J . Chem. Tech. Biotechnol.

1981, 31,279-284

Separation of Close Boiling Substituted

Phenols by Dissociation Extraction
Vishwas V. Wadekar and Man Mohan Sharma
Department of Chemical Technology, University of Bombay, Matunga Road, Bombay 400 019, India
(Paper received 8 June 1979, revised 8 August 1980 and accepted 31 August 1980)

Some mixtures of substituted phenols, which are difficult to separate by established

methods such as distillation, crystallisation, etc., have been separated by dissociation
extraction. Di-n-butyl ether was found to be an excellent solvent for the systems:
phenol-o-chlorophenol; p-chlorophenol-2,4-dichlorophenol; o-cresol-6-chloro-o-
cresol. In the case of m-cresol-2,6-xylenol and p-cresol-2,6-xylenol, benzene was
found to be a good solvent. For the system: 4-chloro-m-xylenol-2,4-dichloro-m-
xylenol dissociation extraction in a solid-liquid system without a solvent gave higher
values of separation factor than a liquid-liquid system. In all the cases, agreement
between the experimental and theoretical values of separation factors was found to be
reasonable.

1. Introduction
Dissociation extraction is a two-phase separation technique which utilises the difference between the
dissociation constants of the components to be separated, along with the difference in their distribu-
tion coefficients. This separation technique is particularly attractive in the case of organic acids and
bases which are difficult to separate by common methods of separation such as distillation, crystall-
isation, etc. In essence, the process involves equilibriating the mixture of components (say, organic
acids) with a stoichiometric deficiency of a neutralising agent (an alkali, in thiscase)inanother phase-
this is generally water. The alkali, being in stoichiometric deficiency, preferentially reacts with the
stronger acid, thus resulting in a compositional difference between the two phases. This process has
been used by many workers to separate various isomeric and non-isomeric mixtures.l-* Some
theoretical work has also been reported for binary and multicomponent sy.~tems.~.~.S.~
Laddha and Sharmalo have considered separation of close boiling non-isomeric chlorophenols
by dissociation extraction. The present paper is concerned with the separation of some industrially
important chloro- and methyl-substituted phenols. Thus, in the manufacture of 4-chloro-o-cresol,
which is an intermediate in the production of a weed-killer, there is some problem of separating
o-cresol and 6-chloro-o-cresol which have practically the same boiling points. Similarly, in the
manufacture of Cchloro-m-xylenol, which is an important germicide, the problem of the separation
of 4-chloro-m-xylenol and 2,4-dichloro-m-xylenol occurs. The separation of 2,6-xylenol from m-
and p-cresol is also of practical importance and these compounds have very close boiling points.
The separation of these substituted phenols is not easy by any established means of separation.
However, in view of the considerable differences in their dissociation constants, it was thought
desirable to consider their separation by dissociation extraction (Table 1).

2. Materials
Isomers of cresol, 2,6-xylenol, phenol, o-chlorophenol, p-chlorophenol, 2,4dichlorophenol and
4-chloro-m-xylenol were obtained from commercial sources. To obtain 6-chloro-o-cresol, 0-cresol
was chlorinated in a bubbler by passing chlorine at 4045°C until no unreacted 0-cresol remained.
0142-0356/81/0500-0279 502.00 0 1981 Society of Chemical Industry
219
280 V. V. Wadekar and M. M. Sharma

Table 1. Physical properties of various phenols

B.p. at
P Kn 101 kPa M.p.
Compound at 25°C ("C) ('C)
~~

Phenol 10.00 181.4 42-43

o-Chlorophenol 8.48 175-1 76 7
p-Chlorophenol 9.18 217 4 1-43
2.4-Dichlorophenol 7.75 210 45
o-Cresol 10.28 191-192 30
6-Chloro-o-cresol 8.69 191-193 -
m-Cresol 10~10 202 11-12
p-Cresol 10.28 201.8 35.5
2,6-Xylenol 10.62 203 49
4-Chloro-m-xylenol 9.70 246 115.5
2,4-Dichloro-m-xylenol 8.28 - 95-96

The mixture of 6-chloro-o-cresol, 4-chloro-o-cresol, and 4,6-dichloro-o-cresoI thus obtained was

fractionally distilled at reduced pressure to obtain 6-chloro-o-cresol as a distillate. Similarly,
4-chloro-rn-xylenol dissolved in benzene was chlorinated until no unreacted 4-chloro-m-xylenol
remained. This gave a mixture of 2,4-dichloro-m-xylenol and 2,4,6-trichloro-m-xylenol. Benzene
was evaporated and the resulting solid mixture extracted with a stoichiometric deficiency of an
aqueous alkali. This dissociation leaching was repeated two or three times until the necessary purity
of 2,4-dichloro-m-xylenol was attained. These substances were then analysed by gas-liquid chroma-
tography and found to be at least 99 % pure. Other materials used (e.g. benzene, di-n-butyl ether
and sodium hydroxide) were of reagent grade. Distilled water was used whenever needed.

3. Experimental procedure and analytical techniques

For both liquid-liquid and solid-liquid dissociation extractions, the experimental procedures and
analytical techniques used were those previously reported.1° The analysis was performed using an
AIMIL dual column gas-liquid chromatograph. For the p-chlorophenol 2,4-dichlorophenol
system a copper column (1 m long, 6 mm i.d.) packed with 10% Carbowax 20 M and 2% ortho-
phosphoric acid on Chromosorb W/AW was used. For all other systems a copper column (3 m
long, 6 mm i.d.) packed with 25% Apiezon N on alkali-treated Chromosorb W/NAW was used.
For all the analyses, hydrogen was used as the carrier gas with a thermal conductivity detector.

4. Theory
Anwar et al.1 have developed a theory for the prediction of the separation factor (a) based on a
knowledge of dissociation constants and distribution coefficients of the two components:

DRKA
(I)

Values of distribution coefficients of individual phenols should be measured when the relevant
phenol is distributed between the specific organic solvent and the aqueous alkaline solution.
Laddha and Sharma'o have previously shown that the distribution coefficient of the solute distri-
buted between organic solvent and water can also be used with reasonable accuracy. Hence, this
approach was adopted for the measurement of distribution coefficients.
Since all the substituted phenols used here are sparingly soluble in water, gas chromatography
Separation of phenols by dissociation extraction 281

cannot be used conveniently for the determination of distribution coefficients. Therefore, use of a
U.V. spectrophotometer for distribution coefficient measurement was thought desirable. For this
purpose, the organic solvent containing a known quantity of the desired substituted phenol was
contacted with water until equilibrium was attained. The phases were then separated and the aqueous
phase analysed using a Beckmann DK-2 UV spectrophotometer. Organic-phase concentration was
determined by material balance. Values of the distribution coefficients remain reasonably constant
over the wide range of solute concentrations. Results of these measurements are shown in Table 2.

Table 2. Distribution coefficients for various phenols:

organic phase concentrations in the range 0.1-1 .O
mol dm+

Solvent

Di-n-butyl
Compound ether Benzene

Phenol 11.64 4.2SR

o-Chlorophenol 71.6 37.5"
p-Chlorophenol 61.4 20.6"
2,4-Dichlorophenol 280 139a
o-Cresol 28.2 8.67
6-Chloro-o-cresol 278 202
m-Cresol 30.2 I I .2
p-Cresol 33.2 12.4
2,6-Xylenol I10 13

See reference 10.

5. Results and discussion

The separation factor ( u) was calculated from the equation:

a=- LAIS [B*la

[A*laX [Bls
where: [A]. and [B]. refer to the molar concentrations of A and B in the organic phase, respectively.
[A*]& and [B* ]a refers to the total molar concentration of A and B in the aqueous phase at equilibrium
i.e. the sum of dissociated and undissociated A and B in the aqueous phase, respectively. A
represents the weaker acid of the two.
5.1. The phenol-o-chlorophenol and p-chlorophenol-2,4dichlorophenol systems
These systems have been studied by Laddha and Sharmalo using benzene as solvent. In the present
work, a remarkable improvement over the separation factors reported10 has been achieved by using
di-n-butyl ether as solvent. Separation factors obtained here are 1.5- to two-fold higher than
the corresponding values obtained by Laddha and Sharnia. Figure 1 illustrates the variation of a
with the molar ratio of phenol: o-chlorophenol and p-chlorophenol :2,4-dichlorophenol. In Figures
1-6, the solid lines represent the predicted values of a based on equation (I), while the points
represent a values determined experimentally.
5.2. The o-cresol4-chloro-o-cresolsystem
The importance of the difference in the distribution coefficients (along with the difference in PKa
values) in dissociation extraction can be emphasised with this system. While practically no separa-
tion occurred with solvents such as benzene, di-n-butyl ether gave separation factors between 3 4 ,
which can be considered to be relatively good. Figure 2 illustrates the variation of a with the molar
ratio of 0-cresol :6-chloro-ocresol with di-n-butyl ether as solvent.
282 V. V. Wadekar and M. M. Sharma

6to
0
0

tEq"ol,.n I 1I 0

I I ,

5.3. The m- and p-cresol-2,6-xylenol systems

Benzene was found to be an excellent solvent for these systems, an observation which is in agreement
with the findings of Kiseleva et d4With benzene as solvent, m-cresol-2,6-xylenol system separates
with a in the range 2C23, while di-n-butyl ether as solvent gives a values in the range 10-13. A
similar trend was obtained for the system p-cresol-2,6-xylenol. The effects of the molar ratio of
2,6-xylenol:m-cresol and 2,6-xylenol:p-cresol, molarity of neutralising alkali, and total molar
concentration in the organic phase, on the separation factor are illustrated in Figures 3-6.

5.4. The 4-chloro-m-xylenol-2, 4dichloro-m-xylenol

With di-n-butyl ether as solvent, separation factors of 5-6 were realised. However, much higher
values of separation factors were realised by using solid-liquid dissociation extraction. As can be
seen from Table 3 a values as high as 10 have been obtained. In this case, the solid-liquid dissocia-

I I I
2 1 6

Figure 3. Effect of molar ratio of a 2,6-xylenol:m-cresol system in benzene ( 0);and di-n-butyl ether ( D) on LY
(T 2 0.5 mol d ~ n - M~ =, I )
Figure 4. Effect of molar ratio of a 2,6-xylenol:p-cresol system in benzene ( 0 ) ;and di-n-butyl ether (7)on a
T zz 0.5 mol dm+, M = 1)
Separation of phenols by dissociation extraction 283

0 0 0
/"
0

Figures. Effect of molarity of sodium hydroxide solution (0) (6=0.25, T N 1 mol dm-8); and total concentration
of phenols in benzene ( 0) (6=4,M= 1) o n a for the system m-cresol-2,6-xylenol and using benzene as solvent.
Figure 6. Effect of molarity of sodium hydroxide solution ( 0 )(6=0.25, T N 1 mol h - 9 ; and total concentration
of phenols in benzene (0) (6=4, M = I ) on 01 for the system p-cresoI-2,6-xylenol and using benzene as solvent.

Table 3. Separation factors for the system : 4-chloro-m-xylenol-2,4-dichloro-m-xylenoI

Molarity Molar ratio of 4-chloro-

of aqueous m-xylenol: 2.4-dichloro- Separation Total concentration of
NaOH m-xylenol in the organic factor chloro-xylenols in the
(M) phase/leached solids (6) (4 Solvent used phase (mol d m 3 (r)

I .o 0.52 5.10 Di-n-butyl ether 0.52

1 .o I .so 5.56 Di-n-butyl ether 0.51
1 .o 4.82 5.72 Di-n-butyl ether 0.50
0.2 5.60 9.97 No solvent -
0.2 9.00 10.53 No solvent

tion extraction has two advantages: (i) use of solvent is avoided: and (ii) higher separation factors
are realised.
The distribution coefficients of 4-chloro-rn-xylenol and 2,4-dichloro-m-xylenol are exceptionally
high and their measurement may not be accurate. For other systems (seeFigures 1-6) the agreement
between experimental and theoretical values of separation factors is fairly good.

6. Conclusions
In the case of some systems such as rn-cresol-2,6-xylenol, p-cresol-2,6-xylenol and 4-chloro-m-
xylenol-2,4-dichloro-m-xyleno!,exceptionally good separation factors are obtained. This brings
out the usefulness of employing dissociation extraction for separating difficult systems. Separation
factors for the other systems are also promising.
The combined importance of the difference between the dissociation constants and the difference
between the distribution coefficients of the system components is highlighted in this study. In the
case of the o-cresol-6-chloro-o-cresol system, practically no separation occurs when benzene is used
as a solvent, while di-n-butyl ether gives separation factors of 3-4. Systems such as rn-cresol-2,6-
xylenol and p-cresol-2,6-xylenol also give separation factors 1.5-two-fold higher when the solvent
is changed from benzene to di-n-butyl ether.

Acknowledgement
One of the authors (VVW) wishes to thank the University Grants Commission, India for a scholar-
ship which enabled this work to be carried out.
284 V. V. Wadekar and M. M. Sharma

Nomenclature
[A19 [BI Concentration of undissociated A/B (mol dm-3).
IA*]a. D*Ia Total concentration of A/B in aqueous phase, i.e. sum of concentrations of undissoci-
ated and dissociated A/B (mol dm-3)
DA, Dn Distribution coefficient of undissociated A/B between the organic phase and the
aqueous phase
KA, KB Dissociation constant of A/B in water (g ion dm-3)
M Molarity of the extracting reagent
T Total molar concentratiod of A and R in organic phase = [A], + [BIB(mol dm-3)
a Separation factor
6 Ratio of concentration of A and B in organic phase [AIs/[Bla

Subscripts
a Refers to the aqueous phase
S Refers to the organic phase

References
I. Anwar, M. M.; Hanson, C.; Pratt, M.W. T. Trans. lnstn Chem. Engrs 1971,49,95.
2. Anwar, M. M.;Hanson, C.; Pratt, M.W. T. Proc. of International Solvent Extraction Conference Society o f
Chemical Industry, London, 1971, p. 91 I.
3. Anwar, M. M.; Cook, T. M.; Hanson, C.; Pratt. M.W. T. Proc. of InternationalSoluent Extraction Conference
Society of Chemical Industry, London, 1974, p. 895.
4. Kiseleva, E. N.; Belyaeva, V. A.; Gel’perin, N. I. Khim. Prom (Moscow) 1971, 47, 178.
5. Milnes, M. M. Proc. of International Solvent Extraction Conference Society o f Chemical Industry, London,
1974, p. 895.
6. Wise, W. S.; Williams, D. F. The Less Common Means of Separation (Pirie, J. M., Ed.), The Institution of
Chemical Engineers, London, 1963, p. 112.
7. Anwar, M.M.; Cook, S. M.T.; Hanson, C.; Pratt, M.W. T. Proc. of InternationalSoli~entExtraction Confer-
ence ISEC 1977 (C.I.M., Montreal, 1979). p. 671.
8. Pratt, M. W. T.; Spokes, J. Proc. of InternationalSolvent Extraction Conference ISEC 1977 (C.I.M., Montreal,
1979). p. 723.
9. Kafarov, V. V.; Vygon, V. G . ; Chulok, A. I.; Kostyuk, V. A. R1m.J. Phys. Chem. 1976.50, 1618.
10. Laddha, S. S.; Sharma. M. M. J . appl. Chem. Biotechnoi 1918,28,69.