728

Karel Komers,
Frantisek Skopal,
Radek Stloukal,
Jaroslav Machek

Department of Physical
Chemistry, Faculty of
Chemical Technology,
University of Pardubice,
Czech Republic

Eur. J. Lipid Sci. Technol. 104 (2002) 728737

Kinetics and mechanism of the KOH

catalyzed methanolysis of rapeseed oil for
biodiesel production
The reaction of rapeseed oil with methanol catalyzed by KOH is described by a model
consisting of two sequences of consecutive competitive reactions. The first sequence
expresses the methanolysis of rapeseed oil to methyl esters (biodiesel) whereas the
second sequence describes the always present side reaction-saponification of glycerides and methyl esters by KOH. The proposed chemical model is described (after rational simplifications) by a system of differential kinetic equations which are solved numerically by two independent computing methods. The thus obtained theoretical kinetic and equilibrium results are compared numerically and/or graphically with the experimental parameters. The latter were obtained by the determination of the relevant components in the actual reaction mixture by analytical methods. According to the
experimental results, the proposed reaction scheme is fulfilled with the probability of
ca. 78%. The optimal average rate constants and equilibrium constants of individual
reaction steps of the discussed scheme are introduced. The limitations of the proposed
reaction model are discussed.

Research Paper

Keywords: Rapeseed oil, methanolysis, biodiesel, kinetics, mechanism.

1 Introduction

2 Materials and methods

The authors have been involved for more than ten years
in the theory and practice of biodiesel fuel production by
methanolysis of rapeseed oil catalyzed with KOH [1-3].
The here presented study investigates the kinetics and
mechanism of the given reaction which have not been described in detail yet. Their knowledge is not only of theoretical interest but also necessary for the optimization of
biodiesel production. Freedman et al. [4, 5] presented the
kinetics and final state of methano-, ethano- and butanolysis of cottonseed, peanut, soybean and sunflower oil
catalyzed by sodium hydroxide and methoxide or sulphuric acid. Mittelbach and Trathnigg [6] studied the kinetics of methanolysis of sunflower oil catalyzed with
KOH. Bikou et al. [7] described the effect of water on the
kinetics of cotton oil ethanolysis catalyzed by KOH. In this
study [8] the kinetics of the non-catalytic methanolysis of
soybean oil at 220 and 230 C are discussed. Only Kusdiana and Saka [9] studied the kinetics of transesterification of rapeseed oil, but without the application of a catalyst in supercritical methanol.

2.1 Theoretical background

Correspondence: Karel Komers, Department of Physical

Chemistry, Faculty of Chemical Technology, University of
legi 565, 532 10 Pardubice, Czech Republic.
Pardubice, Cs.
Phone: +42-40-603-7055, Fax: +42-40-603-7068; e-mail:
karel.komers@upce.cz

2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

The reaction of rapeseed oil (RO) and solution of KOH in

methanol (M) proceeds according to a simple stoichiometric equation:
RO + 3 M = G + 3 E

(1)

With G = glycerol and E = methylic esters of RO

biodiesel. However, the physico-chemical mechanism of
the reaction is complicated because:
1) Rapeseed oil is a large-scale mixture of more than 100
substances (see [3], chapter 1). Its main part consists of
triacylglycerols (TG) of four fatty acids (FA), namely oleic,
linoleic, linolenic and palmitic acid. The rest (only a few
wt-%) is composed by diacylglycerols (DG) and monoacylglycerols (MG) of these FA, free FA, water (W) and
traces of other substances.
2) Except for the main process, i.e. the methanolysis, all
present substances can take part in various different
reactions with the methanolic solution of KOH. The dominant side reactions are the saponification of TG, DG,
MG and E as well as the neutralization of free FA by KOH
(salification).
3) Methanolysis of rapeseed oil is a set of simultaneous
reactions and is heterogeneous during the whole course.
The reaction mixture consists in each case of two (or
more) liquid phases [10, 11]. As the reaction mixture is
very heterogeneous, the kinetics (equilibrium) of
0931-5985/2002/1111-0728 $17.50+.50/0

Eur. J. Lipid Sci. Technol. 104 (2002) 728737

methanolysis can be influenced by different combinations
of chemical and physical processes and states. The complete mechanism of the reaction is then given by the rate,
range and combinations of particular reaction steps. It
was studied on the basis of the experimentally determined compositions of the actual and final reaction mixtures at different conditions (temperature, initial composition), considering the fact, that the reaction can be influenced by either chemical (i.e. the chemical reactions) or
physical (e.g. diffusion, adsorption, reaction on phase interface, hydrodynamic conditions, density, viscosity etc.)
parameters, in the most complicated case by their combination.
In this work we consider the chemical reactions as the determining reaction parameters.
Nevertheless, it was necessary to presume several simplifications. However, all of them have a real basis, as will
be shown in the following.

Biodiesel from repeseed oil, methanol and KOH

729

2.1.2 Presumed model of the reaction of

rapeseed oil and the solution of KOH in
methanol
We presume a reaction scheme with two sequences of
consecutive competitive reactions. The first sequence describes the main part of the process namely methanolysis of TG to methyl esters, the second describes the side
reaction saponification of glycerides and methyl esters
by the catalyst to potassium soaps. The reaction scheme
is expressed by the stoichiometric equations (2-12). In the
equations following abbreviations are used:
OH = OH, X = CH3O, DG = anions of DG, generally
CH2OCOR1.CHOCOR2.CH2O or CH2OCOR2.CHOCOR1.
CH2O or CH2OCOR1.CHO.CH2OCOR2, where R1, R2
are rests of the four fatty acids mentioned above, MG
and G = anions of MG and G, A = A (anions of potassium salts of fatty acids of rape oil).

2.1.2.1 Formation of methoxide X

2.1.1 Proposed simplifications
For the theoretical processing of the mechanism we assume that:
1) Of the above mentioned four FA only TG are present in
the initial reaction mixture, thus RO TG.
2) Only two reactions from all theoretically possible are
proceeding: the methanolysis of glycerides (TG, DG, MG)
with formation of E and G and saponification of TG, DG,
MG or E by KOH with formation of potassium salts of the
mentioned FA (soaps, KA) and G or M.
3) All the present isomers of TG react in the given type of
reaction (alcoholysis, saponification) with the same rate
and mechanism. The same is valid for isomers of DG, MG
and E, but with different rates in every group of isomers.
This simplification is possible, as methanolysis and
saponification take place at the carboxyl group of the FA,
whereas the velocities of these reactions depend only
little on the length of the hydrocarbon chain, number or location of the double bonds in the various FA of the oil.
4) Methanolysis is catalyzed by OH or CH3O ions. Concentrations of OH and CH3O ions are much smaller than
those of TG and M and they would stay constant if
methanolysis was the only reaction taking place. The particular reaction steps may be reversible or irreversible.
In saponification, OH ions are the reactants and their
concentration decreases with increasing reaction times.
Formed KA practically cannot be esterified by free M, DG
or MG. Therefore saponification can be considered as irreversible.

k1
M + OH = X + W
k1r

(2)

2.1.2.2 Methanolysis
k2
TG + X = DG + E
k2r

(3)

k3
DG + M = DG + X
k3r

(4)

k4
DG + X = MG + E
k4r

(5)

k5
MG + M = MG + X
k5r

(6)

k6
MG + X = G + E
k6

(7)

k7
G + M = G + X
k7r

(8)

2.1.2.3 Saponification
k8
E + OH M + A

(9)

k10
DG + OH MG + A (11)

k9
TG + OH DG + A (10)
k11
MG + OH G + A

(12)

whereas = depicts an equilibrium (reversible) reaction,

indicates an irreversible (only one way) step and ki or
kir are the reaction rate constants of the direct or reverse
steps of the given reaction. In the reversible reaction the
ratio ki/kir defines the equilibrium constant of the given reaction Ki. The irreversible step is the reaction with Ki ,
i.e. ki >> kir (at a given pressure and temperature). Its final
state is characterized by the practically full exhaustion of
the reactant with lower initial concentration.

730

Komers et al.

Eur. J. Lipid Sci. Technol. 104 (2002) 728737

The scheme presumes that methanolysis of TG to G is

catalyzed by methoxide X which is primarily formed by reaction (2) and regenerated by the reactions of M (4), (6)
and (8) with anions of diglycerides, monoglycerides and
glycerides (DG, MG and G). According to step (2) an
important influence of water in the reaction mixture must
be expected.
The methanolysis proceeds in liquid medium (i.e. at a
practically constant volume) and at constant temperature
and pressure. Therefore its common kinetics could be described, with respect to the rules of the formal reaction kinetics for the isothermal-isochoric reactions, by means of
the molar concentrations [I] (mol.dm3) of all 13 assumed
reactants M, OH, X, W, TG, DG, E, DG, MG, MG, G, G
and A, thus by a system of 13 differential kinetic equations
of the type concentration-time d[I]/dt = .. .
For the solution of kinetic problems it is advantageous to
express the amounts of the reactants in dimensionless
relative concentrations. In our system of rate equations,
the initial concentration of TG, i.e. [TG](t=0) [TG]o = a,
was used as the norm for all reactants except of M, X and
E. For these components the initial concentration of M,
i.e. [M]o = b was chosen as the norm. Thus, the following
relative concentrations with the values in the interval (0;
1) were defined as follows:
TG = [TG]/a ; DG = [DG]/a ; MG = [MG]/a ;
G = [G]/a ; A = [A]/a ; OH = [OH]/a ;
W = [W]/a ; M = [M]/b ; X = [X]/b ; E = [E]/b

(13)

However, it is known that in such complicated reaction

schemes rarely all reaction steps influence the real reaction rate to the same extent. Generally some of them are
dominant with respect to their great or small velocity in
comparison with the other steps. We assume the same in
the proposed scheme for following reasons:
1) The alkaline-catalyzed methanolysis of the rapeseed
oil takes from several tens of minutes to several hours
(according to ratios n and p) at room temperature till it
reaches an equilibrium. On the other hand the formation
of methanolate X, i.e. the exchange of proton between M
and OH by reaction (2) is a matter of seconds [2]. Therefore
dW/dt = 0 W const.

(14)

2) Similarly we suppose that also all other exchanges of

protons between anions DG, MG, G ,X and the neutral
molecules M, DG, MG, G, i.e. reactions (4), (6) and (8),
are in both steps much faster than the reversible transformations of TG, DG, MG by X to E and DG, MG, G, i.e. reactions (3), (5) and (7), and much faster than all the irre-

versible saponifications (9-12). In other words, we presume that

k2 , k2r << k3, k3r ; k4, k4r << k5, k5r ; k6, k6r << k7, k7r ;
k3, k3r, k5, k5r, k7, k7r > k8, k9, k10, k11
(15)
On this basis the stationary state for following reaction
components is valid
d[DG]/dt = d[MG]/dt = d[G]/dt = d[X]/dt = 0

(16)

Application of these steady states leads to following expressions:

DG = X.(k2.TG + k3r.DG)/(k2r.E + k3.M)

(17a)

MG = X.(k4.DG + k5r.MG)/(k4r.E + k5.M)

(17b)

G = X.(k6.MG + k7r.G)/(k6r.E + k7.M)

(17c)

X = (k1/k1r).M.OH/W = K1.M.OH/W

(17d)

3) With respect to inequalities (15) and because relative

concentrations of all compounds are mostly in the interval
(0.01; 1), following inequalities can be further presumed:
k3r . DG >> k2 . TG ; k3 . M >> k2r . E ; k5r . MG >> k4 . DG ;
k5 . M >> k4r . E ; k7r . G >> k6 . MG ; k7 . M >> k6r . E (18)
Using the simplifying conditions 1), 2) and 3) in the complete reaction scheme (2)-(12) we obtain a simpler reaction scheme:
TG + M + OH = DG + E + OH

(19)

DG + M + OH = MG + E + OH

(20)

MG+ M + OH = G + E + OH

(21)

E + OH = A + M

(22)

TG + OH = A + DG

(23)

DG + OH = A + MG

(24)

MG + OH = A + G

(25)

which can be described by the system of rate equations

for only 8 reaction components (TG, DG, MG, G, E, M,
OH, A) in the form of differential kinetic equations, type
relative concentrationtime:
-dTG/dt = b.OH.(k2`.TG.M - k2r`.DG.E) + a.k9.TG.OH (26)
-dDG/dt = b.OH.(-k2`.TG.M + k2r`.DG.E + k4`.DG.M k4r`.MG.E) +
(27)
+ a.OH.(k10.DG - k9.TG)
-dMG/dt = b.OH.(-k4`.DG.M + k4r`.MG.E + k6`.MG.M k6r`.G.E) +
+ a.OH.(k11.MG - k10.DG)
(28)
-dG/dt = b.OH.(-k6`.MG.M + k6r`.G.E) - a.k11.MG.OH (29)

Eur. J. Lipid Sci. Technol. 104 (2002) 728737

Biodiesel from repeseed oil, methanol and KOH

-dM/dt dE/dt = a.OH.(k2`.TG.M - k2r`.DG.E + k4`.DG.M

- k4r`.MG.E +
+ k6`.MG.M - k6r`.G.E -k8.E)
(30)
-dOH/dt dA/dt = b.k8.E.OH + a.OH.(k9.TG + k10.
DG + k11.MG)

(31)

and in form of balance equations, type relative concentration-relative concentration:

1 - (TG + DG + MG + G) = 0

(32)

M+E=1

(33)

p - (OH + A) = 0

(34)

n.E - [3 - (3.TG + 2.DG + MG + A)] = 0

(35)

Equations (32-35) are valid in every moment t (0; ) of the

reaction.
Reaction rate constants ki` and kir` have the following definitions:
k2` = k2.K1/W ; k2r` = k2r.K1/(K3.W)
k4` = k4.K1/W ; k4r` = k4r.K1/(K5.W)
k6` = k6.K1/W ; k6r` = k6r.K1/(K7.W)
[1/(time.concentration)]

(36)

where Ki are the equilibrium concentration constants of

the reversible reaction steps of the common reaction
scheme (2)-(12)
K1 = k1/k1r = X.W/(M.OH) ;
K2 = k2/k2r = DG.E/(TG.X) ; K3 = k3/k3r = DG.X/(DG.M)
K4 = k4/k4r = MG.E/(DG.X) ; K5 = k5/k5r = MG.X/(MG.M)
K6 = k6/k6r = G.E/(MG.X) ; K7 = k7/k7r = G.X/(G.M) (37)
The initial relative concentrations of the reaction components are:
TGo = 1 ; Mo = 1 ; OHo = c/a = p ;
DGo = MG o = Go = Eo = Ao = 0

(38)

The stationary relative concentration of water W = [W]/a

is, regarding (14) small and practically constant. Its value
is in the interval (0; q/a). The initial molar concentration of
W in the reaction mixture TG + (M+KOH) is q = q1 + q2 +
(mol.dm3). Quantities q1 or q2 are concentrations of water
from the dosed (M + KOH) or RO, is the range of the reaction (2) of KOH with M in equilibrium. With respect to
the definition of K1 (37) is the value of given by the equation

731

analysis of the reaction mixture at t = , i.e. in its final

state (for the reversible reaction in its equilibrium) than in
its course [12-15].
At the end of the reaction it generally holds for all reaction
partners that d[I]/dt = 0. The composition of the equilibrium reaction mixture is dictated (besides initial composition, temperature, pressure etc.) only by the equilibrium
constants (Ki) of all simultaneous steps (i.e. by ratios of
relevant rate constants ki /kir) and is therefore independent on time. In irreversible reactions, i.e. reactions with
Ki , the final concentrations of all components are given by the reactant with the smallest initial concentration;
its final concentration being namely zero. The dependences of the final (equilibrium) concentrations of the reaction components vs. the ratios of the initial concentrations of the reactants n and p, can be sometimes advantageously used for the (partial) explanation of the reaction
mechanism. This method of final concentrations was
successfully used in the analysis of kinetics and mechanism of several simpler reactions similar to the studied
methanolysis [12-15].
The equilibrium concentration constants Ki for the reversible reaction steps of the given reaction scheme (2)(12) are defined in (37). The saponification steps (22) to
(25) irreversibly decrease the concentration of OH in the
reaction mixture. Besides, initial concentration of KOH (as
a catalyst) is in the discussed methanolysis always so
small that it holds c 3a. Therefore at the end of the reaction (if reactants TG, M and KOH are waterless) it
holds:
OH = X = Y = U = Z = W = (for t ) = 0

(40)

The combination of (37), (32) and (33) gives the relation

TG vs. E in the form
TG = 1 / {1+K2`.(1-E)/E + K2`.K4`.[(1-E)/E]2 +
K2`.K4`.K6`.[(1-E)/E]3}

(41)

in which K2, K4 and K6 represent the products of pairs of

original equilibrium constants (37).
K2.K3 = DG.E/(TG.M) = K2` ; K4.K5 = MG.E/(DG.M) =
K4` ; K6.K7 = G.E/(MG.M) = K6`
(42)
Relations DG vs. (TG, E), MG vs. (TG, E) and G vs. (TG,
E) are
DG = K2`.TG.(1-E)/E

(43)

MG = K2`.K4`.TG.[(1-E)/E]2

(44)

2.1.2.4 Final state of reaction

G = K2`.K4`.K6`.TG.[(1-E)/E]3

(45)

Often informations about the kinetics and mechanism of a

complicated reaction can be obtained more simply by the

By substitution of (41) and (42) into (35) we obtain the desired dependence n vs. E

= ([K1.(b + c) + q1 + q2] - {[K1.(b + c) + q1 + q2]2 4.(K1 - 1).K1.b.c}1/2) / [2.(K1 - 1)]

(39)

732

Komers et al.

1 E
1 E 2

+ K 2 ` K 4 `
3 + 2 K 2 `

1
E
E
n = 3
+ p (46)
2
3
E
1 E
1 E
1 E

1 + K 2 ` E + K 2 ` K 4 ` E + K 2 ` K 4 ` K 6 ` E

which is, besides K2`, K4` and K6` also the function of ratio c/a = p.
By means of equations (41)-(45) the values of n, TG, DG,
MG and G can be theoretically calculated for every chosen E (0; 1) at given combination of K2`, K4`, K6` and p.
The corresponding value of M can be obtained from (33)
as M = 1-E.

2.2 Experimental
2.2.1 Chemicals
The sources and quality of rape oil, methanol and KOH
used are described in [3]. Concentrated hydrochlorid acid
of p.a. quality, 36 wt-% aequous solution, was from
Lachema, Brno, CZ. The solvents for HPLC: Acetonitril,
Lichrosolv were purchased from Merck (Praha, Czech
Republic), 2-propanol and n-hexane, gradient grade for
LC, were purchased from Riedel-de Haen (Seelze, Germany).

2.2.2 Realisation of experiments, drawing of

samples and monitoring of reaction
All experiments were realized at a constant temperature
from 22.7 to 22.8 C and carried out in a thermostated
batch reactor.
The individual experiments differed in the initial reaction
mixture by molar ratios of M and TG (n = b/a), of KOH and
TG (p = c/a) and of W and TG (w = q/a).
The value of W was given by 1), the water content in KOH
(q1), 2) in the reaction of KOH with M (), 3) the water content in RO (q2) and 4) neutralization of free fatty acids in
used RO (q3). Thus it holds w = (q1++q2+q3)/a.
The batch reactor was realized by a closed glass double-mantled vessel. On the top of the vessel there was a
filling opening closed with a rubber plug resistant against
the reaction mixture and vapors of M. Through the next
opening with a similar plug a sound of a digital thermometer was placed. First, the rapeseed oil was
weighed and put into the vessel and an effective electromagnetic stirrer covered with teflon was turned on. The
stirrer had to be able to homogenize the reaction mixture
also during the first 2-3 min, when it is very viscous. To the
thermostated and vigorously mixed TG the calculated volume of the solution of M with the chosen content of KOH
(thermostated to the same temperature) was added by

Eur. J. Lipid Sci. Technol. 104 (2002) 728737

means of a polyethylene syringe [3]. The end of dosing of
the solution (M + KOH) was taken as the start of the reaction (t = 0). The volume of the reaction mixture was practically constant during the reaction; so the reaction was
taken as isochoric isothermal. The reaction time was
measured in the first 40 min with an electronic
stop-watch, the following considerably longer time periods by an exact electronic watch. During the reaction,
samples (2-20 cm3) of the reaction mixture were taken by
a syringe through a rubber plug closing the opening of the
reactor. At the beginning of the reaction samples were
taken in approximately 1 min intervals, later in longer time
periods. The number of samples was limited by the total
volume of the reaction mixture, which was 243-320 cm3.
That corresponds to maximum of about 15 samples. In all
experiments the last sample was taken when the composition of the reaction mixture was identical with the one
previously taken. This composition was considered as the
composition of the final (equilibrium) reaction mixture.
Two methods of stoppage of the reaction in the taken
sample were used:
1) Stoppage of reaction by dilution with the mixture
ethanol:toluen = 1:1
The sample (ca. 1-2 cm3) taken from the reaction mixture
by means of a syringe was quickly injected into the previously weighed and vigorously mixed surplus (about 1:20
by volume) of the diluent. The resulting mixture was
weighed again and from the difference of weights the
mass of the sample was calculated. The mixture was
stored in the refrigerator at temperature 0-5 C until analysis. In this mixture the concentrations of OH and A were
determined by acidimetric titration (see [3]).
2) Stoppage of reaction by acidification
The sample of the actual reaction mixture was quickly
mixed with the surplus of concentrated hydrochloric acid
(about 2.5 times in moles regarding the initial KOH concentration in the sample). The pH value of the mixture after neutralization was 2-3. The neutralization was realized
in a glass test tube of volume about 50 cm3 with a side
tube (used for later demethanolysis) closed by rubber
plugs. After shaking, the mixture was turbid by the precipitate of KCl.
Such modified sample was demethanolyzed by a combination of mixing, vacuum and increased temperature of
ca 40 C. After the complete removal of M, the residual
fluid spontaneously separated into an upper ester phase
(EP) and a lower glycerol phase (GP). EP contains all TG,
DG, MG, E and free FA. GP contains only G, W, the rest
of HCl and its potassium salt. The concentration of M was
not determined but calculated.

Eur. J. Lipid Sci. Technol. 104 (2002) 728737

2.2.3 Analytical methods

Analytical methods used for the analyses of above mentioned reaction components in EP and GP and calculation
of the composition of the actual reaction mixtures are described in detail in [1] and [3].

2.2.4 Solving of kinetics of the reaction model

The proposed course of the studied methanolysis is described quantitatively by the system of 8 differential kinetic equations (4 independent) concentration-time (26-31)
and 4 algebraic balance equations concentration-concentration (32-35) resulting from appropriate stoichiometric
equations (19-25). All these equations are expressed in
nondimensional relative actual concentrations of the reaction components. No differential kinetic equation concentration time can be integrated. Therefore their solving had to be done numerically by PC by two independent
computing methods:

Biodiesel from repeseed oil, methanol and KOH

733

2.2.4.2 Method GEPASI [16-18]

This computing program is freely available on Internet
(http://gepasi.dsb.aber.ac.uk./softw/gepasi.html). Its use
is simpler because it requires only the input of the system
of stoichiometric equations describing the studied model,
initial concentrations of all reaction partners and the estimations of all rate constants. The use of special rate
equations for some reaction steps (some of them typical
for biochemical reactions are even preprogrammed) and
the simulation of heterogeneous reactions is also possible. The simulated theoretical model can be compared
with the experimental set (or sets) of dependences concentration-time for one (or all) reaction components. In
this case the output includes optimal values of the rate
constants for the given reaction scheme and the list of
theoretical dependences concentration vs. time calculated by means of these rate constants in a table form. The
objective criterium of correctness of the studied model is
the value of sum of squares of deviations. The theoretical
and experimental results can be also compared graphically on the computer screen or on printer, both in colors
and in 2D or 3D execution.

2.2.4.1 Method Runge-Kutta with optimization

This method is based on solving the given reaction
scheme by means of the method Runge-Kutta and optimizing of the kinetic parameters with respect to the given
set of experimental data concentration-time for all or only
for some reaction components (J. Plocek, A. N e mcov,
Department of Process Control and Computing Technics,
Faculty of Chemical Technology, University of Pardubice,
personal communication). Its use requires the input (besides initial concentrations and estimations of max. 25
rate constants) of the given reaction model in form of
max. 50 differential kinetic equations. The output information contains a set of optimal values of all rate constants
of the given scheme, a table of on their base calculated
dependences concentration-time and relative average
difference (error) of the given experiment according to the
selected model - S% as an objective criterium of the correctness of this model. It is given by the formula
m t
S% = { yi(t)exp yi(t)cal / yi(t)exp }*100 / N [%] (47)
i 0
where m is the number of reactants, yi(t) concentration of
component i in time t, exp - experimental value, cal - calculated value and N - number of measurements in interval
(0; t). Hence, S% indicates in % the average relative difference between all experimental and relevant calculated
optimal concentrations of all determined components in
the given experiment. In the case of the full consent of the
model and experiment it holds S% = 0.

3 Results
3.1 Initial conditions
Pure rapeseed oil and the solution of KOH in methanol
were used as initial reaction components. Initial conditions of single experiments vary in the ratio of the initial
molar concentrations of TG (a) and M (b), n = b/a in interval n (0.5; 10) and in the ratio of the initial molar concentration of catalyst KOH (c) and TG, p = c/a in interval p
(0.046; 0.25), which corresponds with 0.29-1.59 wt-% of
KOH regarding the weight of rape oil (TG) as 100%. Tab.
1 contains the values of n, p for all 14 realized complete
experiments.

Tab. 1. Initial ratios of reactants n = [M]o/[TG]o and p =

[KOH]o/[TG]o in experiments No. 1-15 ordered in groups
with decreasing p (i.e. [KOH]o). Closed, mixed and thermostated (22.7-22.8 C) glass reactor.
n
2.0130
3.0007
5.9238
0.9997
2.0233
3.0117
4.0000
6.0032

experiment

experiment

0.2468
0.2449
0.2506
0.1265
0.1225
0.1197
0.1252
0.1251

15
14
13
1
2
3
4
5

1.9735
2.9816
5.9828
1.9882
2.9830
6.0376

0.0775
0.0769
0.7775
0.0461
0.0468
0.0462

9
8
10
11
6
12

0.1462

measured for n = 0.5, 2, 2.5, 3.5, 4, 5, 6, 10 only at t = .

734

Komers et al.

Eur. J. Lipid Sci. Technol. 104 (2002) 728737

Tab. 2. Values of rate constants ki` [dm3.mol-1.min-1] and

of the average difference S% or sum of squares of deviations (SQD) of the experiment No. 2 calculated by the
method Runge-Kutta with optimization (column 1), by the
program GEPASI (column 2) and the average values from
14 experiments (column 3).
1
k2`
k2r
k4`
k4r`
k6`
k6r`
k8
k9
k10
k11

7.779
3.843
8.594
2.528
23.65
0.7029
0.0234
0.1365
0.3504
0.1925

2
5.949
2.980
9.399
7.311
15.18
0.6982
0.0133
0.3436
0.7474
0.4654

3
5.005
3.545
4.929
2.987
29.67
0.7932
0.127
0.194
0.3591
0.727

S% = 16.3 SQD = 6.10-6 S% = 26.1

graphically. An example of these graphic comparisons for

experiment No. 2 is depicted in Fig. 1 using the optimal
combination of the rate constants given in column 1 of
Tab. 2. The value of S% is 16.3%. For comparison, the
method GEPASI gives for the same experiment the optimal combination of the rate constants presented in column 2 of the Tab. 2 with the sum of squares of deviations
6.106.
The average values of the optimal rate constants computed by the Runge-Kutta method for all 14 realized experiments, are given in column 3 of the Tab. 2. The average
value of the objective criterium of the validity of the used
reaction model S% = 22.1%. The average values of the
equilibrium constants of reversible steps K2, K4, K6 computed from the relevant ki` according to (37) are presented in Tab. 3, first line.

3.2 Dependences actual concentration vs. time

3.3 Dependences equilibrium concentration

vs. ratios n and p

The dependences of relative molar concentrations TG,

DG, MG, G, E, A and OH vs. time t were determined for all
experiments. An example of the results for the experiment
No. 2 is given in [3], Tab. 2. By means of the method
Runge-Kutta (section 2.2.4) and based on the experimental dependences concentration vs. time of the measured
reaction components, theoretical relations concentration
vs. time of these components were computed for every
experiment from Tab. 1 using the calculated optimal combinations of the rate constants for the above assumed reaction scheme in the time period 0-20/40 min (i.e. for the
most important part of the reaction). These computed and
experimental dependences were compared tabularly and

The final (equilibrium) concentrations of the measured

components in all experiments (i.e. for all used combinations of ratios n and p) were determined (example see
Tab. 2 in [3]). By their means the values of K2, K4 and K6
could be also calculated. The average values of these
constants are given also in Tab. 3, second line. Using
these two trios of average constants K2, K4 and K6 and
our original computer program the dependences TG, DG,
MG, G, E (at t ) vs. n for p = 0.12 were calculated by
means of relations (41-46) and then compared graphically with experimental dependences measured at the same
conditions. An example of these comparisons for TG, G,
E vs. n for p = 0.12 is shown in Fig. 2.

Fig. 1. Experiment No. 2 (n = 2.0233, p = 0.1225). Comparison of the theoretical dependences of actual relative concentrations TG, DG, MG, Gcal, E, A and OH vs. t , computed with the optimal combination of the rate constants (see Tab. 2, column 1), for this experiment by means of the program Runge-Kutta with optimization (full curves), with the experimental data (points), see [3], Tab. 2. S% = 16.3 %.

Eur. J. Lipid Sci. Technol. 104 (2002) 728737

Biodiesel from repeseed oil, methanol and KOH

735

Fig. 2. Comparison of the experimental (points) and theoretical (full or dashed lines) dependences of final (equilibrium) relative concentrations of TG, Gcal, Gexp, E vs. n at constant p = 0.12 (experiments No. 1-5). Theoretical dependences were
calculated by means of (41-46) and Ki` from (A) rate constans and (B) final concentrations, see Tab. 3.

3.4 Dependence concentration of water

vs. time

4 Discussion
4.1 Correctness of analyses

The concentration of water in the reaction mixture has a

significant influence on the whole course of the described
methanolysis. Therefore in some experiments the dependence of the concentration of water vs. time in the actual
reaction mixture was measured. The experiments No. 13
and 14 were chosen because their initial composition is
used usually in the biodiesel production (n 3 to 6 ; p
0.24). The water content was determined by two independent methods, namely by gas chromatography (GC) (see
[1], section 2.4.3) and by the Karl-Fischer (see [3], chapter 2.9.2) method. Although the results obtained by both
methods are different (the value from the GC determination is always greater), the water concentration (cw) remains during the course of the reaction (except of the initial minute) practically constant. The average determined
values are:
Experiment No. 14: Karl-Fischer: cw = 0.412 0.04 ; GC :
cw = 0.882 0.40
Experiment No. 13: Karl-Fischer: cw = 0.262 0.10 ; GC :
cw = 1.149 0.60 mg of water/g of the reaction mixture.

Tab. 3. Average values of the equilibrium concentration

constants Ki` calculated from the corresponding rate constants ki` and kir`, see (37) , and from the equilibrium (final) concentrations of suitable reaction components, see
(42).
from

K2`

K4`

K6`

rate constants
final concentrations

1.55
1.06

5.18
1.71

36.4
132.8

The correctness of the group of relative actual concentrations of TG, DG, MG. G, E, M and A, determined in the
given experiment by independent methods, can be
checked by the balance equations (32), (34) and (35).
The experimental data (e.g. Tab. 2 in [3]) were substituted
into these relations for every measured reaction time in
every experiment and the average absolute differences D
(in %) between the left sides of these equations and zero
were tested. The values 1 in (32), p in (34) and n * E in
(35) were taken as 100%. From the obtained results we
consider all determined actual concentrations as correct
(D < 5%) with the exception of G. Therefore in every experiment two dependences Gexp vs. t and Gcal vs. t were
determined. The values of Gexp are experimental (i.e. G
determined according to [1], chap. 3.2.5 and [2], chap.
2.8), the values of Gcal were calculated using experimental data of TG, DG, MG and (32).

4.2 Criteria of validation of the presumed

reaction scheme
The validity of the presumed methanolysis model (19-25)
was verified by comparison of:
1) experimental dependences of relative concentrations
of a set of reaction components vs. time with corresponding theoretical dependences calculated for this reaction
scheme using the optimum values of the rate constants
(see section 3.2).
2) experimental dependences of the equilibrium relative
concentrations of the main reaction components (TG, G,
E) vs. ratio n at given ratio p with the corresponding theo-

736

Komers et al.

retical dependences calculated from equations (41-45).

For these calculations average equilibrium constants K2,
K4 and K6 were used from two different sources, namely
equilibrium concentrations and optimal rate constants,
see Tab. 3.

4.3 Dependences concentration vs. time

The average value of S% of all experiments is S% =
22.1%. This means ca 78% agreement of experiment and
theory or 78% probability of validity of the assumed reaction model.
The graphical comparison of the theoretical and experimental dependences (example see in Fig. 1) also shows
a good agreement of the theory and reality of this very
complicated and polyphaseous reaction. The values of
the rate constants for the experiment 2 presented in Tab.
2 show that both used kinetic computing programs (i.e.
Runge-Kutta and GEPASI) give very similar results. The
optimum rate constants of all 14 experiments computed
by the Runge-Kutta method have a dispersion in interval
of approximately one order. This result can be considered
as satisfying with respect to the complicated reaction and
the simplifying presumptions. Besides that, according to
the definitions (36), the rate constants ki`, kir` include the
stationary relative concentration of water W, which is a little different in every experiment (see section 3.4).
Important conclusions can be expressed about the velocities of the single reaction steps: The quickest reesterification step in the proposed scheme is controlled by the
rate constant k6 ; it is about six times greater than constants k2 and k4. The reverse reesterification steps controlled by constants k2r, k4r are slower and by constant
k6r much slower. Saponification is slower than methanolysis (under the used reaction conditions). The saponification of methyl esters is (to our surprise) evidently slower
as of glycerides. This means that the main part of soaps
KA formed in biodiesel production from RO and KOH solution in M is formed by the hydrolysis of TG, DG and MG
and not of E.

4.4 Dependence equilibrium concentrations

vs. ratio n at constant ratio p
Dependences of equilibrium relative concentrations TG,
Gexp, Gcalc and E (t ) vs. n from the experiments 1-5
for p 0.12 and the dependences E, Gexp and M vs. n
from the experiment No. 7 for p 0.14 were determined.
These dependences were graphically and subjectively
compared with the corresponding theoretical dependences calculated using two combinations of 3 equilibrium constants K2, K4, K6 presented in Tab. 3. Fig. 2A,B
show, that the experiment agrees with the theory approx-

Eur. J. Lipid Sci. Technol. 104 (2002) 728737

imately equally well for both combinations of the equilibrium constants.

5 Conclusions
The kinetics and mechanism of a very complicated and in
the whole course multiphase reaction between rapeseed
oil (as a mixture of triglycerides of four FA: oleic, linoleic,
linolenic and palmitic acid) and a solution of KOH in
methanol in a closed, mixed and thermostated batch reactor was studied at a temperature of 22.7-22.8 C. In
sum 15 experiments were realized with molar ratios n =
[M]o / [TG]o in the interval of n (0; 6 ) and molar ratio p =
[KOH]o / [TG]o in the interval of p (0.046; 0.25), i.e. of
0.292-1.59 wt-% KOH owing to TG. From the actual reaction mixture in particular experiments samples were taken
in suitable time periods including the final state. The reaction was stopped by original techniques and the concentrations of TG, DG, MG, G, M, E, A, OH and W in the samples were determined by original analytical methods.
These experimentally determined dependences (concentration vs. time and final concentration vs. n at given p)
were numerically and/or graphically compared with the
corresponding theoretical dependences obtained by PC
solution of the system of kinetic and balance equations
(26-35) valid for the presumed reaction scheme. This
scheme resulted from literary information and from our
own experience with the studied reaction, considering
that the process is controlled only by its chemical and not
by physical and interphase steps. It results from this comparison that the given reaction can be described by the
proposed reaction model with the probability ca. 78% at
given conditions. This scheme can be expressed by the
set of stoichiometric equations (19-25) with optimum rate
constants ki`, kir`, ki and equilibrium concentration constants Ki` presented in Tab. 2 and 3. The validity of this
scheme is supported also by very small and practically
constant (steady state) concentrations of water in the reaction mixture during the whole reaction course.
However, the tested chemical scheme does not describe
the experiments perfectly. The main reason is probably
the neglect of the permanent heterogeneity of the reaction mixture. Errors can arise also from the use of concentrations instead of activities of reactants in the applied
thermodynamic formulas, because the whole process is
running in the mixture of concentrated reactants without
any dilution.
Nevertheless, the described results helped us to optimize
our patented technology of this method of biodiesel production, above all in the adjustment of the initial reaction
mixture composition and in the option of the optimal reaction time at chosen temperature. These parameters decide about the desired composition of the final reaction

Eur. J. Lipid Sci. Technol. 104 (2002) 728737

mixture, i.e. a high yield of biodiesel (E) and G and a minimal content of DG, MG and soaps. Beside this, the right
concentration of water in the reaction mixture affects substantially not only the reaction course but also the duration and perfection of the separation of the final reaction
mixture to biodiesel phase and glycerol phase and their
compositions.
The described kinetic analysis showed us also the antagonistic effect of a majority of the reaction conditions. For
example, the increase of KOH concentration increases
the total reaction rate i.e. the velocity of the consumption
of TG, but more in behalf of the origin of soaps. The same
can be discussed about the increase of the reaction temperature. The most difficult problem is to find out the optimal chemico-physical and simultaneously economical reaction conditions. We hope that this work can help in solving this problem for the methanolysis of RO catalyzed by
KOH. The change of some reaction partners (oil, alcohol,
catalyst) can change totally or partially the kinetics and/or
the reaction mechanism.

Biodiesel from repeseed oil, methanol and KOH

737

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Acknowledgement

[12] K. Komers: Untersuchung des Systems von zwei bimolekularen Folge- und Konkurrenzreaktionen mit reversibler Dis CHT
mutation des Zwischenproduktes. Scient. Papers VS
Pardubice 29 (1973) 161199.

This work was supported by the Czech Ministerium of

Education, Health and Sport, research project CZ
310008/2010/3340.

[13] K. Komers: Solution of the system of two consecutive competitive second order reactions by means of analoge com CHT Pardubice 33 (1975) 11-37 (in
puter. Scient. Papers VS
Czech).

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[Received: February 20, 2002; accepted: June 25, 2002]