Chemical Engineering and Processing 43 (2004) 1487–1493

Kinetic model for the increase of reaction order

during polyesterification
Tapio Salmi a,∗ , Erkki Paatero b, Per Nyholm a
a Laboratory of Industrial Chemistry, Process Chemistry Centre, Åbo Akademi, Biskopsgatan 8, FIN-20500 Turku/Åbo, Finland
b Laboratory of Industrial Chemistry, Centre of Separation Technology, Lappeenranta University of Technology, FIN-53851 Lappeenranta, Finland
Received 29 March 2003; received in revised form 29 January 2004; accepted 29 January 2004
Available online 27 March 2004

Abstract

A simple two-parameter model was proposed for the kinetics of polyesterification reactions. The kinetic model is based on the true reaction
mechanism, i.e. on the shift of the ionic equilibria in the carboxylic acid (RCOOH) protolysis during the reaction, and on the bimolecular
nucleophilic substitution of the protolysed acid with the alcohol (R× OH). The model describes the increase of the reaction order with respect
to the carboxylic acid from 1 to 2 as the esterification proceeds. The rate equation r = kcn cOH was used, where n is a function of the
COOH
carboxylic acid concentration. The kinetic model was tested with the classical data of Flory obtained for diethylene glycol–adipic acid and
the lauryl alcohol–adipic acid reactions. The model provided an excellent description of the data over the entire range of conversions of the
carboxylic acids and it can be extended to new polyesterification systems.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Carboxylic acid; Kinetic model; Polyesterification

1. Introduction
It was shown in the classical work of Flory [1] that the
reaction order of polyesterification reactions increases dur-
ing the progress of the reaction. The esterification reaction
of the carboxylic acid (RCOOH) and the alcohol (R×OH),
RCOOH + R×OH = RCOOR×+ H2O, is of first order with
respect to the carboxylic acid in the beginning of the reac-
tion and second order with respect to the acid in the end of
the reaction. The change of the reaction order was demon-
strated, for example, in the esterification of adipic acid and
caproic acid with several alcohols, such as diethylene gly-
col and lauryl alcohol [1]. By using stoichiometric initial
amounts of the reactants, the total reaction, was determined
to 2 at lower acid conversions, but the order increased to 3
at conversions exceeding 70%. At the intermediate range of
conversions, the rate data cannot be satisfactorily described
by second or third order kinetic models.
+ −
Abbreviations: A, ion pair, A RC(OH)
= 2 RCOO ; MRS, mean residual
square; RCOOH, carboxylic acid; RCOOR, ester; R×OH, alcohol; WSRS,
weighted sum of residual squares
∗ Corresponding author. Fax: 358-2-215-4479.
+ review article of Fradet and Marechal [6], various rate
E-mail address: tsalmi@abo.fi (T. Salmi).
In later studies [2] it has been suggested that the order of
the esterification reactions might be between 2 and 3, but
rate equations having, for example, the reaction order of the
carboxylic acid about 3/2 and that of the alcohol about 1 still
fail to describe the kinetic data at high conver- sions, as
demonstrated by Solomon [3]. According to Fang et al. [4],
the increase of the reaction order is caused by the change of
the dielectric constant and the viscosity of the liquid phase
during the reaction. These authors derived a rate expression
which well describes the experimental data of Flory over the
entire conversion range. The drawback of their model is,
however, that it contains three adjustable pa- rameters in
addition to three equilibrium constants. There- fore, the
model of Fang et al. [4] has not been extensively used.
The change of the reaction volume due to removed water
is an important issue, which is of practical importance in the
design and operation of polyesterification reactors. A simple
approach is to assume instantaneous evaporation of water,
but even more sophisticated calculations have been applied.
In case that the amount of water liberated is measured during
the course of experiment, in it can easily been taken into
account in the determination of kinetic parameters [5]. In the

0255-2701/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.01.006
1488 T. Salmi et al. / Chemical Engineering and Processing 43 (2004) 1487–1493
equations are critically evaluated and simple equations for
volume change are presented.
It is evident that there is a need of a simple rate equation
for engineering purposes, a rate equation, which is able to
describe the polyesterification over wide ranges of conver-
sions. In the present work, a new rate equation is developed,
which predicts the increase of the reaction order in polyester-
ification. The rate equation is demonstrated with the ester-
ification data of Flory [1]. We have selected the classical
data of Flory, since these data are even nowadays presented
in textbooks to illustrate polyesterification kinetics and the
dilemma of a changing reaction order.
2. Mechanism and kinetics of esterification
In this section we consider the polyesterification mech-
anism and kinetics in systems, from where the reaction
product, water is continuously and instantaneously removed.
Thus, the stirring of the reaction system is assumed to be
efficient enough to suppress mass transfer limitations. The
first step in esterification is the autoprotolysis of the car-
boxylic acid. In the absence of a catalyst the carboxylic acid
itself acts a protolysing agent [4]
RCOOH + RCOOH = RC(OH)2+ + RCOO− (1)
In the beginning of the reaction, the cations and anions
formed in reaction (1) co-exist as separate ions. As the poly-
merisation proceeds, and the reaction milieu is dominated by
the polymers, the protolysis reaction gives predominantly an
ion pair
RCOOH + RCOOH = RC(OH)2+RCOO−(A) (2)
The protolysis reactions (1)–(2) are rapid; the rate determin-
ing step in the esterification is the nucleophilic attack of the
alcohol to the cation (RC(OH)2)+ or to the ion pair (A). The
subsequent reaction steps are presumed to be rapid. Thus, all
steps after (1) and (2) can be lumped together, and reac- tions
(3) and (4) are obtained:
RC(OH)2 + + R× OH = RCOOR× + H2 O( ↑ ) + H+ (3)
+ − × ×
RC(OH)2 RCOO + R OH = RCOOR + RCOOH
+ H2O( ↑ ) (4)
where the arrow denotes that the water formed is removed
from the system by continuous bubbling of an inert gas (e.g.
nitrogen) and application of a vacuum. In the beginning of
the reaction, step (3) dominates, but as the reaction proceeds,
the ion pairs (A) are formed, and the influence of step (4) on
the overall kinetics increases. If the amount of water is small,
reactions (3)–(4) can be treated as irreversible reactions, the
rates of which are given by Eqs. (5) and (6), respectively
The total rate of esterification is
r = r3 + r4 (7)
Since steps (1)–(2) are presumed to be rapid, the quasi-
equilibrium hypothesis is applied on them
cRC(OH)2 cRCOO
K1 = 2 (8)
cRCOOH
cA
K2 = 2
(9)
c RCOOH
In the absence of water, the concentrations of the cations
and anions generated in step (1) are approximately equal,
i.e. cRC(OH)2 = cRCOO, and the unknown concentrations
cRC(OH)2 and cA are obtained from (8) and (9)
1/2
cRC(OH)2 = K1 cRCOOH (10)
cA = K2c2 (11)
RCOOH
The expressions (10)–(11) are inserted in rate Eqs. (5)
and (6), and the overall rate Eq. (7) finally becomes
1/2
r = (k3 K1 + k4 K2 cRCOOH )cRCOOH c× R× OH (12)
It should be kept in mind that the constants K1 and K2 are
strictly speaking dependent on the mixture composition.
Rate Eq. (12) can qualitatively explain the experimental ob-
servations: in the beginning of the reaction K11/2 is larger
than K2cRCOOH and the reaction is of first order with respect
to the carboxylic acid, in the end of the reaction K2cRCOOH is
larger than K1/2 and the reaction is second order with respect
1
to the carboxylic acid.
The main disadvantage of rate Eq. (12) is that constants
K1 and K2 are functions of the liquid-phase properties. A de-
scription of the changes of K1 and K2 inevitably increases the
number of parameters in the system. In the characterisation
of industrial polymerisation processes, the basic data con-
sists typically of the acid numbers, i.e. the measured conver-
sions only. Therefore, our goal is to describe the esterifica-
tion kinetics with a global model being as simple as possible.
We thus apply a semi-empirical approach to rate Eq. (12),
and approximate the term in the parenthesis by a power-law
expression kcn−1 The exponent (n) includes the effects
RCOOH
from the shift of the ionic equilibria and the changes of the
component activity coefficients. The rate Eq. (12) becomes
n
r3 = k3 cRC(OH)2 cR× OH (5)
r4 = k4 cA cR ×× OH (6)
r = kcRCOOH c× R× OH (13)
where the exponent n is 1 in the beginning of the reaction
and it approaches the limiting value of 2 as the equilibrium
is attained.
The basic task is to find a suitable empirical function for
the exponent to provide a smooth increase of the reaction
order. We assume that the increase of the reaction order is
proportional to the reaction order itself and to the change of
the carboxylic acid concentration:
dn = −anq dcRCOOH (14)
 T. Salmi et al. / Chemical Engineering and Processing 43 (2004) 1487–1493 1489

where a is a proportionality coefficient and q, empirical ex- n = [1 − (1 − 21−q)X]1/(1−q) (17b)

ponent. Integration of Eq. (14) with the limits cRCOOH =c0, n
1 =and cRCOOH c∗ ,=n 2, =where c0 and c∗ denote the The behaviour of function (17), with different values of q, is
initial and equilibrium concentrations (i.e. concentration of illustrated in Fig. 1. The figure shows that the rapid increase
the carboxylic group obtained after a long experiment in a of the reaction order towards the value 2 at high conversions
closed system, where the equilibrium is attained), respec- can be obtained by selecting a sufficiently high value of q.
tively, gives the value of parameter a: For stoichiometric initial amounts of the carboxylic acid
ln 2 and the alcohol, the concentrations in Eq. (13) are always
a= , q=1 (15a) equal, cRCOOH c=R× OH c,=and rate Eq. (13) is simplified to
c0 − c∗

(q − 1)(1 − 21−q) r = kcn+1 (18)

a= , q 1 (15b)
c0 − c∗ For a well-stirred (semi)batch reactor, from which the re-

Integration of Eq. (14) from the initial values (n 1, cRCOOH

= action product, water, is continuously and instantaneously
c0) to general
= values (n, c) and insertion of the expressions removed, the mass balance equation of= the non-volatile re-
for the constant a give the following equations for n: actant (e.g. carboxylic acid, RCOOH A) can be written as
∗ dnA
n = 2(c0−c)/(c0−c ), q = 1 (16a) = r AV (19)
dt
Σ Σ1/(1−q)
n = 1 − (1 − 2 1−q c0 − c where nA is the amount of substance and V is the liquid
) , q 1 (16b)
c0 − c∗ volume. Inserting the concentration, nA = cAV and differ-

entiating Eq. (19) gives after rearrangement

As the conversion of the acid is denoted by X, X = . Σ
(c0–c)/c0, and the equilibrium concentration c∗ is assumed dcA dV/dt
= rA − c A (20)
to be zero (water is evaporated from the system and thus a dt V

complete conversion of the carboxylic group is obtained), To progress further, an assumption concerning the volume
Eq. (16) is simplified to change is needed. By assuming that the reaction mixture
n = 2X (17a) contains the carboxylic acid, the alcohol and the ester and
Fig. 1. The dependence of the reaction order (n) on the conversion (X) of the carboxylic acid according to Eq. (17) for different values of the parameter (q).
1490 T. Salmi et al. / Chemical Engineering and Processing 43 (2004) 1487–1493

that the contributions of partial molar volumes are negligible, The values of y and the conversion (X) are related by X =
it can be shown that the volume is updated from the formula 1 − y. Integration of Eq. (25) yields
y

V = αnA + βn0A (21) ∫ dy

= kt (26)
The coefficients α and β are explained in Appendix A. The F(y) = − cnyn+1
1 0
expressions nA =cAV and n0A c= 0AV0 are inserted in Eq. By choosing a suitable value of q and carrying out the inte-
(21) and the differentiation dV/dt is carried out. The update gration according to Eq. (26) numerically from y = y0 to the
of the liquid volume is experimental points y(t), a plot of F(y) against t should give a
V βc0A straight line. Alternatively, the original differential Eq. (25)
= (22)
V0 1 − αcA is solved numerically and non-linear regression analysis is
and the balance equation becomes applied directly to the y − t data.
dcA
= rA(1 − αcA) (23)
dt 3. Application of the rate equation on the data of P.
Parameter α is thus a measure of the importance of the Flory
volume change. A rough estimate of it is obtained from the
molar masses the reactants and the esterification product We tested the proposed rate equation with the classical
(see Appendix A). For the data which will considered in the data of Flory [1], on the kinetic results obtained in polyester-
sequel, the role of the correction term αcA is not im- portant ification of adipic acid with diethylene glycol at 166 ◦C and
and it will be approximated to unity. The reaction
in esterification of adipic acid with lauryl alcohol at 202 ◦C.
stoichiometry gives rA –r,= the subscript (A) is omitted, and The data are presented in Tables I and II of the original ref-
equation becomes erence [1], and the normalised concentrations of adipic acid
dc versus the reaction time are shown in Figs. 2 and 3. The cor-
= −r (24) responding test plots for a third order reaction, 1/(1−X)2 =
dt
1/y2 versus t were prepared by Flory [1], and these plots
A dimensionless concentration (y) is introduced, y = c/c0,
were straight lines only for conversions X > 0.8, depend-
and a combination of Eqs. (18) and (24) give
ing slightly on the specific chemical cases under consider-
dy ation. On the other hand, at the initial stage of the reac-
= −kcny0 n+1 (25)
dt tion the plots of a second order reaction. 1/(1 − X) versus

Fig. 2. Polyesterification kinetics of adipic acid with diethylene glycol at 166 ◦C according to Flory [1]. The continuous lines represent model Eqs. (17)
and (25).
 T. Salmi et al. / Chemical Engineering and Processing 43 (2004) 1487–1493 1491

Fig. 3. Polyesterification kinetics of adipic acid with lauryl alcohol at 202 ◦C according to Flory [1]. The continuous lines represent model Eqs. (17)
and (25).

Fig. 4. The plots F(y) = kt according to Eq. (26) for the polyesterification of adipic acid with diethylene glycol. The data of Flory [1].
1492 T. Salmi et al. / Chemical Engineering and Processing 43 (2004) 1487–1493

t gave straight lines, but failed to describe the high conver- Table 1
sion domain. Solomon [3] prepared the test plot for the reac- Determination of the kinetic parameters of the polyesterification of adipic
tion order 5/2—according to the proposal of Tang and Yao acid with ethylene glycol at 166 ◦C by using the data of Flory [1]
[2]—and even this rate equation was unable to describe the q s (%) k s (%) N M WSRS MRS
data at high conversions [6].
8.4 3.4 0.027 0.8 23 2 0.31 × 10−3 0.15 × 10−4
The plots F(y) versus t according to our model (21) for the 1 – 0.035 5.9 23 1 0.22 × 10−1 0.10 × 10−2
diethylene glycol–adipic acid and lauryl alcohol–adipic acid 8 – 0.027 0.7 23 1 0.34 × 10−3 0.15 × 10−4
reactions are presented in Figs. 4 and 5, respectively. As can 9 – 0.027 0.7 23 1 0.36 × 10−3 0.16 × 10−4
be seen from the figures, straight lines are ob- tained for q- q = 8.4 gives the best fit whereas the other values are shown for com-
values of approximately 709 for the diethylene glycol–adipic parison.
acid reaction and for q-values of approx- imately 6–7 for the
lauryl alcohol–adipic acid reaction. Furthermore, we
Table 2
estimated the rate constant k directly from the primary data, Determination of the kinetic parameters of the esterification of adipic acid
using non-linear regression analysis with Levenberg– with lauryl alcohol at 166 ◦C by using the data of Flory [1]
Marquardt method and numerical solution of the q s (%) k s (%) N M WSRS MRS

differential Eq. (25) with Rosenbrock–Wanner method [7].

The value of q was either fixed a priori or it was estimated 6.4 6.4 0.081 1.7 14 2 0.39 × 10−3 0.32 × 10−4
1 – 0.105 6.0 14 1 0.73 × 10−2 0.56 × 10−2
simultaneously with the rate constant.
6 – 0.082 1.3 14 1 0.41 × 10−3 0.32 × 10−4
The results are summarised in Tables 1 and 2 for the di- 7 – 0.080 1.3 14 1 0.46 × 10−3 0.35 × 10−4
ethylene glycol–adipic acid and the lauryl alcohol–adipic
q 6.4
= gives the best fit whereas the other values are shown for com- parison.
acid systems, respectively. The corresponding fits of the
model to the data are shown in Figs. 2 and 3. The optimal
value q is about 8 for the diethylene glycol–adipic acid reac- and 2) and from the fits (Figs. 1 and 2) of the model, the rate
tion and about 6 for the lauryl alcohol–adipic acid system; equation proposed by us provides an excellent descrip- tion
de facto these integer values could very well be used to de- of the esterification kinetics; the differences between the
scribe the kinetics of the actual systems. These values of q experimental and the calculated conversions were typi- cally
provide a satisfactory description of the rapid increase of the less than 0.5%, and the increase of the reaction order was
reaction order at conversions exceeding 70–80%. As can be predicted correctly.
seen from the statistics of the regression analysis (Tables 1

Fig. 5. The plots F(y) = kt according to Eq. (26) for the polyesterification of adipic acid with lauryl alcohol. The data of Flory [1].
 T. Salmi et al. / Chemical Engineering and Processing 43 (2004) 1487–1493
4. Conclusions
A new empirical rate equation (Eqs. (13) and (16)) for
engineering purposes was proposed for the esterification re-
actions to predict the increase of the reaction order during
the progress of the reaction. The model was based on the es-
terification mechanism (1)–(4) comprising the shifts of the
ionic equilibria (1)–(2) during the reaction. The new rate
equation gave an excellent description of the classical es-
terification data of Flory (Figs. 2 and 3). The proposed ap-
proach has perspective in the prediction of polyesterifica-
tion kinetics in laboratory and industrial scale. The effect of
a non-stoichiometric initial ratio of the reactants as well as
the volume contraction the reaction mixture should be in-
vestigated in future, by fitting new experimental data to the
model. We believe that our approach can be used as a source
of inspiration in the engineering modelling of polyesterifi-
cation kinetics.
Appendix A. Nomenclature
a proportionality coefficient, Eq. (14)
c concentration of the carboxylic acid (RCOOH) (mol/l)
c0 initial concentration of the carboxylic acid (mol/l)
c∗ equilibrium concentration of the carboxylic acid (mol/l)
F integral function, Eq. (26) (mol/l)−n
k rate constant (mol/l)−n
M number of parameters
n amount of substance (mol)
n exponent in rate Eq. (13)
N number of experimental observations
q exponent Eq. (14)
r rate (mol/(l min)
1493
s standard deviation of a parameter (%)
t time (min)
V volume
X conversion of the carboxylic acid, X = −1 c/c0
y dimensionless concentration of the carboxylic acid,
y = c/c0
Greek letters
α volume correction parameter (= molar mass of
reactants/densities of reactants − molar mass of
product/density of product) (l/mol)
β volume correction parameter, (= molar mass of
product/density of product) (l/mol)
References
[1] P. Flory, Kinetics of polyesterification: a study of the effects of
molecular weight and viscosity on reaction rate, J. Am. Chem. Soc. 61
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[3] D.H. Solomon, Polyesterification: Kinetics and Mechanism of Poly-
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