Chemicd ,9&w& Scimce, 1976, Vol. 31, pp. 893-W. Pta-@mon Prear.

Printed h Great Britain

SELECTION OF A SOLVENT FOR ADDUCTIVE

CRYSTALLIZATION

J. P. TARE and M. R. CHIVATE

Del#lrtmentof ChemicalTechaology,Universityof Bombay,Matunga,Bombay-400019,
India

(Received2l November1975;accepted20April 1976)

Abshct-A procedure for screening solvents for adductive crystallizationby use of the data on the enthalpy
changeson complexformation,whichcan be easilymeasuredexperimentally,is proposed.Twoparameterschemical
theory of Harris and Prausnitzhas been utilizedfor calculationsof activitycoefficientsand selectivityvalues.This
methodof screeningsolvents for adductivecrystallizationseems to be useful for practicalapplications.

1.lNlRODWllON contribution by chemical interactions. Therefore, the

Extractive and adductive crystallization processes are
established techniques for the separation of close boilii
organic compounds. It is the solvent which helps in
resolving the eutectic or the molecular compound between
the close boiling compounds. A correlation involving
solubility parameters to predict the selectivity of a solvent
for extractive crystallization have been reported by
D&shit and Chivate[l]. However, so far no method of
screening the solvents for adductive crystallization has
been proposed. Essentially, the final selection of a solvent
for adductive crystallization depends upon experimental
evaluation of solid-liquid equiliirium data for the ternary
which contains the components to be separated and the
solvent. It is, however, a time consuming and laborious
process to prepare a solid-liquid equilibrium diagram for
ternary systems. If solvents could be effectively screened
prior to 6nal selection, this work could be reduced
considerably.
The purpose of this paper is to develop a procedure for
screening solvents. One way of doing it would be to
measure the data on enthalpy changes on complex
formation for binary mixtures, which are quickly obtained
experimentally.
2. TEEORY
The solvent in case of an adductive crystallization
process forms a loose molecular compound with either of
or both the components to be separated. The resulting
compounds diBer in melting points. The theory of the
mechanism of adduct formation has not been well
developed but formation of hydrogen bonds appears to be
an important factor when all the successful adductive
crystallization agents are considered.
It is well known that whenever hydrogen bonds are
formed, heat is evolved. It is therefore logical to think that
whenever heat evolved on addition of the solvent to the
components to be separated differ, the solid-liquid
relationship would also differ. The observed value of this
heat evolution, which might be termed as the enthalpy
change on complex formation, consists of the contribu-
tions from the physical and chemical interactions. The
magnitude of the physical interactions contribution in
such cases would be very low &comparison with the
893
contribution by physical interactions is neglected and
observed enthalpy change is taken as due to chemical
interactions alone. The maximum value of enthalpy
change is taken as enthalpy of complex formation.
In case of complex forming solutions the magnitude of
attractive interactions between unlike molecules is much
larger than that between like molecules, thus there is a
strong tendency to form as many unlike pairs as possible.
This would result in strong ordering of molecules in the
mixture by attractive interaction so that an entropy loss is
produced on complex formation. At lower temperatures,
the influence of entropy (TAS) is small[2] and therefore
assumed to be negligible as compared to the contributions
due to enthalpy of complex formation. The free energy
change for the chemical equilibrium
A+B=AB (1)
and therefore the equilibrium constant K for this reaction
then can be determined from enthalpy of coniplex
formation only. The equilibrium constant K is normally
found from the NMR spectral data [3] or from ultraviolet
absorption data[4].
Let Z.+ ZB and ZABstand for true mole fractions then,
K&Q- r;B
(2)
z&l r:r:,
where y’ stands for true activity coefficients. According
to Harris and Prausnitz[5], y’ for any true component is
given by the following correlation:
where 4 is the volume fraction given by the equation:
Vi = liquid molar volume of i, and ai = van Laar
parameter for physical interaction of species i and j. The
894 J. P. TAREand M. R. &lVATE

subscripts i, j and k are understood in this case to range
over the possible species A, B aad AE. The apparent
activity coefficients and the apparent mole fractions are
related to the true activity coefficient and true mole
fraction by
The true mole fractions are related to apparent mole
fractions in forms of the normalized extent of complex
formation [(OS 5 C (l/2))
ZAB',_5
5 liquid components were purified by the conventional
z -x2-5
A 1-t
and
third for the electrically driven stirrer. The speed of the
stirrer was kept such that a thorough mixing was obtained
and the heat of stirring was negligible. One of the liquid
components was placed in the flask and the other liquid
component was placed in the jacketed burette through
which the thermostatic fluid circulated. Both the compo-
nents were maintained at a fixed temperature at which
(9 enthalpy changes on complex formation were determined.
After steady state was reached the components were
(6) mixed and the change in temperature was observed. The
readings were taken throughout the composition range
with a difference of 0.1 mole fraction. Radiation
corrections were applied. Specific heats of all liquid
components were experimentally determined. Water
equivalents of the calorimeter and the contents were
repeatedly determined by the electrical method. The
methods.
The working of the calorimeter was tested using the
(8) chloroform-acetone system since a complex occurs in
this system. Our data agreed with those of Campbell and
Kartzmark[6] as shown in Fig. 1. If an adduct is formed
then the amount of heat evolved would be of the order of
at least a hundred calories per mole, for the measurement

5=
l- Jb-(iS+~> (1o)
of which the present apparatus provides sulliciently
accurate data.
2
4. C-TIONS OF ACTMTY COEFFICIENTS
where, K’ is defined by: ANDs-
The following systems were chosen for selectivity
study: (1) quinaldine-acetic acid; (2) isoquinoline-acetic
(11)

For given values of K and (Y,it is possible to compute

“true” compositions and activity coefficients at any - Present work

specilied apparent composition by simultaneous solution -+ Campbell f6 1

of eqns (3) and (7)-(10). The apparent activity coefficients -O- Hirobe (15 I

are then given by eqns (5) and (6). The procedure of

solution of the simultaneous equations which have been
used here is the same as that used by Harris and
Prausnitz[S] and the iterative calculations were easily
handled by an IBM 1620 computer.
The selectivity values can then be calculated from

s,.,=; (12)

where, 1 and 2 are the close boii components to be

separated. An essential requirement of a good solvent is
to have selectivity values different than unity. In this work
selectivity values of a number of successful adductive
crystallization systems are calculated, to find out the
validity of this hypothesis.
3. DFXERMlNATlONOFEJWEUPYcBANGEs
ON COMPLEXFORMATION
The apparatus consisted of a standard Dewar flask of
0.3 1. capacity. The lid made of thick polypropylene sheet
was fitting the flask tightly. The cover had three holes, one
for the tip of the jacketed burette through which the Mole fraction of acetone

second liquid component was poured in, another for the Fig. 1. Enthalpy charges on complex formation of chloroform
thermometer which was graduated upto O.l”C and the and acetone at 3O.OC
 Selectionof a solventfor adductivecrystallization 895

acid; (3) m -tiesol-t -butyl alcohol; (4) p -cresol-t-butyl

alcohol; (5) m -xylenacarbontetrachloride; (6) p -xylene-
+ Acetic aaid,quinaldine
carbontetrachloride; (7) m-cresol-acetic acid; (8) p- 1400
+ Acetic acid, isoquinollnc
cresol-acetic acid.
The enthalpy changes on complex formation data for t
systems 14 is shown in Figs. 2 and 3 and for systems 5
and 6 data available in literature [7,8] was used. In case of
systems 7 and 8 no measurable enthalpy changes were
observed. The calculations were performed as follows:
Let us consider systems 1 and 2. The maximum
enthalpy change was found to be -1115 Cal/mole and
-1013 cal per mole for systems 1 and 2 respectively. The
equilibrium constants are given by

-1115=-1.98x303.15xlnK forsysteml
and
-1013=-1.98X303.15xlnK forsystem2.

Therefore K = 6.4083 for system 1 and K = 5.4065 for

system 2. The physical interaction parameter, (Y=
(8~ - &)*= 2.8392 for system 1 and a! = 3.7442 for
system 2. With these K and (Y values the activity
coefficients were calculated as described earlier.
The activity coefficients for quinaldine in acetic acid
and isoquinoline in acetic acid are given in Table 1 along
with selectivity values.
The equilibrium constant K along with other proper-
ties needed to calculate activity coefficients for the sys-
tems under study are tabulated in Table 2. The activity
coefficients and selectivity values obtained by this
procedure are termed as calculated and are plotted in
Figs. 47.
For systems 5,7 and 8 where no indication of adduction
was found, the equilibrium constant was assumed to be
XTO.
Mole froctlon of amine
Fig. 2. Enthalpychangeson complexformationof aceticacid and
quinaldine,isoquinoliueat 3O.K.
In order to 6nd the validity of the calculated activity
coefficients and selectivity values, these were compared
with the observed ones which were found out as follows:
For systems 7 and 8 activity coefficients were
calculated from solid-liquid equiliirium data. For adducts
ideal solubilities cannot be determined, hence, activity
coefficients based on ideal solubilities and heats of fusion
cannot be calculated. Therefore, for systems 1-6, activity
coefficients were determined from vapour-liquid equilib-

Table 1. Activitycoefficientsand selectivityvalues

xamine 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Yi 0.1961 0.2557 0.3616 0.5811 0.9961 1.2095 1.1518 1.0675 1.0160

% 0.1686 0.2203 0.3119 0.5018 0.8670 1.0968 1.0927 1.0444 1.0101
83, 1.1633 1.1610 1.1594 1.1579 1.1488 1.1027 1.054 1.0221 1.005

Table2. Equilibriumconstantsand otherproperties

System K V, V, 6, Sg T
(1) quinaldine(A)
-acetic acid (B) 6.408 135.3 88.15 9.187 7.5 303.15
(2) isoquinoline (A)
-acetic acid (B) 5.406 121.87 88.15 9.43 7.5 303.15
(3) m-cresol-(A)-t-
-butyl alcohol (B) 1.6920 104.00 95.00 10.15 9.585 303.15
(4) p-cresol (A)-t-
butyl alcohol (B) 1.484 104.00 95.00 10.15 9.585 303.15
(5) m-xykne (A)
-CCL (B) - 124.00 97.00 8.8 8.6 303.15

“g$A) 1.032 124.00 97.00 8.8 8.6 303.15

(7) m-cresol (A)
-acetic acid (B) - 104.00 88.15 10.15 7.5 303.15
(8) p-cresol (A>t-
acetic acid (B) - 104.00 88.15 10.15 7.5 303.15

CES Vol. 31 No. IO-C

 J. P. TANSand M. R. &VATE

- C-alcufated
- l-butyl alcohol, m - Cresol & Observed

- i-butyl alcohol, p -cresol

Mole fraction of xylenc

I.0 -

- r, calculate

I I I I - 7,~ observed
*2 4 *6 -6
Mole fraction of cresol.
.6- --b Yp observed
Fig. 3. Eothalpychangeson complexfomtim of t-butylalcohol
and fag -cresolsat 3O.K.
.5-
- *6 14
Mole fraction of p-xylenc

I -

-+-
Calculated

Observed
1 Fii. 5. Selectivityof carbmtetracbloridefor m, p-xyleaes.

rium data. The data for the systems l-4 were experimen-
tally determined by authors [9] and for the systems 5 and 6
the data by Rodger et al. [lo] was used. The vapour
pressure data was taken from Jordan[ll]. The values of
activity coefficients by both these methods and the
Mole fraction of amine
selectivity values are depicted in Figs. 47.

5.DIscUSSIONS
From a study of Figs. 4-7, it is found that the agreement
between observed and calculated values of activity
coefficients and selectivity values is satisfactory, coosid-
ering that the two are obtained under diBereot cooditioos.
The differences can be explained well by the fact that as
the temperature increases the system becomes more and
more normal and the influence of chemical interactions
decreases through thermal agitation. Therefore, the
- ‘Vq - cdlculated observed selectivity values are lower than the calculated
-c ?q -observed selectivity values.
e Vi -calculated In case of quinaldine-acetic acid and isoquioohne-acetic
4 ?I -observed acid systems the eothalpy changes on solutioo data dieters
considerably as shown in Fig. 2. This means that acetic
acid would have diBereot degrees of adductioo with
quinaldine and isoquinoline. The binary solid-liquid
equilibrium data for these systems is shown in Fig. 8,
which indicates that acetic acid do have diEereot extents
of adductioo with both the close boiling components. The
observed and calculated values of selectivities are more
0
0
I
0.2 0.L
I I
0.6
I
0.6
I
1.0 than unity as shown in Fig. 4. This means that
Mole fraction of quinoldine
quinaldine-acetic acid adduct would crystallize out
Fig.4. Selectivityof acetic acidfor quinaldineandisoquinoline. preferentially from a mixture of quioaldioe and iso-
 Selectionof a solventfor adductivecrystallization 897

Mole fraction of cresol

- calculated

-
observed

calculated

observed
::Iy Mole
.L
fraction of
.6
acetic acid.
4 I

Fig. 8. Binaryequiliiriumcurvesof (1) quinaldine-aceticacid; (2)

isoquinoline-aceticacid.

quinoline in acetic acid. That is quinaldine-acetic acid

would occupy a greater area of add&on in the ternary
solid-liquid equilibrium diagram, making it possible to
separate the eutectic of quinaldine and isoquinoline by
adductive crystalliition using acetic acid as a solvent. In
I I I I
order to verify this conclusion, the authors have
.2 4 .6 4 constructed a ternary solid-liquid equilibrium diagram for
Mole fraction of p- cresol
the system quinaldine-isoquinoline-acetic acid. It is
Fig.6. Selectivityof t htyl alcoholfor m, p xresols. shown in Fig. 9. This Ggure clearly con6rms the
conclusion of the selectivity study.
For carbontetrachloride and m-, p -xylenes enthalpy
r I changes on solution data available in literature[7,8] was
used. The m-xylene-carbontetrachloride system is en-
dothermic in nature whereas p -xylene-
carbontetrachloride is exothermic in nature. This means
that carbontetrachloride would form adduct only with
p-xylene and not with m -xylene. The binary solid-liquid
equilibrium diagram[l2] for these systems supports this
Mole traction of cresol. conclusion. The deviations between observed and calcu-
lated values are maximum in these systems. These can be
explained well by the reason, as pointed out earlier, that
the adduction takes place at very low temperature (-100
to -7OT), where chemical interactions are predominant.
The activity coefficients of p-xylene in carbontetrach-
loride are far less than those of m-xylene in carbon
-o- Yp-observed.
tetrachloride. Therefore, p -xylene-carbontetrachloride
AYm-calculated.
adduct would have a large area. The observed and
--+-‘Lm-observed. calculated selectivity values, (Fig. 5) are more than unity
thereby indicating that p -xylenecarbontetrachloride ad-
duct would crystallize out preferentially from a mixture of
m - and p-xylenes in carbontetrachloride. The tenary
diagram for the system m -xylene-p -xylene-
carbontetrachloride has been reported by Egan and
Luthy[lZl. Their work supports the above conclusion.
0 0.2 04 0.6 0.6 I.0 The systems m-cresol-t butyl alcohol and p-cresol-t
Mole fraction of p-cresol butyl alcohol are exothermic in nature thereby indicating
Fig.7. Selectivityof aceticacidfor m-,p-cresols. that both the isomers would form adducts with the
898 J. P. TAREand M. R. CHNATE

ocetic acid

Fig. 9. Ternarysolid-liquidequilibriumdiagramfor the system quinaldine-isoquinoline-acetic

acid.

solvent. The enthalpy changes data for these systems is adductive crystallization. It seems that Harris and
shown in Fig. 3, indicating suitability of t-butyl alcohol as Prausnitz’s two parameter theory 151provides an excellent
a solvent. The calculated and observed activity coeffi- means for predicting solvating mixture behaviour.
cients and selectivity values are shown in Fii. 6. Though
the agreement between observed and calculated activity Acknowledgement-One of us (J.P.T.)expresseshis deep sense of
coefficients is good, the selectivity values show opposite gratitudetowardsUniversityGrantsCommissionfor the finam%
trend. The calculated selectivity values are less than unity assistance which enabled this work to be tied out.
thereby indicating that m-cresol-t butyl alcohol adduct
would crystalliie out preferentially from a solution of the NOTATIONS
isomers and the solvent. However, the ternary 132 components
diagram [ 131for this system indicates that p-cresol-t butyl A solute
alcohol adduct crystal&s out preferentially from the B solvent
solution. The cause for such a solution behavior has not K equilibrium constant
been understood. K’ as defined by eqn (11)
As no enthalpy changes on solution were observed for H enthalpy content, cal/mole “K
the systems m -cresol-acetic acid and p -cresol-acetic acid R gas constant, callmole “K
no adduction is expected in either of the systems. The S entropy, Cal/mole “K
physical and chemical interactions in both these systems S I.2 selectivity
seems to be balanced thereby indicating non-suitability of T temperature, “K
this solvent either for an extractive or for an adductive V molar volume, cm3/mole
crystallization process. The observed and calculated z true molefraction
selectivity values are close to unity as shown in Fig. 7. X apparent molefraction
This means that acetic acid would not be able to resolve
the compound between M- and p-cresols. The ternary Greek symbols
solid-liquid equilibrium diagram for the system m cresol- a van Laar physical parameter
p-cresol-acetic acid has been reported by Chivate and A incremental change
Shah[l4]. This diagram justifies the above conclusion. S solubility parameter 9(cal/cm3)‘n
4 volume fraction
y’ true activity coefficient
6. CONCLUSIONS y apparent activity coefficient
It has been shown that enthalpy changes on complex i$ extent of complex formation
formation data can be used to screen the solvents
qualitatively as well as quantitatively for a given pair of Superscript
close boiling organic compounds to be separated by M mixing
 Selection of a solvent for adductive crystaBization 899

Subscript 171Rastogi R. P., Nath Jagan and Misra R. R., J. Gem. Thermo.
i, j, k component numbers 19713 312.
[8] Rastogi R. P., Nath Jagan and Misra J., I. Whys.Gem. 1%771
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719. [lo] Rodger A. J., Hsu C. C. and Furter W. F., J. C/tern.EngngData
[2] Ketelaar J. A. A., Chemical Constitution,2nd Edn, p. 397. 1%9 14 365.
Elsevier, London 1958. [ll] Jordan T. E., Vapour Pressure of Organic Compounds.
[3] Homer J., Everdell hf. H., Jackson C. J. and Whitney P. hf., Interscience 1954.
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Stahtiity Constants. McGraw-Hill, New York l%l. 196810 121.
[5] Harris H. G. and Prauznitz J. M., Znd. Engng Gem. Fundl. [14] Chivate M. R. and Shah S. M., Cheat. EngngSci. 19565 232.
Wilhelm Memorial Issue (May 1%9). [15] Hirobe H., I. Sci. Tokyo 19261 155.
[6l Campbell A. N. and Ka&mark E. N., Can. J. Chem. 196038 [16] Brown I. and Fock W., Aus. Z. Chem. 19558 367.
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