608

ESTERIFICATION KINETICS OF PHENOL WITH

PHOSPHORYL TRICHLORIDE

Miroslav MAGURA4 , Jan VOJTKO b, Eva ZEMANOVA4 , Alexander KASZONYlb and

Jan ILAVSKyb
aChemko. 07222 Straiske and
b Department of Organic Technology.
Slovak Technical University. 81237 Bratislava

Received March 24, 1988

Accepted May 16, 1988

The liquid-phase esterification kinetics of phenol with POCl 3 has been studied at isothermal con-
ditions within the temperature interval from 90 to 110°C. The esterification rate constants of the
first, second, and third esterification steps and the activation energies of these steps have been
calculated. The given system of competitive consecutive reactions can be described by a system
of differential equations which has been solved by the Gauss-Newton optimization method of
non-linear regression in the Marquardt modification. In the sequence of the first, second, and
third step the esterification rate constants have been found to gradually decrease, whereas the
activation energies increase in the same sequence.

Triphenyl phosphate is used commercially as an incombustible plasticizer and

combustion retarder for polymers, especially PVc. The formation of triphenyl
phosphate from phenol and phosphorus or phosphoryl chlorides has been long
known 1 - 3. On the other hand, data about the kinetics of this process are not available
because of the relative complexity of the consecutive reactions offormation of triphe-
nyl phosphate.
At present, triphenyl phosphate is produced usually by the reaction of phenol with
phosphoryl trichloride according to the summary reaction 4

(A)
however, instead of pure phenol its mixture with alkylphenols is used for the esteri-
fication.
The aim of this present communication was the kinetic measurement of the
esterification of pure phenol to give triphenyl phosphate in liqud phase at the condi-
tions of the open system with respect to hydrogen chloride. The intermediates (i.e.
monophenyl- and diphenyl-derivatives C 6H sOPOCI 2 and (C6HsO)2POCI) were
determined by a method developed for this purpose and described elsewhere s .
The esterification rate constants were calculated by means of the Gauss-Newton
method of non-linear regression in the Marquardt modification.

Collect. Czech. Chem. Commun. (Vol. 54) (1989)

Esterification Kinetics of Phenol 609

EXPERIMENTAL

Reagents
Phenol of p.a. purity grade, POCl 3 prepared in Chemko Strazske by oxidation of PCl 3 (Chemie-
-Kombinat, Bitterfeld, G.n.R.), o-xylene of p.a. purity grade, 2-ethylhexanol of p.a. purity
grade, octadecane of p.a. purity grade (Lachema Bratislava).

Apparatus and Methods

The esterification reactor consisted of a three-necked flask equipped with a thermometer, reflux
condenser, and inlet of nitrogen gas. The reflux condenser consisted of two parts, the upper part
serving for the removal of gaseous hydrogen chloride which passed through a system of washing
bottles filled with NaOH.
The whole reactor was immersed in an oil thermostat which allowed to maintain the tempera-
ture chosen with the accuracy of ±0·2°C. The reaction mixture was stirred by means ofa magnetic
stirrer.
Before the measurement the reactor was charged with phenol, catalyst (MgCI 2), and o-xylene
as an inert solvent. This mixture was heated to the reaction temperature, and POCl 3 was rapidly
added under the surface from a funnel. The composition of the mixture was followed by with-
drawing 0'5 cm 3 samples of the reaction mixture at chosen time intervals. The samples were
rapidly cooled to -18°C to practically stop the reaction. Before the analysis the reaction mixture
was allowed to react with excess 2-ethylhexanol at 80°C for 2 h in a microreactor. The alcohol
reacts substantially faster than phenol and converts the unreacted POCl 3 and the intermediate
monochloride and dichloride into the corresponding ester or mixed esters:

IB)

+ 2 C S H 17 0H
C 6 H s OPOCl 2 ~ C6HsOPO(OCsHI7h + 2 HCI (C)

(C6HsOhPOCI + C S H 17 0H ~ (C6HsO)2PO(OCsHI7) + HCI (D)

The mixture modified in this way could be analyzed by means of gas chromatography using
a CHROM 5 apparatus (Laboratorni pfistroje, Prague) equipped with a flame ionization detector.
The chromatography was evaluated quantitatively by means of an automatic integrator Com-
puting CI-l00. The chromatography was carried out in a glass column of 1,25 m length and 3 mm
inner diameter, packed with 5% OV 225 on Chromosorb, the temperature was increased from
100 to 260°C at the rate of 6°C per min, and the following carrier gases were used (flow-rate
in cm 3 min -I): nitrogen (20), hydrogen (30), air (500). The quantitative evaluation was carried
out by the method of internal standard (octadecane).
The orientation measurements of the reaction course were based on determination of reactive
chlorine atoms in the reaction mixture (argentometry).
A possible escape of POCI 3 from the reaction mixture was monitored by determination of
phosphorus in the washing bottles by the colourimetric method after mineralization.

RESULTS AND DISCUSSION

The initial composition of the reaction mixture: phenol 2·6542 mol dm- 3 , POC1 3
0·8912 mol dm- 3 (molar ratio phenol:POC1 3 = 3 : 1), MgC1 2 0,0237 mol dm-l,

Collect. Czech. Chem. Commun. (Vol. 54) (1989)

610 Magura, Vojtko, Zemanova, Kaszonyi, I1avsky:

xylene 5'5072 mol dm- 3. The composition changes with time were followed at the
temperatures of 90, 95, 100, and HO°C (Tables I - IV) by independent analyses of
the individual components. The phenyl phosphates are formed by the following
reactions:
kl
C 6H sOH + POCl 3 ~ C 6H sOPOCl 2 + HCI (E)

C 6H sOH + C 6H sOPOCl 2 --.!:.:- (C6HsO)2POCI + HCI (F)

C 6H sOH + (C6HsO)2POCI -~ (C6HsO)3PO + HCI (G)

where kl' k2' and k3 are the esterification rate constants of POCl 3 to the first, second
and third degree, respectively.
For the conditions of a batch reactor, this system is described by a set of five
differential kinetic equations:

r 1 = -dCA/dt = klC~C~ + k2C~ci + k3C~C~ (1)

r 2 = -dCB/dt = klC~C~ (2)
r3 = dCR/dt = kl C~C~ - k2C~C~ (3)
r4 = dCs/dt = k2C~ci - k3C~C~ (4)
rs = dCT/dt = k3C~C~ , (5)

where CA means the phenol concentration, CB is POCl 3 concentration, and CR, Cs,
and CT denote the concentrations of the esters C 6H sOPOCI 2, (C6HsO)2POCI, and
(C 6H sOhPO, respectively.
The equations (1) through (5) represent a simultaneous system of five differential
equations with three unknowns and with two degrees of freedom which can serve
for increasing the accuracy of the results and for their correlation.
Esterifications are generally known to be reversible reactions of the second order 6 •
As, however, in the above-given arrangement hydrogen chloride escapes from the
reaction mixture, the esterifications ofPOCl 3 with phenol become irreversible.
In order to confirm the presumed validity of the kinetic relations of the second
order, the experimental results were evaluated for four versions of calculations, viz:
(i) In Eqs (1) through (5) zero was introduced for X and 1 for Y (formally the first
order equations), (ii) in Eqs (1)-(5) it was X = 1 and Y = 1 (formally the second
order equations), (iii) in Eqs (1)-(5) it was X = 1 and Y = 2 (formally the third
order equations), (iv) in Eqs (1)-(5) it was X = 2 and Y = 1 (formally the third
order equations). The method of non-linear regression was used to find the dispersions

Collect. Czech. Chem. Commun. (Vol. 54) (1989)

Esterification Kinetics of Phenol 611

of concetrations and the mean deviations of the measured and calculated values
(Table V).

TABLE I
The concentration (mol elm - 3) changes of the individual reaction components during the
esterification of POC1 3 with phenol at 90°C

Time
C 6 H s OH POC1 3 C 6 H s OPOC1 2 (C6 H s OhPOCI (C6 H s OhPO
h

0 2'654 0'891 0·000 0'000 0'000

1'5 2'610 0'668 0'150 0'024 0'000
2 2'507 0'535 0'248 0'058 0'000
3 2'467 0'488 0'276 0'077 0'000
4 2'386 0'392 0'346 0'095 0'009
5 2'236 0'223 0'445 0'161 0'013
6 2·142 0'148 0'463 0'165 0'036
7 2'073 0'111 0'427 0'263 0'040
10 1'968 0'079 0'365 0'307 0'090
12 1-886 0'048 0'298 0'400 0'095
16 1·671 0'011 0'187 0'380 0'264
20 1'589 0'000 0'144 0'364 0'334
24 1-499 0'000 0'094 0'316 0'432

TABLE II
The concentration (mol dm - 3) changes of the individual reaction components during the esteri.-
fication of POCl 3 with phenol at 95°C

Time
h C 6 H s OH POC1 3 C 6 H s OPOCl 2 (C6 H s °}zPOCI (C6 H s O)3PO

0 2·688 0'761 0'000 0'000 0'000

0'5 2'632 0'676 0'081 0'003 0'000
2'520 0'510 0'238 0'013 0'000
1'5 2'234 0'097 0'408 0'055 0'000
2 2'162 0'033 0'478 0'100 0'000
2'5 2'152 0'020 0'531 0'110 0'000
4 2'003 0'004 0'425 0'316 0'014
6 1-829 0'003 0'226 0'428 0'103
8 1-663 0'003 0'075 0'454 0'228
10 1'562 0'000 0'012 0'425 0'324
15 1'532 0'000 0'004 0'390 0'366

Collect. Czech. Chem. Commun. (Vol. 54) (1989)

612 Magura, Vojtko, ZemanovA, Kaszonyi, Tlavsky:

The smallest dispersion values as well as the smallest deviation of the measured
and calculated values were obtained in the case where the exponents at the concentra-

TABLE III
The concentration (mol dm - 3) changes of the individual reaction components during the esteri-
fication of POCl 3 with phenol at 100°C

Time
h C 6 H s OH POCl 3 (C6 H s O)POCI 2 (C6H s OhPOCI (C6H s OhPO

0 2'654 0'890 0'000 0'000 0'000

2'400 0'543 0'265 0'065 0'011
1'5 2'213 0'292 0'480 0'104 0'011
2 2·114 0'139 0'612 0'123 0·013
4 1'878 0'049 0'406 0'409 0'019
5 1-666 0'006 0'192 0·618 0'068
6 1'544 0'004 0'062 0'694 0'128
7 1-473 0'000 0'023 0'654 0·208
8 1-416 0'000 0'007 0'593 0·285
9 1'334 0'000 0'005 0'457 0'422
10 1'245 0'000 0'001 0'324 0'559
15 1-131 0·000 0'000 0'140 0'745

TABLE IV
The concentration (mol dm - 3) changes of the individual reaction components during the esteri-
fication of POCl 3 with phenol at 110"C

Time
C 6 H s OH POCl 3 C 6H s OPOC1 2 (C6H s OhPOCI (C6HsOhPO
h

0 2'469 0·919 0'000 0'000 0'000

0'5 2'172 0'545 0'271 0'103 0'000
1 2'095 0'457 0'355 0'113 0'012
1'5 1-895 0'274 0'402 0'206 0'036
2 1-847 0'197 0'481 0'202 0'037
2'5 1'756 0'098 0'551 0'215 0'055
3 1·694 0'037 0'576 0'245 0'060
4 1-481 0'016 0'275 0'554 0'072
5 ]'275 0'013 0'105 0'560 0'240
6 1'216 0·006 0'085 0'523 0'304
7 1-035 0'004 0'022 0'357 0'535
8 0'931 0'000 0'000 0'246 0'672

Collect. Czech. Chem. Commun. (Vol. 54) (1989)

Esterification Kinetics of Phenol 613

tions of phenol and phosphoryl trichloride were equal to one, which confirms the
presumption of the esterification being a second order reaction. Therefore, in the
subsequent evaluation of the experimental results the set of differential equations (1)
through (5) was solved for the value 1 in all the exponents at the concentration terms.
Table VI gives the rate constants obtained by solving Eqs (1)-(5) by means of the
Gauss-Newton method in the Marquardt modification using an SM 30 computer.
From the absolute values of the rate constants it is seen that the esterification to the
first degree proceeds as the easiest step (the substitution of the first chlorine atom in
the POel 3 molecule is the easiest one also from the sterical point of view), the sub-

TABLE V
Determination of the minimum deviation of the measured concentratin data from the calculated
ones in the esterification of POCl 3 with phenol

Values of exponents Mean differences between the

Dispersions
in Eqs (1) through (5) measured and calculated
of
concentration values,
concen trations
x y mol dm- 3
-----------------

o 0'021 0·147
0'020 0'141
2 1 0'045 0'214
1 2 0'048 0'235

TABLE VI
The calculated rate constants and activation energies of the esterification of POCl 3 ith phenol

Rate constants, dm 3 mol- 1 h- 1

Temperature ------------
DC error error error
in kl in k2 in k3

90 0'055 0'005 0'035 0'003 0'013 0'002

95 0'092 0'003 0'058 0'001 0'015 0'001
100 0'135 0·011 0'083 0·004 0'048 0'001
110 0'240 0'030 0'167 0'020 0'087 0'015
------------------------
Activation
energy 84·1 89'3 119'6
kJ mol- 1

Collect. Czech. Chem. Commun. (Vol. 54) (1989)

614 Magura, Vojtko, Zemanovll, Kaszonyi, J1avsky:

stituion of the secolld chlorine atom being slower and that of the third CI atom (with
formation of the triphenyl phosphate required) is the slowest.
Fig. 1 presents· the values of the measured and calculated concentrations values
of all components of the reaction mixture at the temperature of 95°C, and the
agreement between these measured and calculated values can be denoted as acceptable,
hence the equation set (1) through (5) approximately reflects the behaviour of the
phenol-POCl 3 system during the esterification.
The deviation of the experimental values from the theoretical ones can be explained
by the errors of the (exacting) analyses of the reaction mixture as well as by the fact
that the reaction system represents an open system with respect to escape of hydrogen
chloride (i.e. the kinetics of the liquid-phase process can be partially affected by the
diffusion of the hydrogen chloride escaping from the reaction mixture). Another
source of deviations of the measured values from the calculated ones consists in the
fact that the values calculated theoretically from Eqs (1)-(5) reach zero concentra-
tion values only after an infinitely long time, whereas in the experimental measure-
ments these v es are reached after relatively short reaction time.
The val s k1.; k2' and k3 given in Table VI were used for the calculation of the
activatio energies of the esterifications to the first, second, and third degrees by the
method f linear regression; these activation energies are also presented in Table VI.
The temp rature dependence of the rate constants is given in Fig. 2.

-1 r-,---~-----r----.-~

In k;

-3

-5~~---J----~----~~

2'60 2-65 11T.lO'3 2-75

FIo.l Flo. 2
Composition of reaction mixture in esterifica- Temperature dependence of rate constants
tion of phenol with POCI 3 at 9SoC. The
points repreSent the experimental values,
the curves give the calculated values. 1,
o phenol, 2, a POCI 3 , 3, ® C6 H s OPOCI 2 ,
4, () (C6 H s OhPOCI, 5, t) (C6HsOhPO.
cp the phenol concentration, ce concentra-
tions of the other components

Collect. Czech. Chem. Commun. (Vol. 54) (1989)

Esterification Kinetics of Phenol 615
REFERENCES

1. Hempel A.: U.S. 1 840 335 (1932).

2. FMC Corp.: U.S. 3077491 (1963).
3. Genet R. M.: U.S. 3553 155 (1971).
4. Perry J. H.: Chemical Engineers Handbook. McGraw-Hill, London 1963.
5. Magura M., Zemanova E., Vojtko J.: Chern. Prum. 38, (1988).
6. Lebedev N. N.: Chemia a techn%gia zak/adnych organickych a petrochemickych syntez.
p. 227. Alfa, Bratislava 1979.
Translated by J. Panchartck.

Collect. Czech. Chem. Commun. (Vol. 54) (1989)