn 1300. Ibs

Water 13250. ltr.
Electricity 9. KWh

Operator Labor: one operator per shift

n
 , 1

-5-
,'
L

Capital cost: For a 20-million-lbs/yr. plant for 5 DMA / 3 ~WA /

2 TMA product ratio including tvlO ..reeks raw material storage for

r'
l
methanol, and two weeks storage for all anhydrous products, complete
battery limits process plant, cost is $ 1.6 million based on current
labor and material costs in u.s. (valid for November 1973).

Commercial installations: sixteen companies in 11 different countries

use the process. Est imated total tonnage produced using the process
in 1973 was 150-200.000 tons/yr.

r~

i
l.
2. Extractive distillation and its application in this project.

r ' When a system contai ns components of similar boiling points

I
l. separation by means of ordinary distillation lS often neither easily
achieved due to the low relative volatility nor economically
, . attractive, because equipment and operating costs are usually very

, , high. In such a case a modified distillation procedure is used; this

procedure entails adding an extraneous liquid which changes the
relative volatilities of the original components and thus facilitates
their separation. If the extraneous material is less volatile than
the feed, it is called a solvent, and the operation is called
extractive distillation. To be effective the concentration of the
solvent ln the liquid phase must be at least 40 mole-%, and it is
, 1 usually much higher.
, .' A flowsheet of an extractive distillation column lS shown in Fig. 2.
Accordingly the solvent lS charged to the top of an extractive-distil-
lation column, the bulk of the solvent passing downwards being with-
drawn from the bottom together with the component(s) whose volatilities
are least affected by the solvent. The latter is required to improve
the relative volatilities of some component(s) over the entire height
of the column, so that they would pass overhead.
Separation of the bottom product from the solvent lS easy, because
the volatility of the pure solvent is always substantially .lower than
the former.

The extraneous agent ln the case of separation of aIDlneS lS

l J water. It is charged to the column in a rate which is equal to 1.65
times the mole rate of the feed. The relative volatility of TMA is
n I increased significantly, and hence it passes overhead, while water,
L J

MMA and DMA pass through the bottom of the column to uridergo further

n separation.

rl
 r}
L ·-6-

1. The concept of a real solution

The simplest 'tray to describe the properties of a liquid

solution is due to Raoult's law. Viz., the partial pressure of
any component in a liquid mixture lS e qual to the product of its
vapor pressur e , as pure component at the temperatur e of the
system and its mole fraction in the liquid phase (2).
However, Raoult's law holds only in simple cases in which the
components are chemically similar and becomes exact when they are
r ., almost identical e.g., homologous compounds. It fails to represent
actual behaviour of liquid solutions because of differences in
molecular size and intermolecular forces of the pure components.
It appe ars logical, ther efore, to use Raoult's relation as a
reference and to express observed behaviour of r eal solutions as
deviations from the behaviour calculated by Raoult's law.
A thermodynamic model can be developed by means of which, the
solution can be described. vfuatever this model is, it incorporates
the activity coefficients. The latter are thermodynamic functions
which describe the deviations from ideal solutio:1.

2. Activity and activity coefficients

2.1. The activity of component i at some temperature, pressure and

composition is defined as the ratio of the fugacity of i at these
conditions to the fugacity of 1 1n the standard state, ,{hich is
a state at the same temperature as that of the mixture and at
some specified conditions of pressure and composition (3):

f.(T,P,X)
.1 a. (T, P, x)
1
= 1
(Iv-1)

1n which:
.th
a. activity of the 1 component [dimensionless]
1
f. fugacity of the component 1n the given state [atm. ]
1

l f<?
1
fugacity of the component 1n a standard state [atm. ]

I .
 r ,
I
LJ
-7-
r.
L~

L arbitrary specified pressure ln a standard state

[atm. ]

arbitrary specified composition in a standard

state [mole fraction; dimensionless].

The fugacity is defined as follows:

r' ~.
l
= RT In f. + B(T)
l
(rV-2)

ln which:
r '
,
l _
th
~. - chemical potentialof the i component [cal/gmol]
l
r' O
R - Universal gas constant [cal/gmol K ]

B(T) - Integration coefficient which lS a function of

I '
temperature only [cal/gmol].

On combining Equations (rV-1) and (rV-2) it follows:

, I f.
o
~.
l
~.
l
= RT ln(--l-) = RT In a. (IV-3)
f.o l
l

which means that the activity lS a measure of the difference of

the chemical potentials in the given and the standard states.
I I

Obviously, the numerical value of the activity depends among

other things on the choice of the standard state. If the standard
, ,,
state is chosen such that it lS that of the pure component at
the temperature and pressure of the system, it follows that for
• I a pure substance the activity is always equal to unity,

= o = (Iv-4)
f.
l

and the activity of a component ln an ideal solution lS equal to

its mole fraction, viz.,

f.
l
= al = x.l (rV-5)

n
r
 r'
l ,
-8-
f '

L
I'
2.2. The activity coefficient y. is the ratio of the activity of 1
1
l~ te some conven ient measure of the concentration of i, which lS
usually taken to be the mole fraction:
f'
l _
al
y.
1
= x. (Iv-6)
1

"l . On comparison between Equatiens (IV-5) and (Iv-6) it follows

that for an ideal solution the activity coe fficient is equal
to unity:

ai x.
y.
1
= x. = x.1 = (IV-7)
1 1

( , Another way of describing deviations from ideal solution, by

,
using the activity coefficient lS as follows:

O
K.
1
= y. K.
1 1
(Iv-8)

ln which:
K.1 equilibrium constant which equals Y/X [dimensionlessJ

equilibrium constant ln an ideal system which equals

I '

pO/TI [dimensionless].

r ,
ln which:
l ,

vapor pressure of the pure component at the tempera-

r .,

ture of the system [atm.]

, -, TI total pressure of the system [atm.]

, J
3. Estimation of multicomponent vapor liguid eguilibria
i
, J
3.1. As pointed out above, the core of the problem of describing a
real multicomponent system is to estimate the vapor-liquid
l
• J
equilibria. In most of the cases the required experimental data
are almost never available. In order to make the best possible
estimate with a minimum of experimental data it is efficient and
useful to express the problem in thermodynamic terms which would
consolidate the basis for a molecular model. Because the activity
coefficients are exactly defined thermodynamic quantities it is
possible in terms of them to describe real systems in equilibrium
under various conditions.

n
r
 rl

-9-
r '

L
The us e ful thermodynamic concept for efficiently expressing the
E
nonideálity of a liquid mixtur e is the excess Gibbs energy g ,
which ",as originálly introduced by Scatchard (12). I t is defined
f'
l. as follows (3):

E
I
g = g(actual solution) g(ideal solutio~ at)
(IV-9)
l,
at T, Pand X same T, Pand X
r'
1n which:

E
g Excess Gibbs energy of the solution ~alJ

g Gibbs energy of the solution [cal.]

H'
By means of the function g'" it is possible to derive an expreSS 10n
for the activity coefficient Y for any component K in the system.
K
d . E
nTg )
(
= dOK T,P all n. (i;lK)
1
(IV-l0)

1n which:

n. number of moles of component 1

1
r'
total number of moles.

3.2. There are several thermodynamic techniques for the calculation of

multicomponent solution properties. The latter are based on the
, 1 concept of excess Gibbs energy. Examples are the van Laar-type
(4, 5, 6, 7), the Margules-type (8, 9, 10, 11) and the Wohl-type
(13, 14) equations.

The van Laar equation for a binary system lS as follows:

A
= (IV-11)
1 ln Y
1
[1 +
A X11
2
13 X2 J

~l
In Y
2 =
[ 1 2
+B-X-
A Xl
f (IV-J2)

~l

I ,
 -10-
. '

ln 'lhich:
r~
L •

mole fractions of component No. and No. 2

( ,
I rèspectively [dimensionless].
I
L,

A and B con stants which dep end on pressure and

temperature but are independent of composition
[dimensionless] •
..
L ~ The Margules equation for a binary system lS as follows:
r ,
(IV-13)

= Xl 2 (2A-B) + 2X 13 (B-A) (IV-14)

Note that Vli th systems for ,-,hich A=B. both the van Laa.r and
Margu.les equations further simplify to the common form:

In Yl = AX 2 (IV-15)
2

= AX 2 (IV-16)
1

Another procedure to calculate the activity coefficient Vlas

suggested by Wohl (13. 14). The excess Gibbs energy is expyessed
as a polynomial series in the mole fractions (or volume fyactions)
of the components in the mixture. It is a.s follOYls:
E
g
= L Z.Z.a .. + L Z. Z . Zk a . . k +
1 J lJ "k 1 J . lJ-
RTLq.X. lJ lJ •
.11
1
, j
+ L Z,Z,ZkZl a . 'kl + ... ( IV-17)
ijkl 1 J lJ

,l in which:

J q.
1
a constant which Wohl called the effective molar
volume of the component.

Z. effective volume fraction of the component.

1

~l The effective volumetrie fraction of any component is defined by

the relation:

n
r
l.
[
L...
-11-

q.X.
1 1
z.1 = n
(IV-18)
L q.X.
j=1 J J

Volumetrie fractions like mole fractions are related by the

condition

L:Z. = (IV-19)
j J

Second-power terms in this series represent deviations from ide al

behaviour due to interaction between two molecules; third-power
terms, those due to interaction betwe e n three molecules; and so on.
Thus, one of the advantage s of this method is that some approximate
significance can be assigned to the parameters which appear in the
equation.

3.3. The methods cited above have some inadequacies which must be kept
in mj:'1d while calculating the activity coefficients. The constants
which appear in these equations are a function of temperature and
pressure but are not dependent on the composition. Concerning the
pressure, the dependence is not great; at low and moderate pres s ures
it can be neglected. However, the temperature usually plays a role
ln determining the values of the constants. Only in one case is the
temperature effect on the constants zero. This occurs when the
solution is athermal, viz., I"hen the solution process of the com-
r 1
1
ponents occurs isothermically, isobarically and with ~H = O.
For practical applications it is assumed that the dependence of the
activity constants on temperature at a modest range of the latter
can be neglected.

Another problem embodied in the polynomial serles of Whol

l lS that in principle, binary data are not sufficient to describe
multicomponent behaviour unless the series is truncated af ter the
second power term. The reason is that ternary, quaternary etc.,
data are necessary in order to calculate the higher order terms.

n Thus, this fact greatly complicates the experimental procedure

and makes it less attractive.

n
n
 , ,

-12-
r -

Many ot her methods are available ln the literature for calculating

the activity coefficients. These methods usually require ternary
data and are not always applica1üe to polar systems. Therefore they
r' are not described in this ·paper . The reader is referred to Prausnitz
L (3) for further literature survey .

I. A completely different expression for the excess Gibbs energy has

L.
been proposed by Hilson (15). Accordingly, gE is "ritten as a
logarithmic function of the liquid composition.
It has some very us eful advantages:
(a) buÏ1t-in temperature dependence ;
(b) accurate representation of data with only a few parameters (hro
constants for a binary system;
(c) prediction of multicomponent properties from binary data without
any additivity assumptions;
(d) a semi-theoretical interpretation of the parameters.
For systems which exhibit incomplete miscibility, Hilson's equation
is not applicable.

Wilson's equation was tested by Professor J.M. Prausnitz and his

co-workers at the University of California (Berl~eley) for various
binary and multicomponent systems, including polar, highly nonideal
cases, and they concluded that the equation is a good method for
describing multicomponent vapor-liquid equilibria with only binary
data available.
I . j

• J

~l
.1
:l

1
n
n "
1 ~
,

''l
 r 1

-13-

L
4. The Wilson Equation

Wil son ' s equat i on is a s emitheoretical extension of the

th eoretical equation of Flory (1'7) and Huggins (18) which lS us ed
for the thermodynamic description of mixtures with macromolecuJar
components , viz., polymer solutions (for full derivation see
Appendix A). By means of this equation it is possiblè to find a
relation between the mole fractions of the component s ln the liquid
phase and the respective activity coefficients. This relation is
made using thc Wilson constants, which are defined as follows:
L
v.
( , Aij = -L (IV-20)
L
v.
,I . l

L
v.
l
Aji = (IV-21)
v. L
J

in which:

Aij, Aji Wilson constants [dimensionless].

v L v. L liquid molar volumes of components l, j
i' J
respectively [cm3 /gmol].

Àij, Àji, Àii, Àjj energy coefficient of interaction between

r ' the respective pair of molecules
, )
[cal/grool].
,1
I
, J
Note that, whereas Àij = Àji, in general Aij # Aji.

An ideal solution lS one where A = 1\21 = 1; thi s deviation

l 12
of the parameters fr om unity is an indication of the nonideality of
the solution. If both A and 1\21 are greater than unity, the solution
12
l exhibits negative deviations from ideality (gE < 0), whereas if they
are both less than unity, positive deviations from ideality (gE> 0)

n
, I
results. If one parameter is greater than unity and the other one lS
less, than the deviations from ideality are not large.

n
n
 --14-
I .

I n general, t he r elation between the excess Gibbs energy and t he

a ct i vity coe f f icient lS as fo llows :

l g
E
= RT
n
L
i=l
x.lny .
l l
(IV-22 )

By i nt r oduci ng Wil son' s equat ion int o Equa tion IV- 22 , one get s :

g
E
= - RT
n [ n 1 (IV-23)
L x . ln L xJ' Al'J'J
. 1
l= l . 1
J=

from which it f ollovTs for a ny component k,

X.
= -In [~ x. A .] + 1 - ~ l
n
(IV-24)
j=l J kJ i=l
L x. A •.
j=l J lJ

For a b ina r y sOlution, t he ac tivi ty coeffici ents are a s foll ows:

A12
A2l ] (rV- 2S)
lnYl = -ln(x l + A12x 2 ) + x 2 [Xl + A12 x 2 A21 x l + x 2

A
12 A2l ] (IV-26 )
lnY2 = -ln(x + A x ) - xl
2 21 l [Xl + A12x 2 A x + x
2l l 2

4.2. The Hilson e quat ion h as two rema r k able advantage s which make it
very useful for engineering applications. Firstly~it has a built-in
• 1

temperature dependenc e , which is introduced in the IV'ilson constants ;

, J

the former has at least an approximate theoretical significanc e .

Furthermore, the differences of the energy coefficients of interaction,
viz., - À •• ) and (À •• - À •• ) may be, approximately, considered
(À ••
lJ II lJ JJ
independent of temperature, at least over a modest interval. This means
J that parameters obtained from data at one temperature may be used
reliably to calculate activity coefficients at another temperature not
too far away. Se condly, Wilson's model for a multicomponent solution
requires only parameters which can be obtained from data for the pure

n components and for the individual binary systems. The relative simplicity
of the experimen~al determination of binary data as contrasted to multi-

n component data is a basic advantage . The extension of Wilson's equation

n
 -15-

L
from the binary to the multicomponent case requires no additional
assumptions.

( ,

l.
4.3. There are blO disadvantages of Hilson' s equation which must be

[ : taken into consideration. Firstly, it lS

which exhibit incomplete miscibility. In this case another equation,

not applicable to systems

which is a modification of Hilson's,can be applied; the former is

Renon's equation (30). This equation, which is named the NRTL (Hon-
Random, Two-Liquid) equation is applicable to partially miscible as
r'
L. weIl as completely miscible systems. Renon's equation for the excess
Gibbs energy is as follows:

n
L T ••G.. X.
E n J1 J1 J
iL j~1
= I x. (IV-27)
RT 1 n
i=1
L GR,iXR,
R.=1

where

(g ..
J1 - g .. )
11
T ••
J1 = (g ..
Jl = g 1J
.. ) (rv-28)
RT

G..
J1
= exp( -ex ••
J1
T .. )
J1
(ex ..
J1
= ex 1J
.. ) (IV-29)

The significance of g .. is similar to that of A.. in Wilson's

1J 1J
• 1 equation; g .. is a (Gibbs) energy parameter characteristic of "the
1J
i-j interaction; the parameter a .. is related to the nonr~ndomness
1J
in the mixture.
-1
• 1
A second disadvantage lS that Wilson's equation lS not applicable
for systems where the logarithms of the activity coeffi c ients, when
plotted against xl~ exhibit maxima or minima. Such systems, however, are
not common. Mixtures of chloroform with alcohols do exhibit that
phenomenon; still an approximate prediction can be obtained for the
activity coefficients over almost the whole range of compositions.

n
n
n
 , ,

-16-
I '

V. Calculational Procedure

r'
1. General
l,
In order to design the distillation coluum it was necessary to
calculate some parameters concerning the pure component properti es and
the multicomponent system.
These parameters were calculated by means of computer programs which
are specified in the book "Computer Calculations for multicomponent
Vapor-Liquid Equil ibria" by Prausnitz, Eckert, Orye and O'Connell (19).
[ ,
The .des ign of the column lS base d on a computer program for nonideal
( , distillation. The latter appears in the book "Computation of Multistage
I , Separation Processes" by Hanson, Duffin and Somerville (20). Originally
the program was written with a subroutine based on the Margules equation
to calculate the activity coefficients. This subroutine was replaced by
another one based on the Wilson equation.

2. Calculation of Parameters

2.1. Liquid Molar Volume

It is necessary for a rigorous thermodynamic description of binary-

and multicomponent-phase equilibria to have information on the
temperature d ependence of the pure-component liquid molar volume.
The molar volume of a component at any temperature T may be calculated
when required ln the computer programs as:

L 2
v = a + bT + CT (V-1)
~1
The constants are
L L L L
:1 c
(T -T ) (v -v ) - (v 3-v 1 ) (T -T )
3 1 2 1 2 1
= (v.,.2L
(T 2 _T 2 ) (T -T ) - (T 2 _T 2 )
~1
(T -T )
2 1 3 1 3 1 2 1
L' L 2 2
(v 2-v 1 ) - c(T 2-T 1)
"
n b =
T2 -T
1

n a = v L - bT 1 - cT 2
1 1 (V-3)

n
r
 -17-
r'

r' Tl' T and T a re the temperatures at which the pure component liquid
2 3 L
L L L
molar volumes v l' v 2 and v 3 are avai l able.
( , A computer program for this purpose - VMOL - des cribed ln Appendix B.
L The data was taken from Gallant (21).

2.2. Constants for the Vapor Pr essur e Equat ion

The vapor preSSlITe of the pur e component as a function of ternperature

is written as follOi-ls :

lnP~(atm. ) = (v-4)
l

r .
Cl' C , C4 and C are constants.
2 6

The program according to which these constants are calculated lS

named VAPFIF and is described in Appendix C.
The data for BHA Here taken frorn Felsing (22). The data for TMA
were taken from Felsing (23). The data for DMA were taken from
Jordan (24). The equation for i-later was taken frcm Prausnitz (19).
The equations cited above are intended to represent very precisely
the vapor pressure dependenc e on temperature, but they cannot be
transformed to the more convenient form for interpolation, viz.,
a linear equation.
A modified equation which has recently become very popular lS the
Antoine equation. It has the form:
- 1

, )
B
lnP~(atm.) = A + ---- (V-5)
l

~l

The advantages of this equation are that it is sufficiently preClse

n and at the same time still permits the representation of dependence

of the vapor pressure on temperature by a simple equation.

n This form of equation was used in the design of the distillation column.
The equations for ~1A and DMA were taken froID the Handbook of Chemistry
and Physics (25).
n
n
r-,

I
 ( )
l ~

r '
-18-

l ,

The equat ion for TMA was taken from Felsing (23). The equation
for vlater was taken from Bijwaard (26).
The constants are listed in Table V-1.

Table V-1: Constants fOT the vapor pressure equation of MMA, TMA,
DMA and wate r.

r' L •
Component A B Range
0
C

MMA - 5859 .4 12.048890 - 95.8 .. 144. 6

( . TMA - 4983.9 10.066016 60 .;. 130
DMA - 6031.9 11.780227 - 87.7 .;. 162 .6
r'
I
l.
Water - 8585.1 12 . 809286 0 . 150

{ ,

2.3. The Hilson Constant s - Calculations of Binary-Interaction Parameters

For mixtures of components i and j, the two parameters /tij and 1\ji
can be obtained from vapor-liquid equilibria data. In principle, on ly
one experiment al poi nt (X, Y, T or p) lS required, and sometimes it
is possible to obtain a good estimate of the parametersmerely from
azeotropic composition and boiling point. In general, however, it lS

necessary to have a series of data points, either is othermal or

isobaric.
The method of Barker (27), for reducing experiment al binary dat a to
thermodynamic parameters, was adopted. According to this procedure
'l
total pressures are measured as a function of the compos ition of one
, i

of the phases (usually the liquid phase), and no measurements are

made of the composition of the other ph~se. Instead, the composition
of the other phase is calculated from the total-pressure data with
the help of the Gibbs-Dubem equation:

n
I: X.dlny. = o (at constant Pand T) (v-6)
n i=1
l l

From such information it is possible to obtain the parameters 1\12

n and A of Equation IV-23, or the parameters of any other equation

21
chosen to represent the activity coefficient as a function of

n composition.

r
( )

L~

-î9-
I •

L.

l: Further , the data reduction method requlres information on the

volumet ric properties of' the gas - phase mixt ur es in order to correct
r'
for vapor-phase nonidealities . At low and moderate pressures these
corr ecti ons can be calculated from the virial equation of state:
r '
I
Pv B C
l z == + - + + •••
RT v
r'
I
l.
ln which:

z c ompr essib ility factor [dimensionl ess ]

( . v molar volume [cm 3 /gmol ]
I B the second virial coefficient [cm 3 / gmol j
l.

C •
the thlrd vl•rl
• ••
al coefflclent ,-cm 3/ gmol ) 2 ]
[ f

etc .

rrhis equat i on of state was uti liz e d together .Ti th a correlation of

pure and mixed virial coefficients prepared by O' Connell (1 9 ).

A complete computer program ~ IHLS - for the calculation of 11. •• and 1\ ..

;iJ Jl
is described in Appendix D. The data was taken froill Rohm and Haas Co.
(28), and Gallant (21).

2.4. Design of an Extractive Distillation Col~~.

The distillat ion colliEr! for which the following progran has been
rl designed is that with a total condenser. It is taking into consi deration
the fact that the system is nonideal and the composition effect on the
equilibrium constants is here expre ssed by means of the activity
l) coefficients as follows:

(K)modifi ed = y(K)'d
l eaI
(v-8)

where the values of gamma (activity coefficient) are determined by

the i-lilson equation for multicomponent systems.

n The y values are determined in a subroutine - ACTCO - and are stored

in a two dimens ional array for use by the main program. The y values
are used in bubble-point calculation, and a special bubble-point
n subroutine BUBPTG has been written for this purpose.
(1

-2C-
I'
I
L~

Since the system is nonidcal the competing effects on the composition

map of first temperature and second composition dependent activity
coefficients oft e n result in 8. severe oscillation of the composi tion

r: map from iteration to iteration, with little or no tendency to

converge.
An iterative scheme named thc method of succeSSlve flashes, which
approaches convergence in an asymptotic fashion but with less tendency
to oscillate, was applied here (see Appendix E ).
In the use of this method i t vras necessary to asswne all stage
temperatures and set all vapor and liquid flows. The pressure and
number of stages was set too. In this program no heat balance lS
used and no correct ion to flows is made. Thus, the initial values of

r: flovTs assumed are used throughout the calculation. It is assumed that

the liquid flow is constant for all plates d01m to the point of feed
r '
I
introduction. The liquid flmv from all plates below the point of feed
l.
introduction is assumed to be the sum of reflux plus feed.
I '
In addition the starting composition on every stage must be assumed.
l.
It 15 not nec essary to have accurate compositions, since the steady-
state Golution is independent of any starting compositions. A simple
way of starting is to fill every stage with feed liquid at its bubble-
r ' point while the vapor is in equilibrium.
I •

The equilibrium constants (derived from vapor pressures) can be

represented by the equation:

A
InK = + B
r: (TOF) + 460
rl
I I The constants are listed ln Table" V-2 /j
l J

Table V-2: The equilibrium constant for ~ffi, TMA, DMA and water

Component A B
[1 IvIMA - 5859.4 9.805907
TMA. - 4983.9 7.823033
n DMA
Water
-6031.9
- 8585.1
9.537244
]0.568466
I,
-21-
r'
I
I
l .

Note: The constant B lS taking into consideration the pressure 1n the

column of TI = 9.4 atm.

[: Three error limits are required by the calculation: SillvlliRR, the

accuracy to which all vapor and liquid mole fraction summations
must approach unity; RFERR, the accuracy to which the top and the
bottom recovery fractions of a component must approach unity; and
BPERR, the accuracy of the bubble point calculation. These error
limits have been given the values Sill1ERR = 0.001, RFERR = 0.001,
and BPERR = 0.0001.

A complete computer program - DIS - lS described 1n Appendix F.

r'

l.

r ~1

r 1

\ J

f1
fl
 -22-

[: VI. Results and Discussion

1. Liquid molar volume

The dependence of the pure-component liquid molar volume on the

temp erature lS as follmvs:

r~
= a + (VI-l )
l.
The constants are listed in Talbe VI-l.
These values,like the rest of the values discussed in this chapter,
were calculated using proc edures descri be d in chapter V.
[:
Table Vl-l: Constants of MMA, TMA, DMA and Water ln the liquid
, '
molar eguation.
I
l .

. 3 o
f '
Component a[cm 3 /gmol] b[cm / grnol TK] c[cm 3 / gmol (T K)2]
l •
_4
MMA 5.537 * 101 -1.413 '* 101 3.830
* 10
4
TMA 7.964 * 101 -9. 633 3i 10 2 4.9 118 * 10
101 4
DMA 8.239 * 101 -2.155 * 5.800 ii 10
1 10- 2 4
Hater 2.288 * 10 -3.6 112 * 6.856 * 10

r'
I

2. Vapor pressure
r -,
The vapor pressure of the pure component as a function of temperature
l ,
is written as follows:

lnP~ [atm.] = Cl + ------

The constants are listed ln Table VI-2.

n Table VI-2: Constants of MMA, TMA, DMA and water ln the vapor
pressure equation

n I
n I
I

r
I
 , 1

-23--

[: Tabl e VI - 2 : Constants of MMA, TMA, DMA and Water ln the vapor pressure
equation.

[: Compone nt C C C Range ° C
I
Cl 2 3 4

[:
2 4 -1 2
MMA 8 . 55 12* 10 - 2 . 995067*10 1. 859* 10 -1.420*1 0 80~ Î4 0
1 0
TMA 4 . 3780*10 -3.-(1 5630*10 3 8.818*lÖ 3 -5.821*10 60-i- 11fO
r' 1 4 -1 '1 . -"'-3
2
DHA )0 * 10 81 7 139
I
I 9 .4267*1 0 -3 . 333743*10 2 . 0 11*1 0 -
l.
r'
Water
.
7.0430* 10
1
-7.362690*10
3
I 6- . 950* 10-3 - 9 . 000*10 ° o .:;1 25

I
I, •

r' 3. Wilson constants

l •
3.1. Res ults

The Hilson constants vere calculated for the following binary systems :
(a) M.r-1A- water; (b) TJ"IA-water; (c) DMA-..rater . The ca lculation ..ras carried
, I
out at t emperatures between 70 to 140°C in int ervals of 10°C. The
l •
results are listed in Tabl es VI-3, VI-4 and VI-5.

Tabl e VI-3: Hilson constants for the binary syst em r-.-R-1A-water

Note: the compone nt lS no. (1)
water (W) lS no. (2)

,1
i ,I tOe A A
l' 12 21

r 1 70 5.4647 0.0000
80 4.9892
90 4.4315
f1 100 4.0338 (see Fig. 3)
110 3.6300

D 120 3.2716
,/

o
130
140
3.0000
2.7143 1
n
n
/

r
1
f 1

L~
-24-

Table VI-4: Wilson constants for the binary system

TMA-water

tOe Á Á
12 21

70 0.0801 0.7502
80 0.0835 0.6623
90 0.0890 0.5628
(see Fig. 4,5)
100 0.0950 0.4702
110 0.0969 0.4114
120 0.1009 0.3474
130 0.0000 1.4387

l, Table VI-5: Hilson constants for the binary system

D~1A-Ylater

l •

tOe Á Á
12 21

70 0.2418 1 .7253
80 0.2603 1 .5802
90 0.3560 1.2178
100 0.3031 1 .2854
110 0.3198 1 • 1520 (see E'ig. 6, 7)

120 0.3289 1.0233

130 0.3342 0.9193
140 0.3167 0.8599

rl
The characteristic ener~T differences (À .. -À .. ) and (À •. -À .. ) were
• lJ II lJ JJ
calculated for the binary systems mentioned above at temperatures between
fl o
70 to 140 e. The results are listed in Table VI-6.

o
fl
n
~
( ,

L -25-
r •

L.
Table VI - 6 : Energy coefficients of interaction ( À.. -À .. ) and (À . . -À .. )
lJ II J-J JJ
for the binary systems:
( a ) HMA-H ; (b) TMA-W; (c) DMA-W.

tOe cal. cal.

syste::l P12- À 11 ) gmol (À 12- À 22) gmol

]·IIifA- H - 1865 . 23108.

70 TMA-H 534. 1382.
DMA- H - 0.22 596.

MMA- W - 1868 . 22888.

80 TMA-\\T 509 . 1522 .
DMA-W - 63 . 687 .

W\1A-H - 1848 . 12688 .

90 TMA-W 465. 1694.
DMA-W - 303. 871.

MMA-Vl - 18 1n. 21720.

100 TMA-Vl 417 . 1887.
DMA-I{ - 204 . 903.

MMA-W - 1826 . 20466.

110 TMA-W 401. 1023.
DMA-W - 263. 2051.

MMA-W - 1806 . 26057.

120 TMA-W 368. 2249.
l J
DMA-W - 304. 1155.

MMA-W 24520.
[1 130 TMA-W
- 1797.
27630. 1180.
DMA-W - 337. 1283.
n MMA-W - 1774. 24180.

n 140 TMA-W
DMA-IV - 314. 1381.

n Note: there was no data available for the binary systern Tr"IA,-W at 140°C.

n
 , )

-26-
r '

3.2. Discussion

The scop e of this p aragraph is: (a) to discuss the method according
to whjch, the Hilson equation was applied to the various binaries
which compose the r:mlticor.'lponent syst.em under discussion ; (b) to
clarify some points c oncerning the computer progrrun (see Appendix C),
by means of .rhich the Hilson parruneters a r e obtained ; (c) to analyse
the values obtained for the paramet.ers ; (d) to disc u ss some other
methods for the calculation of the activity coefficients.

r~ The approach of attack to th e problem was the following: Sinc e there

\ .
was no information availabl e concerning the G-L equilibria of the
r'
bi nary systems (a) MMA- DHA , ( b ) r-1MA-'l'l'fJil., (c) TMA-DMA; and since these
l. are binary systems composed of n early homologous compounds they were
tr eat ed as ideal systemS:the Hilson constants were set equal to 1. 0 .
Therefor e , the problem ,-laS foc used on cale ulati!1g the parameters for the

r '
the binary systems: (a) HHA-W, (b) TVlA-H, (e) DMA-H for vlhieh only
0
j , bubbl e -point behaviour was a vailable in the range 70 ~ T ~ 140 c and
a eoncentration rang e of 0.0 to ea. 40.0 mole-% of the resp ee tive
am1ne.

As it was discussed 1n Chapter V, the parruneters were ealeulated by

means of a computer progrrun (see Appendix C) whieh was described by
Prausnitz (19). This progrrua ineorporates a eertain subroutine nruned
LSQ. The latter lS a nonlinear multiple-regr e ssion subroutine whieh
adjusts the parameters of a function being fitted to data in sueh a
manner as to yield a least-square fit. The Wilson parameters are
obtained according to the optimal fit of the total pressure. The sub-

n routine LSQ was not deserib ed in the program, and therefore another
subroutine nruned oppm" replaced it. The latter has been used at the
T.H. Delft and gave good results for ealeulating the minimum sum of
n squares and thus finding the best fit between a eertain function and
given data.

n In order to check the entire progrrun (including the new subroutine),

an example whieh appeared in Prausnitz ((19), p. 155) was programmed
n and run on the computer. To the writer's surprise the Wilson parrur.eters
whieh were obtained differed up to 15 %, as compared with the results
n in Prausnitz's book.

n
L J

r
( ,

L ,

-27-

In the light of these r esults it was suspe cted that a mistake was
made vrhile punehing the program on eards. The listing .TaS ear efully
eheeked several times but no mistakes eould be found. The only two
reasons whieh might e ause the di sagreement in the results eould be
the following :
(a) subroutin e LSQ is more effieient 1n ealculating and minimizing
the sum of the squares .,hil e fitting a function to data in compari son

r: vrith subroutine OPPOW;

( b) there is amistake either 1n the original progr am or ln the exan!ple
1n Prausnitz .
It might be a good idea to try and get the subroutine LSQ and make a
t est -run with the original progrmn and the example whieh appears in
the book . Because, however, the differ ence was not too l arge (~ 15% )
and bee aus e no err or in the program eould be found, it was neverthe less
decided to carry on the calcul ational procedure using the modified
program with s ubrouti ne OPPOH .

, ,
eoncerning the calculat ed Wilson constants , the system DM.4. ( 1 )-H( 2)
exhibited normal behaviour ln its variation of A and A with tempe-
12 21
ratur e . The rate of change of A and A is r egular and indee d the
12 21
r ,
parameters do not vary mueh over a modest range of temperatur e .
0
At 70 e A = 0.2418 and A = 1.725 3; at 140 0 e A has increased to
12 21 12
0 .3167; while A has decreased to 0.8599.
r- 21
I
I,
For the binary systems TMA(1)-H(2) and MHA. (1)-W(2), however, anomal ous
behaviour is found. For the former system the change in the values of
0 0
A and A with temperatur e from 70 to 120 e is normal. At 70 e,
12 21
A12 = .D.0801 and A21 = 0.7502; at 120 0 e A12 has incr eased to 0.1009
~l and A has decreased to 0.3474. This rate of change is regular. But at
0
21
130 e there is an abrupt change in the trend of the values of the
parameters. A decreases to 0.0 and A increases to 1.4387.
12 21

The constants of the binary system MMA(1)-W(2) vary too much in a small
n 0
range of t emperatur es ; e.g., at 70 e A = 5.4647, while at 90 e
A = 4.4135. A
12
0

r emains constant through the whole range of tempera-

n 12 21
0
tures 70 ~ T ~ 140 e and is equal to o.o.
Bearing in mind the fact that th e se constants are not supposed to vary

n much over such a temperature range (the difference lS usually in the

order of a few tenths), this trend seems strange.

n
r 1
I
L~
-28-
I.
l~
The values obtained for the energy coefficients (1.. -1.. ) and
12 11
12-1.. 2 2) raised some questions , namely:
(1..

(a ) the tre nd in the values of (1.. -1.. ) and (1.. -1.. ) of the binary
12 11 12 22
system TMA (l )-H(2) suddenly rcverses in direction at 130 0 C (keep in
mind the abrupt change in A and A for this system mentioned above ).
12 21
Up to 130 o C, ( 1.. -1.. ,) lS 1n the order of a few hundreds cal. / gmol .
12 11
At 130°C , (1.. 12 -1.. 11 ) lS equal to 27630 .ca l. /gmol. This jump seems
strange;
(b) the r esults for the binary systems at 80 0 e are, for example:

cal. cal.
Component ( 1 ) ( 1..
12-",1) gmo l (1.. 12 -"22 ) gmol

TMA 509. 15 22 .
DMJI.
- 63. 687.
I
l J MMA - 1886 . 22888.

l ,
Note: water(W) l S no.(2).
Based on these resul ts the following statements can be "rri tt en , in
which r = energy of interaction in c al. /gmol. Recall the fact that

12 ,1..1..11 and "22 are ah.rays less than zero.

1..
r '

1. r(THA-W) < I(TMA-TMA )

r'
2. r(DHA-\v) > r (DMA-m,1A )
l.
3. r(MMA-Vl) > r (MMA- MI.1A)

4. r(TMA-H) < r(w-w)

5. r(DMA-W) < I(\<l-W)

n 6. r(MMA-W) < r(W-H)

n and:

n (>..
. 12
-À )
22 ('l'MA-W)
À )
22 (DMA-W)
= 835. cal/gmol

n
n 7. r(D~ffi-W) > r(TMA-W)

L ) - = -21366. cal./gmol
l; ( À
12
-
'ë2 (THA-W)
(1..
12
À )
22 (MMA-I-l)
 -29-
r '
I
I
L•

8. I (TMA-H) > 1 (HMA-H)

Thus, combination of 7 and 8 gives:

9. I(DMA-W) > 1 (THA-iv) > IU-1tvfA-1;.,r)

It must be born in mind that the lflilson equation i s a semitheor etical

equation, and applying theoretical significance to the parameters is
only an approximation. In any case, statement no. 1 seems incorr ect .
L From the standpoint of organic ch emistry ( see belOW) the interaction
r' of water and TMA must obviously be greater than the interaction of
l. two TMA molecules due to the polari ty of \-later, viz.,

H
r ~
H - 0
1
1
TMA-I'l interact.ion
r ,
CH - N - CH
t., 3 3 .J

CH
3
r ï
?H3
I ' 1
2
TMA-TMA int e raction
CH
3
- n - eH 3
( , eH
3
- N- eH
3
l, IL CH
3 .....
Concerning the other statemen~ it lS difficult to say defineteiy whether
they are correct or not, since two opposing effects must be taken into

n consideration; these are: while substituting methyl groups for hydrogen

atoms in ammonia two effects occur:
(a) the basicity is' increased,' thus. increasing the solubility in water;
(b) hydrophobia is increased since methyl groups have no affinity for

n water; thus)the solubility in water is decreased.

Because the writer, after much thought and consultation, could not

n explain the cause of all these ancmalous results obtained for the Hilson
parameters a letter was sent to Professor J.H. Prausnitz of the University

n of California, Berkeley (see Appendix G). Professor Prausnitz is a world

authority in the entire area of molecular thermodynamics and the writer
hoped to receive comments which could shed light on the problems, (his
· 1

r '

L_

answer lS given ln Appendix H). In his lette~ Professor Prausnitz

mentioned a few points which are very important when applying the
Hilson equation, namely:
(a) Wilson equation is applicable only to completely miscible systems,
and immiscibility may occur in the system (8) under discussion;
(b) Wilson equation is a semitheoretical equation;
(c) the data necessary to calculate the parame t ers must be very accurate;

[: (d) various sets of parameters can be obtained for varlOUS sets of data;
(d) the parameters obtained depend on the reduction method of the data,
viz., the fit of vapor composition data, or the fit of total pressure
data.

Concerning point (a), as pointed out earlier one of th e disadvant ages of

the model is its inab ility to describe immiscible syst ems . When Vlilson's
equation is substituted in the equations of thermodynamic stability for
a binary system (s ee Prausnitz (3), p. 233), A and A cannot indicate
12 21
the existence of two stable liquid phases. This is a cardinal point and
must be absolutely clear. Concerning the binary syst ems treated above and
the multicomponent system of t&4A, TMA, DMA and Water, it is not certain
that these mixtures are completely miscible, especially at high tempera-
r' tures. If indeed they are not,another model may be applicable.
The latter is Renon's equation which, unlike Vlilson's is applicable to
partially miscible systems. Since there was no information about the
miscibility of these systems, it would seem wise to check this point
experimentally. In any case, it is recommended to try to apply the Renon's

[~
equation to this problem.

Concerning points, (c) and (d), the data used to calculate the parameters
[1- were taken from graphs published by Rohm and Haas Co. (28) and Gallant
(21). No tables were found with TI vs.T for the binary system under dis-
cussion. Because the data for TI appeared on a logarithmic scale it was
difficult to read it accurately • .On top of that the graphs of TI vs.T

n covered only the concentration range from 0.0 up to approximately 40 mole-%.

Thus, it is very well possible that if more data were available and if it
were more accurate another set of parameters could have been obtained.
n
n
n
L-I

i . -3'-
L_

Because of some unc ertain values of the Wilson constants it was decided
to try and calculate the activity coefficients for the multicomponent
system under discussion by means of the three suffix Margules equation.
Some methods are described in Hála ((2), p. 41), from which it i s
poss ibl e to calculate the constants A and B in the Margules equation
without a knol-Jledge of the equilibrium G-L composition of the binary
systems; only a knowledge of the bubble-point behaviour is required.

[: However, these methods cit ed above could not be successfully applied.

One method, suggested by Carlson and Colburn (29), is bas ed on the fact
t nat in those c ases where the vapor phase can be treated as an ideal
one, then: (a) the fugacity of the component in the system c a n be r eplac ed
I' by the partial pressure; (b) Dalton's lm'J holds for the vapor phase.
l. Then by definition for a binary system:

0
TI - y 2P 2X2
Y , =
0
(VI-3)
l , P,X,
0
TI - y,p,X,
Y2 = (vI-4)
0
P X
2 2
r'
I
l !
As X ~ '.0, Y ~ '.0 so that an apparent activity coefficient can be
2 2
calculated for component' by assuming Y = '.0. By plotting these
2
apparent activity coefficicnts on semilog paper vs.X, an extrapolation
may be made to find the terminal values of the activity coefficient s ,
whose logarithms are the constants in the Margules equation.

n Unfortunately the assumption of an ideal vapor phase seems to be incorrect

in this case because of the polarity of the components.
Furthermore, when substituting Y, = '.0 into equation v-4, a negative
value is obtained ln some cases for the apparent activity, making it im-
possible to continue with the calculations:
n Another method to obtain the constants A and B is by plotting log TI vs.X

n and drawing tangents to the curve at X = 0.0 and X =

data and some mathematical manipulations the constants can be calculated.
'.0. Based on these

n But the data for the binary systems and the respective amines cover only
concentrations range up to approximately 40.0 mole-%. Therefore a tangent

r
!
 -32-

to the curve at X = 1.0 could not be dravrn, and . thus the method could
not be applied.

Summing up, the values obtained for the Wilson parameters exhibit
different trends for the various binary systems under discussion. The
parameters cannot be rega.rded as reliaole until certain points viz.,
miscibility, range of data and its accuracy can be clarified. In any

r: case it is reasonable to try to apply Renon 's equation.

4. Extractive Distillation Column

The column was supposed to be designed by means of a computer program
which was vrritten especially for nonide al distillation (se e Appendix F).
The deviations from ideality were expressed by means of the activity
coeffici ents) vhich vtere calculated in a special subrout ine . Originally
the calculati on was carri ed out with the three suffix Margules equation.
Fo!' reasons already indic ated a new subroutine, based on the Hilson
equation, was introduced in the program.

The program v;as punched on cards and a test-run vTaS made wi th the example
which appeared in Hanson's book (20)~ however, no solution vas obtained.
I ' The program was checked several times and according to the writer, there
are two mistakes in it, namely:
(a) statement no. 23 is written as follows:

r 23 DO 24 J = 1,JC

it should be written:

n 23 DO 24 J=1,JD;

n (b) the statement following statement no. 25 1S written as follows:

DO 26 J = 1,JC

n it should be vTri tten:

DO 26 J = 1,JD
n
I '
Î
l _
- 33--

Af ter c or recting these statements , a sOlution , ident ic al wi t h the one

which appear ed in t h e book , .Tas obtained .
!' The Wi l son parameter s \.,rh i ch wer e used in the ca l culations "Te r e as f ollows :
For t he binary systems MMA (1 )- DMA(2 ), MI,1A ( 1 )-TMA ( 2 ) and DMA (1)-T.t..1A ( 2 ), the
par amet ers were set equal t o 1. 0 . For the ot he r b i nar y sy s tems vi z .,
MMA ( 1 ) - We2 ), DMA ( 1 ) - H( 2) and TMA ( 1 ) -Vl( 2) the parameters .Tere the averages
of t he ir r espcctive v a lues between 70o C a nd l 4OC 0
. They a r e list e d i n
Table VI-7.

[ : Tabl e VI-7: Average Wils on par amet er s fo r t he systems : ( a ) MMA (1)-W( 2 )

(b ) TI.1A (1)-Vl ( 2 ); ( c ) DMA (l )-W( 2 ), in the temperat ur e r ange
0 o
70 C 14 0 C.
r' ,
I

·~ i
I

r '
.

A I
MMA( 1 )-vl( 2 ) TMA (1)-H( 2 ) I DMA ( 1 )-Vl (2)
I

1\1 2 3.9418 0.0909 0.3076

I
I
I iI

l 1\21
I
0.0000
I
0.53 110
I
1. 2279

i
I , Note: ln the cas e of the binary system TMA(1)-W( 2 ) the anomalous

r '
value s at 130 0 C we r e neglected in the calculation of the

I 1
avera ge.

n The reason for averaging of the parameters was that an actual column, which
separated TMA from the syst em under discussion by means of extractive

n distillation, was operating at about the same temperature range. By using

average value s the parameters ar e less accurate for the whole temperatur e
range, but this procedure is areasonabIe approximation for a first design.
n The next step would certainIy be to rewrite subroutine ACTCO (for y's),
in such a manner that it would read a new set of parameters for about each
n 10 0 C and caIcuIate accordingly the activity coefficients. Thus the built-in
temperature depe ndence of the Hilson parameters would play its proper role

n in calculating the activity coefficients.

 , 1

r ' -34-
I
I
l ,

r'
I Many trials were made vrith vanous reflux ratios (0.5 R .: 2.0 R) and
l.
various rates of extrac tive "Tater (0.75 F :. 1. 65 F in kgmol/hr).
Unfortunately, none provided an optimal desigr... All of them exhibited
an -anomalolB change of t emperatures along the column and an insuffic ient

[ : separatioll of TMA.
As for exampl e

SOL V:ccEN,-,-T_~ OVERHEAD

---'~~-PR 0 D uCT
.D

( ,

SOLVENT PLUS
eorrOM PRODUCT
S
,,
F
1 = 142.8 kgmol/hr r 22 .4 kgmol/hr MMA
20.3 11
TMA
18.4 " DMA
r'
i \..81.6 " w
l ,

F
2 = 233.3 kgmol/hr W

l)
The column consists of 60 plates, and the feed lS introduced above the
50th plate. The extractive water is introduc ed above the 55 th plate.
[1 The reflux ratio is set equal to 1.0, thus R
L
=D = 1.0.

r1 The results obtained after 93 iterations are listed 1n Table VI-8.

Note the following order of the components, viz.;
[1 (1) MMA
(2) TMA

n (3 )
(4)
DMA
W

n
n
 .------, ..--------, r- ~ , r- - '[ I

~ '--:1 :=J .::=J ~ ~ ------"

,.
"
l

1-3 PROBlEM NO. ~

~
f-'
CD
<:
11ERATION NO. = 93
H
J
CP MOLE FRACTrONS LISTED AS COMPONENTS PCR PL~T~

en ~
BOTTCM P~ODUCT
p, «en CD I .
)-'.
en c+
en
~ (t) O.62077902E-01 (2) O.124825<J 13!: -C'1 ( 3)O .4~ ~SJ2 i2~- Ol ~ 4 ' O .8 J ~40160E na
c+ CD f-'
)-'. S c+
f-' en RE88ILEI\ VAPOR
f-'
Pl
c+
)-'~ ~
,0
H:l 0.22443ó28E ro O.225874 90F. nn () .2 :l6262tnE ;')11 :) • 2 G) 3 ',I ~ 12 E 00
0 J CD I
::s ><
~ Rf FLUX W
c+ V1
en >-j
,l .l H328154E rIJ I
J Pl O.15ó7C86oE-Ol Oo7~313231~ CO J.gFt':ÏC' ,)69[- Ol
() t::J ()
c+
~J
0
::sp, )-'.
TOP PROfJUC T
)-'. ~
<
CD
ei- O.15670866E-Ol O.7H:H32.31F 00 \~.11nL(H')41: 'I r) "I.13245CSb '}E-01
)-'. P,
0 )-'.
::s en
BorTOM PRODUCT RECOVERY rR~CTrGNS
en c+
)-'.
~ f-' O.0S57ó367E 00 O.21765nOOE 00 '1.d6C) CH4J::3 [ 00 Cl. C1 94:i'ltZ5E 00
CD f-'
>-j-
CD ~
)-'. TOP PRODUCT RECOVERY FRACTIONS
en o 0.14271677E-01 0.7~313226E 00 fl . LH 1 391'5 E >') (1 0 . 5341J~73E -02
"d ::s
CD
()
)-'.
o
H:l
H:l SUft'MATION OF R.EC I)VERY fRACTIUNS
~
)-'.
CD 0.lCOC0353E 01 O.lO(')782')E I)!. \I • l('\{) 0 1 5 1 6 E iJl l:" . :) j09U 2S5E ClJ
P,

~ ~ HOLES OF Fé~D ANO PRODUCTS

0 o
<
CD
S
c+ COMPONENT FEED ~OTTC\I r ~o; ) uc T r ;) P P ; ~ IJ uU C T
::r MMA O. 2239t:l 9 q1t[ 02 O. J 1 'V) 8 " ") 2 F () '. )
CD 1 O .. 22!l!.l1100[ l'2
"'~1A 2 O.203S9994E 02 o • '+1+ ~t J () ') F 1C (l 1 () 0 1 5 ') 7 ? 8 q lt t= ;) 2
nMR 3 o • 1 i33') ) 9 ') 4 r:
0l () .. 1 ':) g BS ~ p~ 'i [ r) 2 ~ '). 2 4 1 2 9 It 1 ,) r ei i
0.31't80<)<] I)[ 03 n.JIJIU72,sE ()3 ') • 1 6 'H 9 9 (~ ó I-: () 1
~ :.
\vATER 4

--!) ,. :3 S c,u <; ---_ Id--

\:: ():> n • Z 0 3 '1 n I. ~ < I [
O.37r,OQ)85F 03 :L~
..
:) 2 _. ---?- . '"--- .._-- --.-_._-
~
- - --- ---- _.~- ...- . -- - - - - -- --- .~
 ( .
I
I ~

-36-

The change and rate of change of the temperatures along the c olumn
r
l ,
are v ery strange, namely :

(a) the temperature of the "reboiler lS equal to 13 1o C;

( b ) the temperature of the lst plate l S equal to 118°C;
( c) the temperature of the 2nd pl ate equal to 117°C;
l S
o
(d) the t emperature of the 50th plate is equal to 11 2 C;
(e) the t emperature of the 5 1st plate (above the introducticn of the
0
f eed to the column) lS equal to 132 C (!) ,.,hich is physically
imposs ibl e ;
0
(f) t he temperatur e 1ncreases up to 152 C at the 56th plate (above the
introduction of the extractive water to the column);
r-'
I ( g ) the t emperature of the 60th plate lS equal to 97°C;
I
(h) the temperature of th e distillate lS equal to 82 o C.
( I

One of the causes of this anomalou s behaviour may be that no heat

balanc e is incorporated in the program. Thus, there is no corr ection
of the mass fl ows , and they are assumed to remain constant throughout
the calcul at ion. This may be too rough an approximation for the present
r '
system.

Another r eason may be connected with the Wilson parameters, some of

which exhibited irregularities. This point has been discussed previously
and i t is very well po ss ibl e that the Hilson equation is not applicable
r -,
in this ca se . In any case, befor e trying to clarify the anomalous results
concerning the temperatur e gradient in the column, and th e insufficient
separation of TMA, the question concerning the Wilson parameters must
l J
definitely be clarifi ed.

f1 As a general remark it should be said that it is worthwhile to develop

a more comprehensive , efficient program for . nonideal distillation which

n would incorporate heat balance and would converge more quickly after a
small number of iterations. A basis for such a program can be found in

n an article written by Naphthali and Sandholm (31), which describes new

calculational methods for distillation,

n
n
 f '
L
-37-

l~
VII. Figures
, l~
I
--------------

I [:

[~

r
r
~
I [:

r ,

l.
, ~

I
,I .

[~

r
n
l 1

n
n
n
n
n
n
r
l.
:-l ==:J ==:J ==:J :=:J ==:J =:Jo .---,
...
~
J
..----,
J ,
r - !I ~
'---'
r----: r---'
L

CRUOE
CONVERTER PRODUCT ' NH) TMA MMA DMA
STORAGE COLUMN COL UMN ' COLUMN COL UMN

..,.
~
METHANOL
WATER
.. - ;; .~

H2+ CO

~COOling-
AMMONIA
..
~a ttr
~',
'- Î

-..) ~~ ...
.A.....
.... ~-­
.,- ~
~
I
W
CD
I

, } ANHYOROUS
IL-----:-1....
to PRODUCTS

I
=J ''8 -1-
.! -~ç}",""",
WASTE

METHYLAMINES (th. ,LEONARD PROCESS CO, INC) J , Fr.nk.\

Moi 19'14

Fig. 1: Flowsheet of the Leonard Process for production of methylamines

 J.

r . -39-

SOL V[ NT

[ FEEP--oI

SOLVENT PLUS
80TIOM PRODUCT

Fig. 2: Extractive distillation column

n
n
( 1

( .
I
L.

Fig . 3 : Wilson constant 1\ 12 vs. T[co J, f or t he b i n~ry system HMA( l )- 1-1(2 )

r
A .A /2
\

5.S· \
\\

5 .0
; __ __..,.__. _L __ --=-_ ._.:. __ .. __ .;-__ _ ....
~

~ I

r~.
t
i
f--- - r ..

: _. - I
1

L
r
n
n
n ,I . t ,

_o r'
n 1-'
I ,I

~
!
( ,

-41-
!'
l .

Fig . 4: Hilson constant 1\12 vs. T(co) for the binary system TMA( 1 )-vl( 2 )

___ i - - .- ..L _ •• _ _ ~ •. _
,
__ • • L ____ _

. ,
----- _ ._~

i
L ___ J
l_.l
r~
l .

n
n
n ,
! -

- • -
;
! -. ·- 1-

,
i
r I
, •• 0 .
r-- :
.- - 1---' -t·--·- ..-
i ;
r·-- :----· :· ---:··- Ij--'-'-' T ··_·_·1----··-
I 1
, 'I ' . ,
I

0 .00
70 ?D 90 Ic".) 11 :-;
 ( 1
I I
(

- _. _.;----- --.-,--., --

r ' ,
- j.
I
- "--- ----- --. - ,- ------
!

- .;

Fig. 5: 1,1ilson constant 1\21 vs. T[co], for the binary system TMA( 1 )-W(2)

r
A '2./

( ,

r '

! ,
1.5 I-_. __ _~. _____ j ._-~.- _. __ J.. ____ __ -- -- _ -:---_._---j.,------~. -_._- . -- ..
i : I .
. . I

L
r~

fl
n
n
, _·: .. ··t··.. ;·..·r... -
n f.
~ I
i .•. - -Ol

LJy~t----~i--~Ir---~I----TI--~Ir---TI----~I------~....
. I

70 20 ~o Ico Ilo Ilo 130 Ka T [Cc)

~
1
( 1
i'
L .. . .. r···

( . - 43- . ; .....- ... - 1'---

I j .
L

L
L
[
Fig . 6 : \·;::..:....3on::onstant A
l 12
v s . T[ co ], for the binary system Dîv1A( 1 )-H( 2)

r:

i
f _..; ,··:- 1

n
n
D

i·

n I !
,. .

o ,ZO _
n r··
._ - " ... . . . ... .. .,-- - . -_ .••. r ..' I ... _. . ~ _. r . . .. 1
I
r· !

1 I
-tv I I I
!?("
I
Ho
I
H')
I
.. T [C")
70 ë-: I')') li') I~
f 1
I
LJ .,
I

( . -44 -
I
l.

L
r

[~ .
Fig . 7 : vlilson constant 1\2 1 v s T [ co ], for the binary system DMA( 1 )- W(2)

[:

r'

n
n
n
1.0

n I
j

I
--- .•
i
:

:
---- - --- t-
i
-···-----t-----
'
._-,--_... _- . i

lo() 11 0
r 1

l~

-45-

VIII. Nomenclature
L
A a constant ln the van Laar 2.nd t-1argules equation [dimensionl ess J

a activity [dimensionless J

B a constant ln the van Laar and MG.rgules equation [dimensionless J

B second virial co efficient [cm3 /gmoll J

3 2
c third virial coefficient [ (cm / gmol) J

f f ugac ity [atm. J

fugacity at standard state [atm. ]

E
g excess Gibbs energy [cal. ]
E
h excess enthalpy [cal. ]
( ,

I. K equi libriun constant [dimensionless ]

p pressure [atm. J
[,
pr essure at standard state [atm. ]
r '
P<?1 vapor pressure of pur e compon ent 1 [atm. ]

R univers al gas con stant [cal/gIJlol TOK]

excess entropy [cal/ToK]

T t emperatur e [TOK or TOF]

liquid molarvolume [cm3 /gmol]

x mole fraction [dimensionless]

arbitrary composition at standard state; [dime nsionlessJ

f'I usually mole fraction
I
l j
z compressibility factor [dimensionless]

y activity coe fficient [dimensionless]

À.. a const ant proportional to the energy of interactions [cal. / grool]

11
between i-i molecules

idem; between i-j molecules [cal. / grool]

A·11. Wilson constant [dimensionless]

Wilson constant (dimensionlessj

n
A· .
1J

n
ri
(
11
I
\
1-1
-46-

l
chemical potential [cal. / gmol ]
L 11

11 total pressure [atm. ]

L 0 fugacity coefficient [dimensi onle ss J

r
r
L
["
1~
[.
r .
1

r:
L
r
f:
lJ

~1
n
r
n
r
r'
I
(
 -47-
, '

I
l .

IX. Literatur e cited

1. Jlydrocarbon processlng , ~, 150 ( 1973) .

2 . Ha.la , E. , et al. , "Vapor-Liquid Equilibri '.llIl"
(2nd English Ed i t i on ) , Per gamon Pr ess , 17, ( 1967) .
3. Pr ausnitz , J . H., "t·folecular 'l'hermodynami cs of Fluid- phase Equilibri a ",
Prentice- Hall , Inc ., Englewood Cliffs , New J ers ey , p.p. 186 (1 969 ).
4. Black, C. , Inc . Eng . Chem. , 2Q , 403 (1 958) .
5 . van Laar , J.J., Z physik chem 83, 599 (1913).

[ 6. van Laar, J.J., Z a norg allgem chem 185,35 (1 929 ).

7. Hhjte , R.R. , Trans. Am . Inst . Chem . Eng .,~, 539 (1 945 ).
8. Benedict, M., et al. , ibid .,~, 371 (1 945 ).
9. Gerster , J. H., et al. , Ind. Eng . Chem ., 39 , 797 (1 94 7).
10. Redlich , 0 ., a nd Kister , A.T., J. Chem . Phys. , lL, 84 9 (1 947).
1: 11. Scatchard, G., and Ticknor , L. B., J . Am . Chem. Soc ., 74, 3724 (1 952 ).
12. Scatchard , G., Tran s . Faraday Soc. , 33 , 160 (1 937 ).
13. \Vohl , K., Trans. Am . Inst . Chem . Eng . ~, 2 15 (1 946).
14. \Vohl , K., Chem . Eng . Progr. 49 , 2 18 (1 953 ).
15. \Vilson, G.t1., J. Am. Chem . Soc ., 86,127 (1 96 1+).
16. Prausnitz, J.M., Orye , R.V., Ind. Eng. Chem., 57, 2, 18 (1 965 ).
17. Flory, P .J., J. Chem. Phys .,.lQ., 51 (1 942 ).
18. Huggins, M.L., Ann. N.Y. Ac ad . Sci ., 43,1 (1942).
19. Prausnitz, J.M., Eckert, C,A., Orye, R.V., O'Connell, J.P., "Comput er
Calculations for t-1ultic omponent Vapor-Liquid Equilibria", Engl ewood
Cliffs, N. J ., Pr entic e - Hall, Inc., (1 967).
20. Hanson, D.N., Duffins, J.H., Somerville, G.F., "Computation of Multi-
state separation Proc ess lO , Rheinhold, New York (1962).

n 21. Gallant, R.W. , Hydrocarbon process ing

22. Felsing, vLA., Thomas, A.R. , Ind. Chem. Eng.
~, 151 1969.
~, 1269 ( 1929).

n 23. Felsing, W.A. , Day, H.O.,J. Am. Chem. Soc. , 72, 1698 (1950).
24. Jordan, T . E. , "Vapor Pr es sure of Organic Compounds" Interscience

n Publishers, Inc., New York, p.p. 190 (1954).

25. "Handbook of Chemistry and Physics", 54th edition, CRC Press Cleveland
Ohio, p.p. D-162, (1973-1974).
n 26. Bijwaard, H.M.J., Graduate paper, T.H. Delft, p.p. 83, September (1973)
27. Barker, J.A., Australian J. Chem., ~, 207 (1953).

n 28. "Methylamines", Product Bulletin of the Rohm and Haas Co.

n
r
 1
-48-

!'
L_
29 . Carlson, H. C., and Colburn , A. P ., lnd. Eng . Chem ., 34, 58 1 (1 9 42 ).
30. Renon, H., and Prausnitz, J.M., A.I.Ch.I. Journal~, 135 (1 968).
31. Naphthali, L . N., and Sandholm, D.P., A.I.Ch.E. Journal, 17, 148 (1 97 1).

r'
Il

( ,

l,

~
n
n
n
~
1
I 1

l,
-49-

l.
t: ~!?!?::~~~::::::

L
L
['
f'
e
L
L
!'
r'
r
r~
. J

n
n
n
fl
n
~
!" , .
 :!
I
L ... -1-

The "Hilson Eq uation

Deviations in the ideality of the l iquid phase can be described making use
of the concept of " excess funct ion s ". The molar exce ss Gibbs energy , for
example , is defined as follows:
[.
E g ( actual soluti on ) g(ideal solution at)
g = at T, Pand X same T, Pand X
[.
This function is th e most u sefnl one fo r our purpose , because i t c an be
dire ctly r e lat ed to the activity coefficient by means of the rela ti on :

n
E
g = RT L x .lny.
l l
i=l

Th? excess Gibbs ener gy l S formed from two , parts the excess enthalpy and
the exc ess entropy :

E
r '
g =

,. , Th e s implest assumption conc ernl ng gE is to assume that it is equa l to zero.

This l eads to the c oncept of ideal solution. The next assumption, l es s
drastic, is to assume that hE or SE equals zero. Most of the equaitons for
g E are obtalned
. .
by settlng SE In '
equal to zero. thlS way h E can b e des crlbed
.

by means of a polynomi a l expr es sion ln the mole fractions or the volume

.
f ractlons. The assumptlon
. SE = 0 l eads to the concept 0 f regu 1 ar so l '
utlons.
The theory of r e gular solution for molecules of e qual size was deve loped
by van Laar.

E
v,T}}en molecules of unequal Slze are mixed, hOIvever, it lS better to set h

r1 equal to zero.
Solutions in which hE = 0, are temperature independent because mixing o~curs

n . without evolution or absorpt ion of heat. The theory of the temperature

independent solutions has been developed further by Flory and Huggins during

n their study of polymer solutions. The Wilson equaiton is a semi-theoretical

expansion of their derived relations. Wilson also considered molecul es not
only of various sizes but also of various intermolecular forces.

The Flory-Huggins equation for athermal solutions is derived on the basis of

statistica l thermodynamics, and the derivation would not be presented here.
lJ
-2-
I .

I
l,

The Flory-Huggins equation l S as f ollmrs :

( , E
n 0.l
g = RT E x.ln
l i=1
l
x.
l

r- J.n ,.rhich :

0.l - the volume fraction of component i [d imensionless ]

x. - the mole fraction of component i [ dimensionless ]

l

The se are r elated to one a nother by :

L
x.v. "
l l
0.l = n
L
E X.v.
l l
i=1

ln "hich:

v~l - molar liquid volume of pure l [cm 3 /gmol]

For a mixture of molecules of equal molar liquid volume 0. = x .. For this

l l
cas e the Flory-Huggins equat ion prediets ideal behaviour.

In order to obt ai n the i-lil son equation a binary solution of components 1 and
2 is, firstly, considered. If a central molecule of type 1 is considere d,
r: then the p robabi lity of finding a molecule of type 2 instead of type 1
around this c entral molecule is given by the relation:

x exp(- À /RT)
2 12
= (6)
x exp(- À ,1RT)
1 1

À and À are, respectively, proportional, to the 1-2 and 1-1 interaction

n 12 11
energies. Analogous to this is the chanc e to finda molecule of type 1
relative to molecules of type 2 around a molecule of type 2; this is:

x exp(- À /RT)
1 12
n = x 2 exp(- À /RT)
2

n With the help of these definitions Wilson redefined the volume fractions of
the Flory-Huggins equation into what he called local volume fractions ~1 and
~2'

r
I
 -3-
r '

L
x v exp (- À1/ RT)
1 1
[. ~1 = L L
(8)
x v exp(- À /RT) + x v exp(- À /RT)
1 1 1 2 2 12

[: and
L
x v exp(- À /RT)
2 2 2
~2 = L L
x 2Y 2 exp(- À2 /RT) + x 1v 1 exp( - 1. 1/RT)

If we define
L
v
2
A
12 = ~ exp[-(À 12-À
11
)/RT] ( 10)
v
1

and
L
v
A 1
21 = L
exp[-(À
12
-À
22
)/RT] ( 11 )
v
, ' 2
l,

and substitut e local volume fractions ~1 and ~2 in place of 01 and O2 in the

Flory-Huggins equation, we obtain the Vlilson equation for the excess Gibbs
energy of a binary solution:
r'

E
L
RT
= ( 12)

The generalization for a multicomponent system lS as follovrs:

E n n
IE-
RT
= LX. • ln ( LX. A. . ) ( 13)

n
i=1 l j=1 J lJ

ln which

n A. .
lJ
=
v.
~ exp[-(À .. -1. .. )/RT]
vi lJ I I

11 v.
A. . = ~ exp [- (À .. -À. . ) IRT]

n Jl vj Jl JJ

The activity coefficients can easily be found by introducing Wilson's

n equation into Equation 2, viz.:

, ,
,
:
L.J
-4-

I .
n n x.A· ·
l l k
= ln[ L x.A .] + 1 - L ( 16)
l. j=l J kJ
i=l
n
L x.A ..
j=l J lJ
r'
L In the special case of a binary system one gets

r = ( 18)

[ :
[,

rl
II
l J

n
n
 -1-

The program , by means of ,rhieh the constants in the liquid molar volume
equation are ealeulated is essentially sclf-explanatory . It ean be desc rib e d

[:
seh ematieally as fol l ows :

Read v T-'-~ -'-"'- -- I

1 l' .

v 21'2 ; v3'l'2 I
v
Caleula~~l

~
v._-'-" --- J
Caleulat e b
---_.

'v
I
Caleulate a

Print result s

I ~
2
= a + bT + cT

n
n
n
n
.. --- ,.....
i ) .---. ,----, ~
r--; r--: r--- ~
,
~ ::-=;J ~. ] ~=:J c:::::J :==J

*\~ A TF ! V
c V,'.ID l
C
C
C lHI S PRO GR lIM CAlC ULAI t:S T H~ I) Ef'tN iJb~ CE lJF rHE PU I<. t:-CI)I'If'UNFI~r
C U QulU MOLIIR VOLUME UN THE TEI'IPERATURE
C TH! S OEPENDENCE HAS lH E HJlliJW IN(; t'Üf(N
C VN OL(CM* * 3/G MO l) = A + 8* 1 +C*T**2
1 011'1 EN S lOr. A ( 10) ,B ( lO ) ,C ( lO ) , T ( lO,3 ) ,V ( 10.3)
2 RE ,\ I) ( 5 • 1 ) l
3 ~O R~I AT( 1 2 )
4 DO 2 1=1, l
5 2 REAU (~,3)(V(I,J).J=l.3)
6 3 FOR i~A T( 3Fó .3)
7 DO 4 1= 1 • L
8 4 REAU ( 5 ,3)(T( I,J),J=1,3)
9 DO 5 !=1,l
10 C(I)=((T(!,3)-T(!,1)) * (V(!,2)-V(I,1))-(V(I,3)-V(!,1))*(T(),2)-T(),
11)) )/(((T(I, 2 )* * 2 - T(I,1) **2 ) * (T(I,3)-T( 1,11 11-( (T(I,3)**2-T(I,11**
22P(T(!,21-T(I,l))))
11 R ( 1 ) = ( ( V ( J ,2 )- V ( I ,1 ) ) -C ( I ) * ( T ( I , 2 ) ""2 - 1 ( 1 , 1 1 ,;,,;, 2 ) ) / ( T ( I ,2) - T ( I , 11 I
12 A (I)=V(I,l)-(fHI) * T(I,l))-(C(I)*T(I,U ~";'2 ) ·
13 5 CON TI NUE
14 6 WRlTE (ó,7)
15 7 F OR I'l AT(1H1,'VALUES OF A(I) , B (I) , C(I) , HILlli'tl 'In
ló ,oJRIT E(ó, 8 )
17 8 FOR"IAT (lH ,'VMOL(I)(CI~*"3 / GM() U A(I)" B(I)~'T + C(ll~' T * *2 '
lil)
18 \-JR ITE(6, 9 )
19 9 FORMAT(IHO,'NO.',T9,'A(ll',T24,'l\(ll',T40,'C(ll'l
20 WR ITE(ó,lOI(!,A(Il, B (ll,C(I),I=l,Ll
21 1 0 FORMATl1RO,I2,T9,OPF10.3,T25,lPEI0.3,T41,lPEI0.31
22 20 STOP
23 END

*DA TA

---
,. i

L-,
-1-
r'
l ,

[:

L The prograo , by means of which the constants in the pure component

vapor pressure equation are calcuJ.ated can be described schematically
as follovrs:
L
[~ ,/
Read pure
component dato

L
"
L
Compute matrix
etements

[~
[ , Sotve tor
C1 • C2 • C4
~

r'

l, Compute sum
square % error

r~

r~ Change C6

l.'
No

n
0 \

D l Flgure 6-1. Schematic diagram ror the program VAPFlT,

n
n lnpo( atm. ) = C
1
+
C
2
(ToK)
+ C (TOK) + C 1n(ToK}
4 6
(taken fro~ Prausnitz (19) pp. 75; detailed discussion and nomenclature
G' is given en p.p. 155)

r
----j ' __ J -------. .-------, ...--,
::=J ::=::J c:::J ~ ===:J :-J
.-------, .-------,
J
,......---.
:--l :---J ~ r---: ,...--, ~ ..------.

•.'
... ATd V
l 'IAI''VIT
l
(. fï, ...H:'"MI TC' llhTAHJ PAPfli'tf'TE, - ::, U~ ~lllif( r - " :'_ \M f' T~, VAP. P ~c,. f -, J ~~
l
1 Hl t ... ! II T ~ c ~l ,. Ol I A- Hit HAL" IJ I û- L I
<: OIMLi":>lUN Tn 1181, lUfiHIZI. TilJu), CP~flTllultPI1.001,
ifllL"rdlOOI,YCALllOOI, ti:Ll1001 ,I-CO(- STl1. n O). [ll(\FST(1(lOI
3 LAI-MAJ\ "C=
4 1 .... LAU 15,':, H![l = 9991 JO
5 UlhllN =
0.00001
ó lû~,",AT I1RA41
7 "t':'''' 15,10IN, rer'IT, I-(.I.,IT, .. U ('rlT, TrIX, PFJX, Ffl~"AX, IDUIT
U 10 ~u l,i1"T I IE,6F9.4,16X,<:A4)
4 If lid 9S<;,S°<l, 11
dl 11 ~ U! iiT::. = N
11 :>I"ut';,,,, = PIJIN~<: f~rMAX * •• 2
~2 f,EAU 15,201 Tl, Dl, T2, 02, T3. ';3
U 40 n",,'MAT I bF 12."1
J.4 vl "clGIéT / [11
l~ "Z "U(.HT / D2
lu V3 "êl(.HT / ~3
17 Tl Tl .. TH X
lb U T Z .. TI' IX
19 TJ T3" "-FIX
20 uO .;;0 1 1, ~I
LA. kEf,U 15,ZOI rl!), Pil)
22 TI -I) = (Til) .. TFIXI I 100.0
~J PI ij = i'II) / f'FIX
24 ~o C0 " T HWI::
.:.5 LAt 0 =
20 T::'"i'I C.O
21 T"::'ur·\ 0.0
~6 r::,;:, UI1 C.O
~9 14;:'u/·' 0.0
~O OU 40 J =
1, N
.:>1 l:"uM lSl;H .. TIJ)
>, ' )
... ~ T 2;:'U,-\ TZ SUM .. TlJI*.Z
j:; T ;,;:'ul-\ T?5L!1 .. TIJ)":;
.) 4 T4;:,U~i 145UM .. T( J )**4
,,5 40 l..UiI·IIIWE
3ó l..l>;:'Aï(ó) 0.0
j -r Jlf'::.AT -10.0
:: 0 S-i U t:" r = 1.OrnO
J'j .,vi\..>~P '" 1.Of"30
40 5~ L Af' = LM .. 1
'.1 1';:' u1'1 0.0
4.! Fi'::'ûll =0.0
4"
,.4
I T ,;:'0"
lJ0 55
C.C
J=l.N
45 n = IlJLU«PIJII - CPSAlioJ • ULûGITlJI!! • TIJ!
4ó PS0M PSUM.. PT
4'1 I-T~UM PTsur·, + PT. TIJ!
4tl !-T,SuM PT2SUH" PT * TIJI*.Z
49 55 l..01'11' lNUi..
')u d = I-~UM * T3 SU., - PTSurl * T2;,UM
,1 L~ = PTSlJM * T4SUM - ~lZ:>UH • T~SUM
:'2 All PUINTS * T?SUN - TSUM • T2SUM
53 Al, TSUM * T'SUM - T2SUM • T,SUM
54 A21 TSUM. T4SUM - T.!SUH • T3:>UM
~

~ ::::-J :=J =-=:J c::J C=:J c-=J ~

...------,
.J
.---..,
J
.-----, :--l
,..--.----, r------
r---: r------' ...... r - -.

~~ ~~~ = T~~U~ * T~SL~ - lJS0N • lj~UM

50 ~P~M(I~1 lA2 2 . II - L2 • A121 I lAl! • ~22 - A12 • A?11
'j , C~~~Tl11 = III - All. (pSArlZII I AL?
'>11 l..t':. A" 1 3 I c.o
'>~ l.,f':.A i 141 1,",~Uf~ - PIlJrllS * Cf'~ATl21 - TSU"I. CPSATl111 I T2SU :1
toU CF :' AT I 51 0.0
° SuM~~ = ~.O
6 ULI 1::; I = 1, N
° tl..ALlII= r: " XPICPSATI1.1 + (.F:,ATl21 I TlII + CPSATI41 * TIII
1+ Ct.:>AT(ól *
flLOGITIIIIl
tJ4 iJl.. I ij = P I I I - PCAL I II
05 FC 1 u , h, I 1 I =DM\ SI 100.0 *
(JE LIl I I Pil II
00 S0îl!:> .. = SUî1SQ + PCT!' !, "III **2
67 7'> ~J~TI~U ~
/:,(; i F I L Af' - ! I 1 21, 12 1 , 11 9
6'1 ll~ IF I LAl' - LAPM;\XI 120, SOU, 500
70 i. lU lF 1 ;,uj~St,/ - SUIlEST I 121, 1'-5, l;::S
7i. 121 Swd ~ ST SUM~Q
7~ ll'bL.:>T = L~P
7J UJ 1 2 .: 1 = 1, q
i't f' l..ut::" ril 1 PC AL( 1)
75 iJLth.. !:> TII) =
f1FLll)
70 III CJ ,H illUé
77 Llu tS T = C? SATI!I - CPSATlol * DLOGI10n.a~O)
78 ~~JL:.r =CPS~TI21 * IUD.
79 ~~dtST CPSATI31
dO C4 U L~T = CP 5ATI41 I
IOC.
Ul ' l..::; Gc.ST = CPSA-:-1 5 1 I 10011U.
til C 6 u [~ T = C? SA T l h j
dj H ISI<uLST - SH1PSQI 500, 50J, 130
uit L'S lr l.;.uNS" - SIII·15QP) 130, ljU, 1~6
R5 i~b . 0C~.;.ÄT =- D[P SAT I 10.0
Ol) iFI[j ;.uS! lJ CP SATI - OC PMltl/ 500, 500, 130
d7 l~u Ct'SATlol' = CP~AT(6) + OCt'SAT
88 S uil:' ", i' = S U ~1SI./
tl 9 vU Tu 52
\/0 !:iuU LJ iH WUl
':11 " 1"b C:i<l' =lJSQrTI 5QU EST I POINTS
92 I"d 'I <.: 10, 5 20) j()
~~ 520 ' F~ " M~T 1 J~l, 1 8A4 1//11
94 ~ldT i... Ib,5301 Cl Or-ST, L;: b L~T, C~l)FSr, C413':5T, C5l\"ST, C63(ST
'}) 5JO OFdl .l·li\T 14F,H r ' Af ' i\f~fT r!{ S rU" THr. SATU ,; ATj'l'1 Pkl'<;C;U!lE CURV~ 1/,
~l) .. rli..l~n' c,,1.I =
l.I1I + CldIlC'-,)+T1 ... CI41*T +CI'3I*r"2 • C(6)*UHT
d l / ,!':11 crS .' Tlll =,
1'14.01 lal crSIIT(2) .: , F14.bl 12H U ' :'; AT 131=
;, , 1'~4.f,1 12H CPSAT\4i ,4X, =
[lll•• bl 1211 CPS~TI"I "", I.X,
4 ui " .6/ 12f1 crSAT(6) =,
~l't.6/11
~ tJ ~ K jYL 16,~ 6 01
':/7 5~U UFJ~~AT Il~0,lOx,51HTrM~<.:RATU~~ ~EXP FCAlC DFlTA PCT.E
it", . ,11)
98 SeiN.: 0.0
\Iq MV~~CT 0.0 =
1(; u uU 5 ó 0 I 1, N =
lJ 1 Til) =
Tl J I • 100.0
1J, ""lil. lo,57:)1 TlII, f' III, H;i3lSTlII, I1UFSTIII, 0CH""II)
lJ) 57ll tJ" ,I':'T Ilnx, FlO.3, .3l'1u.:., rlUd)
lUit ~U M = SuH + D ftb S ICLl\~STI1)1
1U~ A y~t'.;r = AVGPCT ... f'CTFt-I, I1I
lUb 5t1u Lu,.."T HllJè:
lU7 ~~UM~~ ~uH I POINTS
106 AV"FCT = AVGP(T I POINTS
""' ..----, r---------, r----o ..----, -.. ,.-----,
~ ~ ==:J =-=:J :==J ::::=J ~--] -.J :-J :--l ~

lu'l "t..i -Il 1::>,5 <;0 ) AVnHAS

liO 5')0 üt.J b ,' IATI1HO, 5X, 44I1M r:AN Id1S:JLUTt:: MfIl'Nl:0UF. !)~ TH !' ['l"VlflT!u r,/s
Jo Fli.::')
111 ~~ ITL 16,5 ~1 ) ~ V G fC~
1!.O:: ~ 'h ILl h,'I':'l ItX, 3HII 1rAN MbLl LUit. t'th,-l'H~l;r ' nl', VI !\111)~ ,F1::. ':; )
L J 1 ,'.{ = O. 7 * TC; /T
114 .~7 =~EXt'(C18f S T + C2tl~~T I T~l + C~B~~T * T~l
1+ Coc:.ESl *
OL['JGITF: ll) I f'CKH
li5 UM E GA =
-1.0 - 0.43429448 ULUG(P~7) *
11D v~~JT =
lo.za! - 0.08 * OMfGA) * lCk!T * H2.0~7 I PCklT
H7 '1 ,:dTt: (o,&CO) T C~IT, f'Lt<lT, V~~, lT, LJM:GA
Lid bUu J~U ~~M T ISHCTC ~ JT =, fB. 3 , ~X, YH PCQIT =, FA.3, ZX, 9H VC ~ IT
l, I· J • .;> , ;2 X, 911 IH·I F. G A = , I' ti. 4 )
llY ",dl ... (o,6C9) Tl, VI, T2, Vl., T3, \Ij
12U b08 FJ :, NAT 19/tOTf/1I' J • Fil. "" <:X. Yrl VUL J. = FfI.3, 2X. 'JH H 11P2
1r'0 • .). 2X. 9H Vnt 2 =•
f-G. :> . 2X. 9H TEMP] ,F .1 .3, 2X, 9H VUL3
<. , FtJ • .:. 111
12. " .. JH (6,5251 SQIH:S T, LPdL~T, kM~t:Kk, LAP
122. S::5 OFU "MA l (j7HO~UI·'
OF S;,J UMlS uF PCi. IJ rVIATlf) "'S , F8.4, 6X, lUIt!
nST LAP = , 13, I 31H t\l.lLJT l1i::Ao'l SI./UAr.l : PE !,CE'IT ('''V!ATION F8.4, =,
.. óX, IlilLAST LA P = , 13, 4X In
: .. 3 GU TU 1
124 999 l..,kL eXIT
US h':T u ,.: N
ld. t,.lJ

*LJATA
 , ,

-1-
r '
l,

Appendix D
-----------

The program by means of which' the Hil son constants ar e calculated can
be described schematically as follow s :

Read pure component Cata ,

par amete r €slimales,
and expp.rimcfllol binary dala
~~~~
, ~
'~~~1~~
B
I

L -
fi.-Yi. )!'J,o(P OI exp (P V/R~ '
i,I) ,

:r:
r'
l,

Intermedia te
printoul

r
I New eslimate of Parameters '
( J mode by subroutine oPPc\f;
. . ._ _BR-P'UIm...·!ll
·.:., .'"'~

n Yes

D
o ,
i' F'gure 6·2. Schema tic diagram for program to fit Wilson parameters
-, ;

to total pressure data.

n
n (taken from Prausnitz (19) p.p.
is given on p.p. 162}
77; detailed discussion and nomenclature
 .----., --------, ,----, ...-----, ,..-----, ,..----. ,..----. - r--
~---"J =--=:J ::::=:J ~ :==J ===:J ~_---.1
-' :--J . ~ ~ L
"

TI U, r-UllUlilliG PRUGRAM IS NUMBEREO: WilS

CHVYFTW WILS
C WIL S 2
C HAIN PRuGRAM fUR NONLINEAR LEAST S~UARES fIT OF TUTAL PPESSURE ij ILS 3
C DATA WITH WIl~UN PARAMETERS IN THE SYMMETRIe CONVENT ION WILS 4
C hJR EITHEK lS0TIIERMAL OR ISOBARIC SYSTHIS WIL S 5
C WILS 6
C- THlS PROGRAM REQU IRES TlfE FOLLOW ING SUBROUTINES INPUT, VIRIAl,WILS 7
c RSTArE, PHIMIX, CALPHW, CAlCFX ANO UPTPUW WILS a
C WILS ?
C MAX(NCOi'lP) =10 WILS 10
C I1AXINPT:i1 =50 WILS 11
C MAXINL IGHTI =10 WILS 12
C MAX(NALTCOJ '" 3 WILS 13
C WILS 14
IMPLlCIT REAl*BIA-H,O-ll WILS 15
RlAl*4 TITLE WILS lb
CUHMUN IOPT/WIIOI WILS 17
LUMMUN IFX/UATA,PT,PCAL,RTEMP,NPTS WILS la
eOMMUN TeRIT,PCRIT,VCRIT,OMEGA,Vll~,CVlIQ,PSAT,CPSAT,CACTCO,GAMMA,WllS 19
1 A,SUMX,V,SUMV,P,T,TOLO,PHI,B,BMIX,VMIX,lMIX,F,FREFER,HENRY, WILS 20
2 lHENRY,VlIQl,CVlIQL,OHEGAH,OIPOLE,ETA,VRATIO,RT,RRT, WILS 21
3 lITl..l,I~CUMP,NLlGHT,NACTCO,IOENT,NREFER,NCRIT WILS 22
c OOIMeNSION TITlEIla), TCRITIJO,301, peRITI30,30l, VCRIT(30), WilS 2J
c lOHtGAI3ül, lüENTI)O,2I, VLIQI301, CVlI~130,3I, PSATI30l, WilS 210
c 2LI'SAr(J0,61, CACTCOD0,30,31, GAM/1AUOh XI30), YIJO), PH(f30), WILS 25
c 3UIJO,JOI, FIJOl, FREFERI30), NREFERIIOI, HENRYIIO,JOI, WILS . 26
c 4C~ENRYIID,30,21, VLIQlI 10,301, CVlI~lllO,30,2), OMEGAHI30l, WilS 27
C. 501POLEI301, ETA(30) WILS 28
OOIMC I.::.lLlN TITLElla" TCRITI10,lOI, PCRlTUOtiOI, VCRITl101,· WILS 29
lUMllJÄIIOl, IOE:NTllO,2I, VLIQIlOI, CVLll.IllOrlJ, PSATIIOI, WilS 30
2CPSATllO,61, CACTCOII0,lO,)), GAMMAIlOl, XIlOI, YIlOJ, PHIllOl, WILS 31
Jbll0,lOl, Flli}l, fREFERII0), NREfERIIO), HENRYIlO,lOJ, WILS 32
4CHENRYIIO,16,2l, ~LIQLII0,lOI, CVlIQll10,10,21, OI1EGAHIIO), WilS 33
50IPOLEIIO), ETA(10) WILS 34
OIMcNSIUN PARAM(Zlo CATAI50,l0), PTl2J, PCAU50), E(2) WILS 35
tXTERNAl CAlCfX WILS 36
SUMX = 1.0 WILS 31
lAPM = 40 WilS 38
NPARAM = 2 WilS 39
1000 eALL INPUT lOl LS 40
500 READ (5,911) NPTS, NPUNIT, OP WILS 41
11' I,,<PTS) 660, 400, 510 WILS 42
51J WRITE (6,811) ~PTS, NPUNIT, OP WILS f.3
PHlll) = 1.0 WILS 44
PHl(~) = 1.0 wILS 45
l = 1 WilS 'tb
NPUN!T z NPUNIT + 1 WilS 47
00 5LO I • 1, NPTS WilS 48
REAO 15,910) IDATAII,JI, J = I, 4) WILS '.9
WRHEI6,SlOJ lOATAIl,J), J = 1, 41 WILS 50
 ....
I~·-l .------.
.----, ......---, .----, .-----, ....---, ,.....---, ~-_
==:J c.:::::J ===:J , - -. ..J ~J J.
~

I CUNTINU~TIUN UF PROGRAM: WILS

Gu TU 1520,512,515,511), NPUNIT WilS 51
I 512 UAIAII,J) UATAII,3). 0.068046 WILS 52
Gu T~ 510 WILS 53
515 UATAI1031 OATAII,31. 0.96184 WilS 54
GO TU 510 WILS 55
511 OATAII,31 OATAll,31. 0.00131519 WILS 56
SlO CONT HWE wILS 57
WRITE 1~,901) WILS 58
RTF.M~ = 1.9012 • CATAll,4) WilS 59
PARAMlll • CACTCOll,2,1) I RTEMP WILS 60
PARAMIZI = CACTCUI2,1,1) I RTEMP WILS 61
OU 000 J = 1, NPARAM WILS 62
600 EIJI = 1.0E-4 • PARAMIJ) WILS 63
CAll UPTPU~IPARAM,E,NPARAM,SQ,5.00+3,2,1.lAPH) WilS 64
OF = NPTS - NPARAH ' WilS 65
SEE =US~RTIS~ I Ofl WILS 6&
WRITEI6.901J WILS 61
WRITE Ib.91ll SEt: WilS 66
WRITt 16,1001) IUENTII,I), IOENTll,2). IOENTll,ll, 10ENTIZ,ZI WILS 6')
WIUTE 16.10021 UTLF. WILS 70
WRIT [ Ib,9021 WILS Tl
Ou ~09 M = I, NPTS WILS 12
DEL = OATA'M,31 - PCAllMI WilS 73
WRITt 16,903) UATAIM,II, OATAIM.21. OAT41",51, 04TAIH,31, PCAlIMI,WILS 14
1 UEL, 0.\TAII1,61, 04TAIH,11, OATAIM,/lJ, 04TAIH,91, OATAIH,10I, WILS 15
2UATAIM,41 ' WILS 76
609 CONTIWUE WILS 11
T = uATAll,41 WILS 711
CALL VIRIAL WILS 19
CALL RSTATE wiLS 80
VRAT I.j :0VLIQIZI I VUOlll wILS 8l
XlAMll = VRATlu .UEXPI-PARAMIII) WILS 82
XLAM.!l :oDt:XPI-'PARAMIZII I VRATIO WILS ' 83
CACTCUll,Z,ll = PARAMlll • RTEMP WILS 84
CACTCLJI2.1tll = PARAM(ZI • RlEMP WILS 85
OOUll = L• • 6'1,21 - BII,ll -BIZ,ZI WILS 86
WRITf: 16,9001 WILS 87
WRllt 10,904) XLAMll, XLAMl1, PARAHIlI, PAR4MIZ), CACTCOIl,2,lI, WILS 80
1CACrCOIZ,l,lJ, VLlQIl), VlIO(2), BI1,1), U(2,l), 00012 WILS 89
GO TU 500 WILS 90
6bO eALl EXIT WILS 91
900 FURMAT 11111 WILS 92
901 rORMAT 195H1 LEAST SQUARES wllSUN PARAMETER FIT TO VAPOR-LIOUIWILS 93
lD E"JILlORIA IN SYMMETRie CONVENTlUN) WILS 94
902 fuRMAT Ill6H Xl YIEXP YlCAL PEXP,ATM PCAL,ATM OELPWllS 95
1 fl,ATH fZ,ATM GAMMAl GAHMAl ~EXCESS T'K WILS 96
l 111 ) WILS n
903 fORMAT (3F9.~, 5f9.5, 2F12.4, lfll.31 WILS 98
904 fORMAT 113H AT I-TEMP(1)/, 10H lAMBUAIZ-. F30.41 10H lAMBOA21= , WILS 99
lflO. '.1 1211 lll-lll/RT-, F28.41 12H Lll-LZURT-, FZ8.41 9H L12-Ll1=WILS 100

- ----- ---------------
 r----; .-----, .------, ,----. --~---:-
~~ ~ ~ __ J ==:J c=J ~ _ . _ . ..J
j
~
:--l ~
~
r-----; r-----o

(.(JNTlI~UÄ T111t~ Of PROliRAM: 11' LS

lo, I-Jl.4, 4H CALI WILS lOL
19H Ul-Lll:, F3L.41 23H MOLAR VOLUMb CU/W. 1= WilS 102
l,11I.4, tlH CC/"MOl! 23H MOLAR VULUMt:, (;OMP. l.=, F11.41 lOIl 2ND VIRWllS lIJ3
3Ul CUMP. 1=, Fl.O.4, 8/1 CC/GMOLI ZOH ZNO VIRIAL COMP. 2=, F20.41 WILS 104
4l.4H U~LTAll. = l.~1l.-BI1-B22a, F16.4, ZOX 1I11H11 WILS 105
BLO FUR!-IAT (lH ,lOFtl.41 WILS 106
910 FURMAT 1101'6.41 WILS 101
911 fORMA r (;! Ilo, FO.41 WilS 106
611 FURMAT IIH ,.!.Ilo, F8.41 WILS 109
912 fURMATI4UH CÛMPARISON OF INPUT DATA ANO CAlCUlATEO RESULTSI WilS 110
13UII STANUARO ERROR OF ESTIMATE • , 1:20.8, 5X, 36ti ABSOLUfE PER CENWllS III
l.T [RROR IN PRESSURE 111I WILS 112
1001 FORMAT (1IIZ5X, 7HSYSTEH , 2A~, lH - , lAIo 111I WiLS 113
1002 I-URMI\TllUX, 111Aio 111 WILS 114
RETURN WILS 115
END WILS 116
C WILS 111
CCALPHW WILS 116
SU8RJUTINE CALPHW WILS 119
C WILS 120
C CALCULATES TOTAL PRESSURE !'ROM ESTIMAHO VALUES UF THE WILSON WI LS 121
CPARAMETERS FOR dlNARY SYSTEHS OF CONOENSAIILE COMPONENTS WILS 122
C WILS 123
IMPLILIT REAL*6IA-H,O-l) WILS lZ4
Kt:AL·4 TITLE WILS IZ5
COMMUlo TCRlT, PCRIT ,VCRI T,OHEGA, Vllil,CVLl i),PSAT ,CPSAT ,CACTCO,GAMMA,WILS 126
1 X,SUMX,Y,SUMy,P,T,TCLD,PH[,B,BHIX,VMIX,lMIX,F,FREFER,HENRY. WILS IZl
Z CHE~RY,VLIQL,CVlIQl,OHEGAH,DIPULE,ETA,VRATIO,RT,RRT, WILS 128
3 rlTLE,NCUMP,NLIGHT,NACTCO,IOENT,NREFER,NLRIT WILS 129
OUIM ~ ~~IUN TITLEI1Sl, TCR[TIIO,10), P(;RITI10,lOl, VCRITI101. wILS 1]0
LOMEGAllOl, IOENTlI0,Zl, VLIQIIOl, CVUQIIO,Jl. PSATlIOl, WILS 131
2CPSATIlO,6). CACTCOIlOdO,)l, GAHMAII01, XliOl, YIlOI, PHII.IOl. WILS 132
3BI1O.101, FILCj) , FREFERIIOI, NREFERII01, HENRYlLO.10), WILS 133
4CHEiit{YII0,10.2l. VlIQ1I10,10), CYllQLllO,lO,Z), OHEGMIIlOI, WILS 134
5UIPOLE(lOI, ETAILO) WILS lJ5
HARK = -1 WILS 136
TOLO = T WILS 131
XLAMI = VRATIU *OEXPI-CACTCOl1.Z,1) I RRT) WILS 133
XLA'IL=OEXPI-CACTCOIZ.l,1) I RRlI I VRATIO WILS 139
XLlZ = Xlll • XLAMI * XI21 WILS 1'.0
XLZI = XIZ) • XLAH2 * XI 11 WILS 141
FACI~K = IXLAMl I XlIZl - IXlAHZ I XL211 WILS 142
GAMMAII) =OEXPIX(2) • FACTOR) I Xl1l WILS 143
GAMMAIZ) =DEXPI-XIl) • FACTOR) f XLZl WILS 144
520 OU 5JO 1 = 1. Z WilS 145
FIII = XIII • GAM~AII) • fREFERll) .OEXPIP • VlIQ(I) 1 RTl WILS 146
530 CUHTINUE WilS 141
540 5UMY z 0.0 WILS 148
51t5 DO 5~O I • 1. 2 WilS 1'+9
VIII = Ft') I lP • PHI(I)I wILS 150
~ :-J ~ ~ C J c=J
r---,
L____ ....---,
, - _- J
......---,
-.J
------, r--
l
,-----... r--'" r--" r---ï
l
r-----' r---' -. r---

CONTINUATIUN Uf PRO~RAM: ~ILS

SUHY = SU"Y + YII) WILS 151
550 ~u1';f Ii.UE WILS 152
PUlD = P WilS 153
P = dll I PHlIU t FIZ) I PtHIZ) WILS 15'.
lP IDA8SIIPOlO-PI / PI - 1.OE-'t1 570, 510, 560 WILS 155
560 CALL PHIMIXIMARKI WilS lSU
If IVMIXI 590, 590, 5Z0 WILS 151
,510 IF IOABSISUMY - 1.01 - 1.0E-41 590, 590. 580 WILS 158
580 CALL PHIMIXIMARKI WILS 159
IF I"MIXI 590, 590, 540 WILS 160
590 IF IMARKl blO, blO, 600 WILS 161
600 I<>KITE 16,9231 MARK, T, P, SMIX, VMIX WILS 162
610 R~TURN WILS 163
923 fURMAT 1///, 10lH VClUME SERIES VIRIAl. E1.IUATION HAS II1AGINARY SOLUW[LS 164
lTIU~S PRtSSURE SERIES USEO FOR flNAL CALCULATION/ lH MARK =WILS 165
2 , 14, l1H TEMPERATURE ~ ,Fl.], 19H 'K PRESSURE • , Fb.3, WILS 1~6
315H ATI1 OMIX·, FIO.Z, 18H CC/110L VMIX· ,F9.1, 8H CC/110WILS 167
4LI WILS 168
END WilS 169
C WILS 170
SU~ROUTINE CALCFXINPARAM,PARAM,SQ) WILS 171
C WilS 172
IHPLICIT KEAL*8IA-H,O-11 WILS 173
KEAl~4 TITlE WilS 114
COMMU~ IFX/DATA,PT,PCAl,RTEMP,NPTS WilS 115
CUMMUN TCRIT,PCRII,VCRIT,OMEGA,VLI~ICVlIQ,PSAT,CPSAT,CACTCO,GAMMA,WllS 176
1 X,SUMX,Y,SUMy,r,T,TOlO,PltI,B,BMIX,VMIX,ZMIX,F,FREFER,HENRY, WilS 117
2 CHE~RY,VLl~L,CVLIQl,OMEGAH,OIPGlE,trA,VRATIO,RT,RRT, WilS 178
3 TITLt,NCUMP.NLIGHT,NACTCO,IDENT.NREFER,NCRIT WILS 179
OOIHl NS IUN TITlEIldl, TCRITI10,10). PCKITI10,101. VCRITII0). WILS 180
10i1EGAI101, IUENfIlO,Z). VUQII01, CVLIQIIO,J), PSATII01. WILS 1Bl
lCf'SI\TII0.bl. CACTCOIIOdO,3I. GAI1MAIIO). XIIOl. YIlO). PHIIlO), WilS 182
36110,101, FIlOI, FREFERIIOI. NREFEkll01, HENRYII0tlO), WILS 183
4CtlENRYIIO,10,4.'I, \/LIQU 10.10). CVLl1.llIl0tlO.2I, OMEGAHIlO), WilS 184
501PULE1101, ETAllOI WILS 185
OIMUblON PARAMI21. OATAISO,lOI. PH21. PCALC501, HZ) WILS Ig6
543 S~ = 0.0 WilS lBl
CACTCull,l.l) = PARAHIl) * RTEMP WILS 188
CACTCUIl,l,ll = PARAMIZI • RTEMP WilS 189
Ou û04 J = 1, NPTS WilS 190
XIII = OATAIJ.1I WilS 191
XIlI = 1. - XIU wILS 192
P = UATAIJ.3) wILS 193
T ~ OATAIJ.4) wiLS 194
11' Ir - TUlO) 600, 601. 600 WILS 195
bOD CALL 'JiRIAl WILS 196
CALL RSTATE WILS 191
VkATlU = VLlQIZI I 'IlIQ'lI WILS 198
RT = 82.057 • T WilS I??
RRT = 1.9072 • T WILS 200
 ..-. ..------, ,...-----. ...--------, .------, ...--------, ...--------, ,.------.
r-

.------
~

~ ~
~
:--J ~ ==:J r==1 r=J r=J ~-:J 1- j j I I

CUNTiNUATIUW UF PRUGRAM: WilS

bOl CALl CAlPtlW WI LS 201
t'CAlIJI = t' WILS 202
OATAIJ,51 = YIII WILS 203
DAfAIJ,ól fll1 WILS 204
DATAIJ,l) FIZ) WILS 205
OATAIJ,öl zo GAI1I1AUI WILS 206
OATAIJ.9J ~ GAMMAI2) WILS 201
OAfAIJ,lOI ., RRT * lXIII * DlOGIGAMMAlll) + X12) • DlOGIGAMMAI2111WILS 206
PCT = COATAIJ,31 - PCAlIJI) • 1100.1 IOATAIJ,3J WILS 209
S~ = SQ + PCT**Z WILS 210
604 CONTINUE WILS 211
TUlO = 0.0 WILS 212
C WILS 213
CALLEEN VUOR WATfiV WILS 214
C WILS 215
R~TUKN WILS 216
ENO WilS 211
C ~lLS 218
CINPUT WILS 219
SUb RUUTINE INPUT wiLS 220
C SUIlRJUrINE TO Rt:AO IN All PURE COMPONENT UATA MlD IHNARY WILS 221
C lNTt:RACTIUN PARAMETERS WILS 222
C WILS 223
IMPliCIT REAl*SIA-H,O-Z) WILS 224
REÀl*4 TITlE WILS 225
GOMMON TCKIT,PCRIT,VCRIT,OMEGA,VLI~,CVLIQ,PSAT,CPSAT,CAeTeO,GAI1MA,WILS 226
1 X,~UI1X,y,SUl1y,P,T,TOL~,PHI,B,BI1IX,VMIX,ZI1IX,F,FREFER,HENRY, WILS 221
2 l.HI:"KY,VllQL,CVlIQL,OMEGAH,OIPOLE,ETA,VRATlO,RT,RRT, WILS 228
3 TITLE,NCOMP,NlIGHT,NACTCO,IOENT,NREfER,NeRIT WILS 229
ODIMtN:;IUN T1TlE!lB), TCHITCI0,101, PCRlTIlO,lOI, VCRlTllOJ, WILS 230
lOHEG,\IIO), IDENTllO,2), VlIQ(101, CVLI~IIO,3), PSAT(lOI, WilS 231
lCPSATllO,ól, l.ACTCOIlOrlO,3I, GAMI1AUO), X(10), YHO), PHI(lOI, WILS 232
30(10010), Fliol, FREFERIIOl, NREFERIIOh tiENRYUO,IOI, WILS 233
4CHE~ R YIIO,lO,2). VlIQlIIO,101, CVllQLl10.10,2I, OMEGAHII0), WilS 234
501PUlEII01, ETAILO) WilS 235
READ 15,9011 TITtE WILS 236
WRITEI6,8011 TITlE WilS 237
RI:AO 15,9021 NCOMP, NlIGHT, NACTeu WILS 238
WRITEI6,802) NCOMP, NliGHT, NACTeo WILS 239
NAcrco = INAcrcu • 11 / Z ~llS 240
NI = NLIGHf + 1 WilS 241
NCOMPI = NCUI1P - 1 WILS 242
OU 90 I = 1, NCUMP WILS 2'.3
OREAO 15,903) TCRITII,I), peRITll,I), VCRITIII, OMEGAlil, OI1EGAHIllWllS 244
1. OIPULEIII, ETAlil, IOENTII,l" IOENTll,21 WILS 245
.RITI:16,803) TCRITII,I), PCRITII,II, VCRITIll, OMEGAlil, OI1EGAHII)WllS 246
1. GIPOlEIII, HAllI, IOENTlItll, IOI::NTll,21 WilS 241
IF IOIPULEIll1 33, 33, 36 WILS 248
33 OMEGAHIlI a OM~GA'I) WILS 249
3b REAO (5,9041 Tl, VI, Tl, VZ, T3, V3 WilS 250
,...
~ ~ :::=J c::J CJ t.::=J c=J ~
..------,
l
...----,
c-= ...----. rJ :--l r--l
,..----.,
~ r ,'" l~

CûNTINUATlûN UF PRUGRAM: kIlS

WRITElb,804) Tl, VI, T2, V2, Tl, V3 WilS 2<;1
KEAD '5,'W41 lePSATII,Jl, J 1,61 WilS 252
WRlftl6,604) ICPSATII,JI. J • 1,61 WILS 2~J
39 If- I T3) 40, 40, 10 wIL S 254
40 CVLIUII,JI: 0.0 wILS 255
lF (T.ó I 50, 50. bO lol IlS 25ó
50 CVlIUII,21· 0.0 WILS 257
CVll~'I,l) 2 V1 WILS 258
(jU Tu 90 WILS 259
60 CV Ll .I (I ,2 I '" I V2 - V1) I CT 2 - T1) lol I L S 260
CVUUIl,l1 '" V1 - CVlIQII,21 • Tl WilS 261
GO Tv 90 WILS 262
10 OCVU .. II rJl 'lr3 - T1I • IV2 - VU - IV3 - V11 • ITZ - TlIl I ti TWllS 263
12 .... 2 - 11**ZI • In - TlI - (nUZ - Tl·.:.! I • !TZ - TlIl WILS 26',
lVll.lII,2) " "V2 - VU - eVlIQII,J1 • lTZ •• Z - TluZI) I (T2 -TlIWllS 265
CVUQ'I,ll = VI - CVlIQ!I,Z) • Tl - CVLlQII,JI • H"Z WilS 266
90 CUNTINUt WILS 267
OU 110 I = 1, NCOMPl WILS 268
OU 100 J = 1, NCOMP WILS 269
TCRl['I,JI =l)S~RTITCRITII,1l • TCRITIJ,JII WILS 270
OPCRIT'I,JI = 4.0 • TCRITII,JI • IPCRIHlr1l • VeRITll1 I TCRITlI,(WILS 271
11 + PCRITIJ,JI • VCRITIJI I TeRITIJ,Jl1 I IVCRITII' •• O.33333333+ WILS 272
2 VC~lrIJI •• 0.J33333331 •• 3 WILS 273
Tl.klTIJrll = TCiUTII,JI wiLS 274
PCRlrlJrll = PCRITlI,J) wilS 275
100 CONT1NUt WiLS 276
110 CONTINUt WilS 271
OJ L30 I = NI, NCOMPI WILS 276
11 = 1 + 1 lol 1 L S 279
UO 220 J : 11, NCOMP WILS 280
RtAO 15,9051 ICACTCOII,J,K), CACTCOIJ,I.KI, K 2 1.NACTeCI WILS 281
WRITtl6,8051 ICACTCOII.J.KI, eACICO(J.I,KI, K. l,NACTeO) WILS 282
2Z0 CONTINUE . WilS 283
.BO CONTliWE WILS 204
240 TOlU = 0.0 WilS 265
Uu ZuO J = 1, NCUMP WilS 286
00 250 K = 1. NACTeO WILS 2al
CAC1CÛ'J.J,KI = 0.0 WILS 288
250 CONTI NUt WilS 209
2uO CUNT l i ~UE WILS 290
901 flJRMAT (t8A41 WILS 291
8;.11 I:ORMATlWl.llJA41 wILS 292
902 füRMAr IJI4) WILS 293
8U2 FtJR.'IATlIH .314) WilS 294
903 FOR~AT '7F8.4, 16X, ZA4) WILS 295
803 t'URMAT !lH ,H8.It, 16X, 2Alt) WILS 296
904 FORMH 16HZ.61 WILS 297
8J4 FuRMAT (lH ,óf12.6) WILS 298
905 FORMAT (8F8.4) WilS 299
805 FURMAT IIH ,Bf9.41 WilS 300
- "... ~

:--l ~ =:J ~J c=J c=J ~ :=--J =----:J --~

.J
----,
, c----: :--l :-l :----l :----l
,---.
l
,..-----,
I
,.---

CUNTINUATIUN ûF PRUûKAH: WILS

R~TURN WilS 301
END WILS 302
C WILS 303
CR STATE WILS 3'JIt
C WILS J05
SU~RUUTINE RSTATE WILS 306
C WilS 307
IMPllCIT REAl*alA-H,O-ZI wilS 308
REAl.4 TITLE WILS 309
LOMMUN TCRIT,PCRIT,VCRIT,OMEGA,VLI~,CVlIQ,PSAT,CPSAT,CACTCO,GA"HA,~ILS 310
1 ~,SUHX,y,SUMy,P,T,TOLn,PHI,B,8MIX,V~lX,ZHIX,F,FREFER,HENRY, WilS 311
2 CHEliIW,IIUQL,CIILlQL,OMFGAH,DIPOLE,EU,IIRATIO,RT,RRT, WilS 312
3 T1TlE,NCOHP,NlIGHT,NACTCO,IDFNT,NREFER,NCRIT WILS 313
ODIMt i'ü IUN TlTLEIlOI, TCRlTIIO,lOI, PCRlTIiO,lOI, IICRITIIOI, WILS 314
W;1l: (;AIIUI, lUENTl10,21, VLlQllOI, CIIUQII0,J1, PSATIlOI, WilS 315
2CPSATlIU,ól, CACTC OIIO,l0,31, GAMMAIllll, XIlOI, YIlOI, PH11101, WILS 316
38110,101, FilOI, fREFERIIOI, NREHKllOlr HENRYIIO,lOI, WILS 311
4LH~NRYIIJ.lO,.!I, ~LlQLlI0,101, CIILI.;jLlI0,l0,21, UMEGAHII01, wiLS 310
5UIPJLEII01, ETAII01 WILS 319
\/APRESIT R,OHEûAI =DEXPI2.3D25 • '111-0.3456 1 TR + 1.4541 I lR -4 WilS 320
1.3181 I T~ t 3.20SI ~ OMEGA. 1'1 0.3~81 I TR - 2.52~1 I TR ~ Z.OOWILS J21
281 I TR t 0.1175111 wilS 322
PIII SUf I TRI = 11 0.57335015 I TR - 3.016574 I I TR + 5.60855951 I TRw ILS 32)
1 - J.5U21356 WilS 3Z4
fHISIFITRI = 111111111' I 0.012089114 I TR - 0.0151721641 I TR WilS 325
1 - 0.060u035161 /' TR + 0.024364b161 I TR + 0.149369061 I TR t 0.18flllS 326
29270371 I TR - 0.121474361 tTR - 0.106651301 I TR - 1.16622831 I TWllS 321
3H + u.12b&&1841 I TR ~ 0.31661171 I TR ~ ~.35387291 I TR - 3.76940WILS 328
418 WilS 329
NI = NLIGHT t 1 WILS 310
IE- Ir - TOLUI 290, 381, 290 WilS 331
290 RT = dl.OS7 * T WILS 332
"'Rif = NlIG~T WilS 333
OU 380 J = Nl, NCGMP WILS 334
TH = T I TCRITIJ,JI WilS 3]5
W = UMEGAIJI wiLS 336
If I TR - 1.01 295, 295, 370 WilS 337
295 If ICPSATlJ,111 300, 310, 300 WILS )ja
300 OPSATIJI ~DEXPICPSATIJ,11 + CPSATIJ,21 I ICPSATIJ,3' ~ TI ~ CPSAT WILS 339
. lIJ,~). T + CPSArlJ,5) * T•• 2 + CPSATIJ,6' • DlOGIT" WILS 340
GO TU 320 wILS 341
310 PSATIJI = PCRITIJ,JI * VAPRES 'TR,WI WilS 342
3.!0 Ir I TR - 0.56) 3JO, 330, 340 wiLS H3
j30 PHI~ =OE~P IBIJ,J) • PSATIJ) I RTl WILS 344
GU Tu 360 WilS 345
340 PHI~ =OtXPIPHISOf,TR' ~ W • PHISlflTRl1 WilS 346
360 VlI~IJI = CVlIQ,J,ll + CVLIQIJ,ZI • T ~ CVlIQéJ,31 • T*.Z WILS 341
FHEFLKIJ) • PSATIJI • PHIS .OEXP( -VlIUIJI • PSAT'JI I RTl WILS 348
GO Tu 380 WILS 349
310 ~CRIT· J WILS 350
,... .----, ,.--., ,.....---. ,.------, r~
,.....--
[___ I
: I ~ :=J ~:-J :---l ~
r------'
~ =-=:J c:J CJ :----l I.. l

•
CUNTINUAflUN UF PKUGRAM: ~llS
380 CONTINUE WILS 3~1
38 1 Rt: TUKI~ lolI LS 352
END WILS 353
C ~IL5 ]54
CVIRIAl WILS 355
SU~RUUTINE VIRIAl WILS 35&
C wILS 351
C SUbROUTINE FOR ÇALCUlATION OF SECONO VIRIAL COEFFICIENTS WILS 358
C WILS 359
lMPllllT kEAl*SIA-H,[-ll WilS 360
REAL*4 TITLE WILS 361
':OMMûi~ reKlT, PCR lT, VCR [T, OME GA. VII IJ, CVU lol. PSAT, CP SAT ,e AC TCD. GAMMA. lol I LS 302
1 X.SUMX,Y,SUMY,P,1,TOLO,PHI,B,8MIX,VMIX,lMIX,F,FREFER,HENRY, WILS 363
2 CHE I ~Ky,IILlI,jL,ClllIQL,O""EGAH,OIPCLE,i::rA,IIRATIO,RT,RRT, WILS 3(,4
) TITLE, N CUMP.NLI~HT,NACTCO,IOENT,NKEFER.NCRIT WilS 365
OOllk l~ 5 IU .'i TlTU1161, TCRITIlO,lOI, PCRlTllOtlOI, VCRITIIOI, WILS 366
LUHEGAIIUI, lUENTIIO,21, VUQII01, CVlHII10,31, PSATlI01, WILS 361
2CPSArllu,6I, CACTCOIIO,lO,3I, GAMMAIlOI, XIIOl, YIIOI, PHIIIOI, WILS 31>6
38110.101, F1101, fREFF.RIlOI, NREFERIIOl, HENRYII0,lOI, WILS 31>9
4CHE I'II\" 10, 10,21, VLIQUI0,l01, CIIU\JlIlU,lOt2I, llMEGAHtlOl, WILS 310
5ülPULE1101, ETAII01 WILS 311
P2VP~ITR,KOI = -5.237220 + DlOGIROI • 15.065607 + DlOGI~DI .( wILS 372
1-2.13j810 + OLOGIRDI * .252537)1) + 15.10~110 + OlOGIRDI * (-6.181WllS 313
, 24l7 + ,OLOGIROI * 12.283270 - DlOGIROI * .L6490741)1 I TR wILS 314
DJ ' 2U2 I = 1, NCllMP WilS 375
Ull 201 J e I, NCOMP WILS 376
TR = TITCRITII,JI WILS 317
' w = (OM EGAlIl 11 + OMEGAHIJII I 2.0 WILS 378
OSECVIK = IJ.1445 -10.330 + 10.1385 + 0.0121 I TRI I TRI I TR + 'W WILS 379
1* 10.073 + 10.46 -10.50 +10.091 + 0.0013 I TR •• 51 I TRI I TR) I TRwlLS 360
211 WILS 381
IF IDIPUlEll1 • OlPCLEIJl1 200, 200, 100 WILS 302
100 IF 10.95 - TRI ioo, 200, 125 WILS 383
125 RO 10.E04 * OIPOL[II) • DIPOlEIJI • PCRITII,J) I ITCRITII,JI WIL~ 384
1*.21 WIL S 335
l~ (KO - 4.UI 200, 2CO, 135 lol ILS 336
135 SECVIK = SECVIR + P2VPFITR,RD) WILS 30r
150 If I[UIl) + ETAIJ)) 200, 200, 175 WilS 388
115 ScCVI ~ = SECVIR - 0.5 * IETAll) + ETAIJl) *OEXPI6.ó • 10.7 - TRIl WILS J8~
200 Sll,JI = SECVIR • 82.057 • TCRITII,J) I PCRIT(I,J) WILS 390
B(J,lI = IH1,JI WILS 3'11
lOl CONTINUE WILS 392
202 CONTINUE WIL S 393
ReTURN WILS 394
END WILS 395
C WILS 3g6
CPHI~IX WilS 397
SUUROUTINE PHIMIX IMARKI WILS 398
C WILS 399
C SUURUUHNt: FOR CALCULATION OF VAPI:R P~tASE FUGAClTY COEFFICIENTS WILS 400
 I
:--J'"
,----, ..----,
:=:J =:=J ==:J c:J [ .1 t=J :---J :---J I ~ ~
,-----,
j
r----' r~, r' ----:'"' r:::-:: I

CUNTINUATIUN UF PKO~RAH: WILS

C WILS 401
IMPLILIT HEAL*8IA-H,O-11 WILS 402
R~AL*4 TITL~ WILS 403
COMMUN TLRIT,PCRIT,WCRIT,OMEGA,WLl~ICVll~IPSAT,CPSAT,C~CTCO,GAHHA,WJLS 404
1 X,SUMX,y,5UMy,P,T,TOLD,PHI,B,~MIX,VHIX,IMIX,F,FREFER,HENRY, WILS ',,)5
2 LIIENR y, VU QL,L VllCL ,O:"EGAH, Ol peLE, ETA, V RAT lO, RT, RRT, WilS 406
3 T lTLE,NCOriP ,NLIGHT ,NAC TCO,I DENT ,NKEFEH,NCRI T WILS 401
ODIME~SIUN TITL~118I, TCRITIIO,10l, PCRITCIO,lOl, VCRITIIO., WILS 408
lCl1EGAIIOl, IOENTllO,2l, VLlQIlOI, CVLlQI10,3l, PSATIlO., WILS 409
2CPSATllO,ó}, CACTCOIIO,lO,3I, GAHM.\(lO), Xl10l, VIlO), PH1C10., WILS 'ilO
JtH10,lO), F110), FREFERIlO), NREFERIlO), tiENRY(lOolOI, WILS 411
4t;Ht .... RYI10tlO,LI, VLICL(lO,lOI, CVLlULllO,10,2 I. OHEGAHI 101. WILS 412
5UIPULEIl0), ETAIIOI WI LS 413
PURT = P/idl.051 * TI WILS ',14
BMIX'" 0.0 WILS 415
DO 1, 1 = I, NCUHP 1011 LS '+16
DO 10 J =
I, Ne UH P WILS ',11
BMIX = BHIX ~ YII) • VIJ) • BII,JI WILS 'd8
1) CONTINUE WILS '119
15 CUNTINUe WILS 420
BrilX = UMIX I SUMY *.2 WILS ',21
IF IMARK) 20,20,22 WILS 422
20 S~AKG =0.25 ~ UHIX • PORT WILS ',23
IF I;,QAHG) 22. 25, 25 WllS 4~4
22 VHIX z BMU ~ 1. I PORT WILS 425
LMIX = PuRT *VHIX WILS 426
DO 24 I = 1. NCOMP WILS 427
SUMd = 0.0 WILS 428
LW 23 J =
1., NCOMP WILS 429
Su/H, = SUHil + YIJ) * BIl,JI WILS 430
23 LUNTINUE WILS 431
SU/'H; = SUHti I SUM Y WILS 432
PHlI 1) =UEXP(j2.0 • SlJ4B - BHIX) • PORTI WI LS 433
2", LUIHI Nut WIL S 434
HAHK = MARK ~ 1 WilS 435
RCTURN WILS 436
25 VMI X = 10.5 +OSi,lR TI SCARG 11 I PORT WILS 431
IMIX = PuRT • VMIX WILS 438
OU 40 I =
I, NCOHP WILS 439
SUM() = 0.0 WILS 440
OU 30 J =
I. NCOMP WILS ', t,l
SUMû = SUMü + VIJl. BII,JI WILS ',42
30 CUIHI NUE WILS 44.3
SUMtl = 5UMB I SUHY WILS 444
PHI!I) =DEXPI2.0 • SUMS I VHIX. I lHIX WILS 445
40 CONTINUE WILS 446
RETURN WILS ',41
END WI L S 4',0
C WILS 449
SUSRuUT lt~E OPTPUW 'X, e ,N. F. ESCAlE, IPR INT, I CON. MAXI Tl WILS "50
~ ,-. r--, ---, ..----, r------' r--, r-----. ...--, .-----. ~ ""
:--J :=--J ==:J ~ CJ CJ c::.::J ~--~ L ~ I J ~
r
l

CUNTI NUA Ti lJN Of PRO\.iR,\/': \Ij I LS

IMPllCIT REAl*SIA-H.O-ZI WilS 451
COMMuN /uPf/WIlO) WILS 452
OIML I.SluN XINI ,t:(NI WilS 45J
DDM,\G=O.l*t:SCALE WIL S '.54
S~~K=û.05/ESCALt: WilS 455
JJ=N*N+N WILS 456
JJJ=JJtN WILS '.57
K=N+ 1 WilS 450
NFCt.=l WilS 459
WLl=l WilS 460
ltiN= 1 WilS 461
00 1 1"1.1'4 WilS 462
Dû 2 J"'l. N WilS ',63
WIII.I -= O. Wil S ','>4
JF( J-J)4.3.4 WilS 46'>
3 W(K)=UAUSI(I"j WilS ',ó6
\/111 =1: SCAlE WilS '.67
4 K~K+l WILS '.68
2 CONT II~U~ WilS 469
1 CUNTWUt WilS 410
lIEil.(..= 1 WILS 471
lSGKAO=l WILS 472
~All CAlCfXIN,X,fJ WILS 473
fKtéP=OABSlfJ+OABSIFI WilS ',14
5 nü"'t:=l IIiLS 475
fP=~ WilS {.76
SUM=O. WilS 477
IXP=JJ WilS '.78
00 b I si. N WILS 479
L<P= IXP+l WilS '.80
W' ~ XP) =X I IJ WILS ',81
6 (;urHIfWE WILS 432
1OIR i'=N+l \iIlS 463
IUlk=l WILS 48'.
7 LlM,\X=;jllllNU WILS 485
DACC=Oi4AX*SCER WilS ',86
OM~~=DMINIIOOMAG,O.l*OMAX' WILS 487
UMAG=OMAXIIOMAG,20.*OACCI WilS 489
DU ilA X'" lO .*OMAG WIl.S 43?
GO Tu 110,10,71l,llONE WllS ', 'JO
70 Dl=O. WILS '.91
D= UliAG WILS '.92
FPKI: 'I=F WilS f,'))
IS=~ WILS 494
fA=F \oIILS 495
OA=[)L WILS 496
8 OO=O-Ol WILS 491
OL=O IiILS 498
58 K:IOIRN WILS 499
00 'I lsl,N WILS 500
 ,,",

:--:J =---:J ==:J c::J :=:J =:J :=::J :---J .----, ~

...---, ~ r------, r---"1
I l-: r-:'-' r-'

COIHINUAT!Of' Ol' PROGRAM: .dLS

X'II=X,l).DO.~'KI WILS 50l
11..=11..+ 1 WilS 502
CJ LUNTINUt WILS )03
CALL CALCFXIN,X,FI WILS 504
I.FCI. =NFCC+l WilS 505
GU TJ 110,11,12,13,14,961,IS WILS 506
14 If'f-FAJ15,ló,2~ WilS 507
16 lF IUA8510J-OHAX) 11,17,18 Wil S 5011
11 D= 0+0 WilS 509
GU T..: 8 WilS 510
18 WRIHI6tl91 WILS SU
19 FURMATI5X,44HVAO'A MAXIMUM CHANGE OUES NOT ALTER FUNCTIONI WILS 512
GU TU 20 WilS 513
15 Ft>=F WILS 514
oi:! = 0 WILS 515
GU Tu 21 wilS 516
24 F8=fA WILS 511
Oi:!=OA WILS 518
FA=F was 519
llA=O WilS 520
21 GO TU 183,231,ISGRAD WILS 521
23 D=Dtii-DO-DA WILS 522
1 S=1 WILS 523
GO TJ 8 WILS 52'.
83 D=0.S$IDA+D8-lfA-FBI/(OA-OBII WILS 525
15=4 WilS 526
IFIIDA-DI*IO-D8JI25,8,8 WilS 521
25 15=1 WILS 528
IfluABSID-OBI-DDMAXI8,8,26 WILS 529
2b a=Uó +OSlGIHDDMAX,DB-DA, WILS 530
I S=l WilS 531
DDMAÁ=DDMAX+DDMAX WILS 532
Dil:-lAG= DDMAG+ODMAG WI lS 533
IFIUDHAX-DMAXI8,8,27 WILS 534
27 DDMAX=DMAX WILS 535
GU TU B WIL S 536
13 IFlf-fA128,23,l3 WILS 537
28 FC"'Fo WILS 538
DC=Oa WilS 539
29 fb=F WILS 540
DB=U WilS 5'tl
GU Tu 30 WILS 542
12 lFlf-FBI28,28,31 WILS 5'tJ
31 FA=F WILS 54'.
DA=D WILS 545
GU TJ 30 WILS 5'.6
11 IFIF-F8IJ2.10,10 WILS 541
32 fA=Fd WILS 548
OA=Dü WILS 549
GO Tll 29 WilS 550
 ,.....
.....- "'" r-
:-l ~ ==:J CJ CJ c::=J ===:J =-~
..------,
r::-: r------" ..------,
J :---l .---. .----. r--~ ,---~

CONTINUATION Of PRO~RAM: ~ILS

71 OL=l. WILS 551
OOM-'x=5. WILS 552
fA=/- P W1LS 553
OA=- 1. WILS 554
Fij=I'HULU WILS 555
00=0. Wll5 556
0= 1. WilS 551
10 fl.=f WilS 556
OC=[) WilS 559
30 A=lDö-OC)*lFA-fCJ WILS 560
S=IOC-OAJ*lfB-FCJ WILS 561
IFlIA+81.l0A-OCJJ33,33,34 WILS 562
33 fA=Fll WILS 563
OA=Uti WilS 5b4
Ftl=f-C WilS 565
UB=DC WilS 56b
(,U TU 26 WilS 5b7
34 D=O.j*lA*lOB+OC)+S*IOAtOC»/IA+S) wiLS 5b8
Ol=llU WI LS 569
F 1 =Fd WILS 510
IF (I: 8-FC J 44,44,43 WilS 511
43 UI=OC WILS 512
fl=FC WilS 513
44 GU TJ 186,86,851,lTONE lol IlS 51',
85 ITOllt:=l WilS 515
GO IJ 45 WilS 516
86 11' lDAB510-01)-OACCI 41,41,93 lol IlS 571
93 Ir ILlABSIo-Oll-0.03*DABSlOII 41,41,45 WILS 578
45 IF 'IOA-OC).lOC-[)) 47,46,46 WiLS 519
46 FA=FtJ WILS 580
UA=LJö WilS 5ill
Fti=t-l. WILS 582
OI:l=O~ WILS 583
GtJ Tu 25 WilS 564
47 15=2 WilS 585
IF II08-01.IO-OC» 48,8,8 WILS 50&
48 IS=j WILS 581
GO Tu 8 WILS 506
41 F=I'I WilS 5t3'l
U=Ol-Ul WilS 590
UO=jS~RTIIOC-Oijl·'OC-OAI*(OA-DSI/lA+8JJ WILS 591
Od .. 9 l=l,N WilS 5n
XIll =X lII+O*WIlOIR~) WILS 593
WIILJIKNI=DU*WII0IRN) WilS 594
lUIK ,.= IUIRN+l WILS 595
49 CUNTltWE WilS 5%
Ijl ILlNEI=WI l11NEI/OO WILS 591
IL INe.= IllNt:+1 WI lS 5'18
IFIIPMIHT-1151,50,51 WILS 599
501IRITt:l6,5ZIITERC,NFCC,F,IX(II,I"'1,NI WilS (,00
 ~
..------, .-------, ..-----, .-----, ..-------, ,--~'"
,:---J ~ ] c:::J c:.::J =:J ==:J r- -,
j
r------"'\
~
r--

CONn~UATI~N U~ PROGRAM: ~ILS

5~ FüR~ATI/IX.9HITERATION,15,115,16H FUNCTION "ALUES, WILS 601
llUX.JHF =.E21.14/15EZ4.14)) WIL') 602
GU TUI 51.'>3) tlPKU~T WILS 60J
51. GO TJ I 5j 038), nONE wiLS 604
55 IFlfPREY-f-SUH) 94,95,95 WILS 605
9, SUM= FI' RI: Y-F WILS 606
JIL= lL lNE WILS 601
94 IF IIDIRN-JJI 7,7,84 WILS 608
84 GO TU 19l,72"INO WILS 609
92 FHUlD=f WILS 610
IS=ó wiLS 611
I XP = JJ f/ILS 61Z
OU 59 I=l,N IOILS 613
IXP=IX!'+l WilS 614
wil XP I = X1 {) - WIl XP I WilS 615
59 \.UNT HIUE WILS 616
DU= 1. WILS 611
GU Tu ~a WILS 618
96 GU Tu 1112,Hl),IND WiLS 619
112 lF IfP-Fl J7,91,91 WILS 620
91 U=l.*IFP+f-l •• fHOLO)/IFP-F) •• Z wILS 621
lF IU~IFP-fHOLD-SUHl ••2-SUHl 87,37,37 WilS 622
87 J=JIL*N+l .. ILS 623
IFIJ-JJ) 60,60,61 WILS 624
60 00 oL I=J.JJ WILS 625
K=I -1'1 wiLS 626
.. IKI=W III WILS 627
6Z CUI'ITI NUt: WilS 62d
00 9 T 1= J IL, N WilS 629
,,1'-1)=,.111 WilS 630
97 CtJI'ITIlWE WILS 631
61 LU 1,((,,= 11) IRN-U WILS 632
lT (J;, t= .3 WILS 633
K=ltJIRN WilS 634
lXP=JJ WILS 635
AAA=J. WilS 636
00 65 1=I,N WILS 631
IXP= IXP+l WILS 638
WI KI =101 IXPI wIL S 639
If IAAA-DAdSIWIK)/EII),) 66,67,61 wiLS 640
6b AAA=DAflSIW(lO/EII)) WILS 6'.1
67 K=Kt-l WILS 6'.Z
65 LUNTlNUt WILS 6'03
OUMAG= 1. WIL S 6'.4
WIN)=ESCAlE/AAA WILS 645
ILlI'li:=N WILS {J',6
GO T~ 1 lol 1LS 6'.1
31 1 xP=JJ WlLS 646
AAA=O. WILS 649
fzfHUlO WI LS 650
 ,... _]
:-J :-;-J ==:J c:.J ...-----,
---...J :==J ~
-----, r-----"'
~ ~-- "'" r---'
CONTJNUATION UF PRO~RAM: wILS
Ull 9'J l=l,N WILS 651
IX?= 1 XP+l WILS 652
XI I I = XI I I -Ij( [XP I WilS oB
IF IAAMUAUSIEII!)-DA8SIWClXPIII 98,99,99 wil S bS '.
98 AAA=UARSIWIIXPI/EIIII WILS 655
99 WNT INUf W1lS ó56
GU TU 72 WILS 657
38 AAA=AAA*(l.+DI. WILS 658
GU Tu 17L,1061,INO WILS 659
Tl IFIlPRINT-2. 53,50,50 WILS 660
53 GO TJ {109,881,lNO WILS 661
109 IF (AA4-0.1I 89,89,76 WILS 662
89 GO TJ IlO,1161,lCON WILS 663
116 Ir;D=L WILS 6ó4
GO TU I10U,101.,INN WILS 665
100 INN=L WIL S ó66
K=JJJ WILS 667
OU 102 l=ltN WILS M8
K=K+ 1 WILS 669
WI"-I=XllI WILS 670
XI I ) = XI I 1+10 • *E I I. WILS 67l
102 CON r lIWE WILS 672
fKE!::P"F 1011 lS 67J
CAll CAlCFX IN,X,FI 1011 LS 6H
NFCC=NFCC+l WILS 675
ODMAG=O. WILS 676
liU TLl 108 WILS 677
·7/.) 11' 'I--F i' I 35,76,78 WILS 1>18
76 WRIrt16,801 WILS 679
80 FURMAT (5X,31HVA04A ACCURACY llHITED UY ERRORS IN FI WilS 600
GU TJ 20 lol ILS 681
8S lND = 1 WILS 68Z
35 ODMAG=0.4*OSwRTlfP-FI W1LS 683
J!>~ k AU=l wILS ó84
108 ITtKC=ITERC+l WILS 685
11' Il rU{(.-MAXI TI 5,5,81 WilS 6t16
61 WRIT[(6,62IMAXIT WilS 6fl1
82 t-URMA1(15,30H ITERATIONS COMPlETEU 6t VA04A. WILS ógO
IF (f-FKEtP) ZO,lO,110 Wil <; /,6~
110 f= ftU:tP WILS 690
DU 11 1 1-1, N WilS 691
JJJ=JJJ+ 1 lol ILS ón
XI 11=ldJJJJ WILS 693
111 CONT 1 NUE 1011 L S 694
GU TLI 20 WrlS 6'15
101 JU.= 1 . WILS 696
FP=FKHP WILS ó')7
IF (F-FKEEPI 105,78,l()l. WILS 690
104 Jll"l WILS 699
fpsf WILS 700
 "...
. :J ,...--, ~----, ~---, ~ ~ ,....------,
~ =-:-J :=--=-J ::::=J o.____...J ... __ ....J j J -----:J r---- "'"

CONT I NUA T I Ui.. UF PRUGRAH: Ij IlS

F=fKEEP ~llS 101
105 IXP=JJ WILS 102
OU 113 ("'l,N wILS 103
(xp= I XP"l \<.IL') 104
K=IXP"N WlLS 105
GU Tu (114,l15',Jll WILS 106
111t lil! XP I KI ="1 WILS 707
GU TU 113 WILS 10B
115 WIIXP'=Xlll WILS 109
JU 1)=01(11.' WILS 110
113 caNT HlUt: WILS 1ll
JIL=~ WilS 112
GU TU 9l WILS 113
106 11' (AAA-O.ll 20,20,107 WILS 114
20 RETURN WIL S 115
101 IN li= 1 WILS 116
GU Tu 35 WilS 717
END WiLS 119

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ~ . . #. ................. .,.. . . . . . . . . . . . . . . . . . . . ... . L . . . . . . . .... ... . .. . . .. . . . . . . . . . . ..... ., . . . . . . . . . . ~ . .. . . . . . . . . . . ' . .. ... .. . ..

l_
 I)
I
l,
-1-

The method of mass balance used in the design of the column lS called
the method of successive flashes ( see Hanson ( 20 ) p.p. 12).
The unsteady state equation for any component i on any stage p of the
column "\wuld be

dy dx
Sv _.2. + S --12. = (v Y +L X )
p de Lp de P P P P

[: ln which:

Sv vapor holdup at stage P , assumed constant, [kgmol ]

P
f: li quid holdup at stage P, assumed constant, [kgllol]
SLP
V vapor flov [kgmol/hr]
I l •

L liquid flol-T[kgmol/hr]

f: x - mole fractio n ln the liquid phase [dimens ionless ]

y - mole fraction ln the vapor phase [dimens ionl ess ]

r'l,
If the equilibrium constant, K is introduc ed into EQuation 1 and it is
furth er assumed that Sv < SL ' th en one gets Equation 2 as follol-Ts:
p - p

= V K
p-1 p-1 p-1
X + L X
p+1 p+1
- X (V K +L )
P P P P
(2)

r'
I
Substituting the definition
l J

T = els lp
rî
or
[1 dT = (4)

n results in:

dx
n . -12.
dT = V K X
p-1 p-1 p-1
+ L X
p+1 p+1
- X (V K +L )
P P P P

n
I l
 r'
I,
L ,
-2-

Defining

(6 )

s = ( V K +L )
P P P

Substi tuting À and S into Equation 5 lead s to Equation 8 a s foll OvTs :

dx
dT = ---"L (8)
À-Xp S

An it erative type of solution can be obt a ined by int egrating fr om the

point X at it erat ion r t o the po int X at iteration r+l, w"ith the
p p
corresponding fi nite differ enc e in T being AT. In order to carry out
this integration it is necessary to assume that À and S are const ant
acro ss the iteration . The resulting equation is:

I [' ,,,hich can be arranged as follows:

À
(X) exp(G~) + D [1 - exp(-~)J ( 10)
p r ~

where
~ = BAT ( 11 )

lJ Since the ob ject of the calculation lS to obtain steady state values

of the composition, it is better to use large valuesof ~ in order to
[1 obtain rapid convergence on the steady state composition.
If it is arbitrarily assumed that the values of ~ are chosen so that
=0
f1 exp(-q')
value of (X ) becomes:
for each iteration, then the basic expression for the r+1st

[1 V K X
À p-J p-J p-J + Lp+J Xp+1
= ( 12)
B V K + L
P P P
l _
-3-
r'
,
L.

This equation has the exact form of the flash equations and that lS

the origion for nruning this mass-balance method as the method of

successive flashes. The latter can be calculated from any stage in
any direction. Its optimum use will vary from problem to problem, and
can only be ascertained for a certain problem by many calculations on
that problem. It has been found that starting at the bottom stage,
provides areasonabIe rate of change in the composition map within
one iteration.

[:

[,

I
L ,

n
n
o
n
n
n
r
l •
11
l J
-1-

Appendix F
----------

The program , by means of which the distillation c olumn lS designed,

can be des cribed schematically as follows:

[R ead input data

[~
Set varlOUS counters to zero

Calc ulate stage dependent indexes

Calculatc total f eed of each c omponent I

V
Fin the X, Y and Y a rrays wi th
starting values

I-
I Calculate boil ing point f "
,; I Calculate plate composi tions 1

[: No
I Ca lculat e yl < ABS[ (SUNX (J)-1.0)-SUMERR ]~0 ] \/
,
rl ', 1[\

Yes
L

"
/
No
I ABS[(SUMY(J)-1.0)-SUMERRJ~0 J
\ Yes
rl
L /
No
I
ABS [(RFSUM-l .0 )-RFERR] <0
-
I

Print results of iterations

n
n
~ I"\ [

~ ] ,.----------, ..----.,
~
...----, ........----, ........----, r- r - ..... ......--
~ =--=:J J =::::J c=J =:==J J .

lirE flJll"" liJ" f' ~:u,-, ,:'\1 IS ~V 1 jFI ( En: ,liS

( lJi\~I\.. f'K ·.JI~"i. . 1 hJK i\rfo,[ !" r,'L fll51lLArldd ,,11i1 T, : r\L 1. · J ! ~UFN~F ['. IJ l :;
C 1:('; ~
C PI 'u v !{ ,. \~ ' 1~ . lt i' I :;
C !J J ') 'I
iJ I i-l L I.J .' u i. ,. All G ,l r. 3 ) , \; H .. Y(
.j ~ 1 r, 1\) .J) , ~ u I '. ,( ( I .; ;) , ~ . )'1 Y ( 1 .d ) , rr "( I' ( I J I ) , l.. I .~ ')

1" .-.rJu KIL ,I j ) , "u I IJ ( 1 \1 J ) t f,' LL IQ ( 1 ,~ ) , f U 1 V,ul ( 1.) I , F IJ .~L! J ( I ' ) I , r n l V ~ I' ( 1'1) , f Ij{ S 0
LIl .... LI.tl L 0 1 ,~ ' U VA P ( 1 (') ., lil trll ,11 ( 1 d ) tC ( I ) I , ._,,\11L ( L:.1, 1') J I, fC ( lOL I t 'i 1'''1 ( 1 n " ('i I
3L I , L .. " ( 1 ,).:) , T 51 1 J ) , RF il" Tl 1 0 I , Kr r [lP ( 1 J I ,Id- :.. U'1 ( 1) I , ,lflT" ( IC) , T Co r L> ( 10) !l1:; IJ
4 , .. JIJ A ( I J I , V;. i'Y ( 1 :J I ,C/,'!:' 1\ ( I ·) I ,~ 1 '; '1
Ctj,.I ,", I. , " L ,.X ,u c.-jy , S L '" ~ , :; U'~Y , rf' Mf' , V:,,'u,{ , ~u I i I, Fr: 1 L I 'J' n; 1 V bI', Fr: ,! L I ','; , f C I: I ~ 1')
l.cV IV, /-1 1 JL I ... , F J:J V"'I' , ~ , 0, C, CA ' IL , h .. t :)f' ,'I, [ .,r- , r s , o1f h ' ) T , ·H rIJP, ~ r <; \, ~ , Hl T P I. Ir, 11
2,TUI'I', wJ 'J X ,~ A "'Y,(~~:'A 111 5 12
c:~Ullr- (A'J,C,II~t:xD(A/(T+4(,C.OJ+Ll+'-"*l 1+ .. ,,0.)11 r [~ 13
100l KE'\il(5, j IL, M ,~L,ML,N 'liS 1"
J I' u 1~ '1 \ r ( :, 1 31 r. I 5 15
lUl>I':,\ L J t. jSU:>I C I'~ 10
i\l i. ul J ' '':~ J I~i:.ól: (I I ,SE IISr: (51 !'1 <; 17
22J Flold'i ,\ T ( ~ L "I I; I S ld
Jl = ooi +1-1 L t i 1.< +;1+ 1 US 11
Jl = J r + L 0 15 2C
J U= JL+ I CIS 21
J,11 1' ; JT-L IJ I') Z2
,{L ,\L'I ?, " ( Tt . ~ i' 1 J) ,J = I, J rJ j) 15 23
'. h J ... ,11\ T ( Ir l.i • ..: I Cl :; 2'.
"Lll l).I ·J, ·.) Iv,\ I' ·..JI( IJ I,J=l, J r. 1 111 5 25
KU\l } I~, !,ll.J(UIJI,J=I · ,J [) 1 DI, 20
H ï~ "iJ I ') , ·, I I ' : 11 lL I .~ ( I I, 1=1, L I U I'; L7
Ku\ ·. )I~, ':' II"' I IVAPIII,I=l,L) D I~ 2 ,J
),L .\l.l 1 ') . -, I (I ,J ': II J ( j I , [ =1 ,L I [; I'; iej
Rb\UI:., .. I(t li 2VA"'lll,!=I,L)
K[ 1. 1: 15 , 'T I 1i ,)j L ( " 1 I I , I = I, LI
.fiS
D( S
30
~ 1
RCÄJI~, ti (I I.. JV i,PI 11 '\=I,lI (;1') 32
d b ruK .'1 AIlL..: l u ....d . US jj
Ri.. AJ 1j , -':.:l I 1 " I I I , I = l,l I Ol S 34
KUw 1 j , 'IJ I I b i ( I , ( = I, L I [ I'i 1',
RlI. J ( :> , d ..J )( l. 1 11 , I = I, L I ~ IS j~
~[A D I5,~IF J llIS,fCl~,s.rC2l1s,F~2VAS.FUJlls,rC3VAS f) I 5 37
Kl I,u 1 J, ft! SJ n U\", RF[ P R , ~; PERR CIS Hl
,., " ITU f. , :>I PIS 31
j t-u Kh Al i '. 'hlll r,PUr f),qA FOR PRCli . NU. us [:'/'; PR O(IIAM '.)
DIS ',0
W" , I T [ 1 (.. , (.. ) l , H , ,., l,l~ 2 ,~; n IS ',1
(, fu KI1 ,\T (Ili,rll ,ü). cr CO ' H'CNFtn5 PLt.ftS [ ~ J S': CTI "J,j ~I PLATfS niS It 2
11 ,. Sl LII J. l ,.IJ. PlATr S IN Sf:I..TIU ii i~": "L"Tr, s UI SrCTIGI>l NII10 1; 1<; 43
.1, I~J, U", li?, 1':;)1 Cl') 44
~~ITtl o ,71~UILIS,fflVA S .FC2LIS,fU~"hS,fJJlIS,f0JVA~ nIS "5
7 rU H:-\.\T (:.i vIIUfLtLl fLtJIIS IN GHOJFil. Of l .J"i..JT EI-<Tf.,'U!'i0 Tij I-l(,HfST/JtH-O l) IS ',0
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A letter vrritten to professor J . M. Prausnitz of the Univers i ty
of California, Berkeley on the 28th of Mareh, 1974 .

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The answer of pr ofessor J. M. Prausni tz from the 9th of April) 1974

Eespreking van het verslag b e b (' rend~ bij h<:! t fabrieksvoorcntwerp van Josef Fre r_keL

Aanwezig: frenkel, Mei jer, Vander W~ele en De Winter.

Het door Frenkel geleverde werk ~ etrof:

I. Beschrijving van het vlo~i st of-dampevenw;'cht voor het systeem mono-, di-, trimethylamine en water.
2. Draaiklaar maken van een pregramma voor destillatie van niet-ideale multicomponentsy~te~p.n.

3. Ontwerp van een destillatiekolom voor extractieve destillatie van methylamines met water.

De bes?reking van het helder ge schreven verslag, dat laat zien dat een aanzienlijke hoevee!heid werk is verzet,
concentreerde zich op de mislukte poging de destillatieberekeniu 3 uit te voeren. Als resultaat van de bespreking
volgt hier eeu korte discus~ie van mogelijke oorzaken en een s amenvatting van suggesties voor voortzetting van
het werk.

Mogelijke oorzaken voor de mislukking van de destillatieberekening.

I. Het destillatieprogramma bevat fouten. Dit is niet waarschijnlijk aangezien het testvoorbeeld goed draait.

2. De evenwichtsgegevens zijn niet correct. Dit lijkt wel waarschijnlijk, temeer daar het destillatie programma
vast loopt op abnormale temp '~rat"ren. Ervaringen van De Winter geven aan dat het dan meestal gaat om foutie-
ve evenwichtsgegevens.

2. I. De hier gebruikte Wi lson-vergelijking zou niet toepasbaar È.unnen zijn t. g.'~. IOOgelijka anomalieën van het
systeem, met name ontmenging van de vlo ei stoffa~e. Frenkel zag hierin een belangrijke mogelijke oorzaak,
mede gezien zijn correspondentie met prof. Prau~nitz, en er.kele vreemde uitkomsten van Wilsonconsr:anten.
Na uitvoerige discussie we,-d dit toch erg onwaarschijnlijk geacht. De P tot -'"r. diagr=cn van de binairen
aminè-water (resultaat voolbespr. dW-vdW) geven vloeiende lijnen die geenszins op ontcenging duiden. De
uit die gegevens voortkome"de Wilson-beschrijving van het multicoDFonentsysteem zal ook vloeiende lijnen
opleveren (Wilson ~ geen ontmenging en dergelijke anomalieën beschrijven.)

2.2. De Wilson-constanten (berei<.end met een programma) zijn niet correct.

2.2.1. De invoerdata (istherme totaaldruk data voor binairen) zijn onvoldoende nauwkeurig, of te weinig in aan-
tal, waardoor de onnauwkeurigheid de ultkomsten te sterk beinvloed. Een andere 1I'.ogelijkheld is dat de
invoerdata niet consister·r zijn: binaire data die niet aansluiten bij die van de zuivere componenten (ach-
teraf bedacht,vdW). Deze oorzaken zijn niet heel waarschijnlijk, maar wel nader te onderzoeke.l.
2.2.2. Het progr~ dat de Wilson-constanten berekent bevat fouten. Het progremca is uit de literatuur oyerge-
nomen (Prausnitz). Alleen is voor minin:alisering bij het "fitten" een Delfts subprogral!!lllB ingezet (OPTPOW).
Een aar.wijzing voor een fout in het programma is dat het testvoorbeel:l niet precies de ge:neläe resultaten
oplevert. Er is lang naaI fouten gezocht, de juistheid van het programua blijft dubieus. Dat de oorzaak
ligt bij de verwisselde subroutine achten dW en vdW erg onwaarschijnliji<.

Sugg~sties voor voort~etting_~~~ .~ct werk.

I. Nader onderzoek van de uitkom i ten van het programma dat Wilson-constanten berekent door met deze uitkorr5tcn
Ptot-~ diagramr.en te mak2u el deze te vergelijken met de inputdata • . Fouten t.g.v. 2.2. I. en 2.2.2. moete"
daarbij tevoorschijn komen, e',l ku.....,nen aanleiding zijn grondig in de programmatuur te duiken.
2. De destillatieberekening cont ' ~oleren door toepassing op een ~engsel met bekende Wilson-constanten (suggestie
verslag Freakel) • Dit is alle,m zinvol als te we., ,,-.i. g vertrOUwd kan worden op de bij het destillatieprogralr.'-'i
gevoegde testberekening.
3. De Renon-vergelijking toepass tln i.p.v. de Wilson-vergelijking (suggestie verslag Frenkel). Dit is sterk af te
raden - zie ook het vergelijk'md onderzoek van D.J. McCann, I.Chem.E.Sym?Series,no .15,pg 4:3 (1972). De Re"on--
vergelijking heeft per binair een parameter meer dan Wilson (dus 3 i.p.v. 2). Eet risico van een inaècqcate ~~­

beschrijving is daardoor veel groter. Wel 1,an in principe ontmenging in de vloeistoffase beschreven worden.

Conclusie.

Een eventuele opvolger van Frer-.k" l heeft na een stevige inwerkperiode uitzicht op goede resultaten voor het ontw0rp
van een extractieve destillatie "an methylamines met water. Constr.lctÎt! en kritische beschouwing van !.~~~ dii!-
grammen voor het mengsel TI-'A-,.,., t c. r of TMA- (water+DMA+NI-'A), waarbij de laatste drie in een vaste verhouding gekczen
\Oordom, kan het inzicht in deze u:atérie vergroten en wel:icht zichtbaar maken of de gewenste scheiding op grond V.ln
de gebruikte gegevens realiseer;;. ar is.

Kvdw / 30-6-1974