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A Method for Esterification Reaction Rate Prediction of Aliphatic

Monocarboxylic Acids with Primary Alcohols in 1,4-Dioxane Based on Two
Parametrical Taft Equation

Article in International Journal of Chemical Kinetics · March 2014

DOI: 10.1002/kin.20845

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A Method for Esterification
Reaction Rate Prediction
of Aliphatic Monocarboxylic
Acids with Primary Alcohols
in 1,4-Dioxane Based
on Two Parametrical Taft
Equation
JÁN VOJTKO, PETER TOMČÍK
Department of Chemistry, Faculty of Education, Catholic University in Ružomberok, Hrabovská cesta 1, Ružomberok
SK-034 01, Slovak Republic

Received 4 December 2012; revised 16 November 2013; accepted 18 December 2013

DOI 10.1002/kin.20845
Published online 7 January 2014 in Wiley Online Library (wileyonlinelibrary.com).

ABSTRACT: Esterification reaction rates of aliphatic monocarboxylic acids with primary alcohols
in 1,4-dioxane as inert solvent were investigated. Acids were esterified with 1-propanol and
alcohols with acetic acid as model reactants at a constant temperature of 60◦ C, at a fixed ionic
strength and pH in a batch reactor with a constant volume. For evaluation of reaction rates, an
exact kinetic equation for the equilibrium reaction was applied. Under these conditions and
for low reactants, concentrations reaction rate depends only on the structure of reactants and,
therefore, can be predicted by a correlation equation with two Taft coefficients (inductive and
steric effects). From these equations, it is possible to estimate the esterification reaction rate
constant for other acid-alcohol pairs. This methodology may also be suitable for other kinetic
systems measured under comparable experimental conditions.  C 2014 Wiley Periodicals, Inc.

Int J Chem Kinet 46: 189–196, 2014

INTRODUCTION contemporary chemical engineering and organic syn-

thesis. Esters such as cetylpalmitate play an impor-
Esterification of aliphatic monocarboxylic acids with tant role as natural waxes [1–3] in the chemical indus-
primary alcohols is a significant chemical reaction in try. Esters are relatively inexpensive solvents (ethyl-,
methyl-, butyl-, or isobutylacetate etc.) and have found
Correspondence to: Peter Tomcik; e-mail: peter.tomcik@ku.sk. novel electrochemical applications as co-solvents for
Contract grant sponsor: Grant Agency of the Slovak Republic.
Contract grant number: VEGA 1/0008/12.
low-temperature electrical double layer capacitors [4].

C 2014 Wiley Periodicals, Inc. Methyl esters of fatty acids (FAME) represent an
190 VOJTKO AND TOMČÍK

ecological biofuel for diesel engines improving their where kE is an esterification rate constant and kH is the
combustion performance [5–8]. Production of FAME rate constant of ester hydrolysis.
has increased today together with the number of en- The thermodynamic equilibrium constant K of es-
gines suitable for biofuel. In addition, esters are the terification is defined as (assuming equal activity coef-
major source of flavors and/or fragrance in flowers and ficients of all species)
fruits. These nontoxic natural products are included
in the FEMA GRAS program and are produced artifi- kE
K = (3)
cially in large amounts, serving as food and cosmetic kH
additives [9–12].
Because of the great diversity of esters and the fact and Eq. (2) can be rewritten as
that esterification is an equilibrium reaction, it is nec-  
essary to know the reaction rate for specific pairs of 1
voverall = kE cAcid cAlcohol − cEster cWater (4)
alcohols and acids. The reaction rate is a crucial re- K
action parameter, especially to determine the required
catalyst loading as well as for estimating the energy re- The differential equation, Eq. (4), can be integrated
quired to evaporate the water or esterification products (see Appendix) and its general solution is
to shift reaction equilibrium toward ester formation. It
is usual to determine kinetic parameters for esterifi- 1
kE = √
cation reactions experimentally on a case-by-case ba- 0
t.cAlcohol b 2 − 4ac
sis [13]. This process is time consuming and requires  √ 
additional energy. 2c − b − b 2 − 4ac x
In this paper we suggest a simple but effective × ln  √  (5)
2c − b + b 2 − 4ac x
method for the prediction of esterification rates of
aliphatic monocarboxylic acids with primary alcohols
using protinic acid catalysis under homogeneous con- where
ditions. Our procedure is based on Taft steric and po-  
c0 1
lar (inductive) coefficients; we show that the reaction- a = 0 Acid 1− (6)
rate constant is dependent only on the structure of the cAlcohol K
acid or alcohol, allowing the prediction of esterifica- 0
cAcid + cAlcohol
0 0
cEster + cWater
0
tion rates under comparable reaction conditions for b= 0
+ 0
(7)
cAlcohol K cAlcohol
reactants combinations not yet tested.
0 0
cEster cWater
c =1− 0 0
(8)
THEORY K cAcid cAlcohol

The process of ester formation in organic chemistry is and x is the degree of conversion as a function of time.
well known. It can be described as Equation (5) together with imposed Eqs. (6), (7), and
(8) allows the determination of the esterification rate
constant kE if the thermodynamic equilibrium constant
Acid + Alcohol ↔ Ester + Water (1)
is known. In our experiments, we used only equimolar
mixtures of acids and alcohols without addition of ester
As can be seen from Eq. (1), the overall chemical
or water; hence,
reaction is an equilibrium process, esterification is the
forward reaction, and reverse reaction is ester hydrol- 0
cEster = cWater
0
=0
ysis. The reaction rate is relatively slow in the absence
of H+ ions as catalysts. It may be autocatalyzed by 0
cAcid = cAlcohol
0
(1 mol dm−3 ) (9)
protons from dissociation of the carboxylic acid, how-
ever their dissociation is poor. Reaction rates are pro- For these conditions, coefficient c from Eq. (8) is
portional to [H+ ] concentration up to approximately equal to 1, coefficient b from Eq. (7) is equal to 2, and
1 mol·dm−3 . the coefficient from Eq. (6) a = 1 − K1 ; and Eq. (5)
At constant concentration of [H+ ], the forward re- takes the simpler form
action rate is governed by the second-order kinetic √ 
√ √
equation. K −1 x − K
K
kE = ln √  √ (10)
v overall = kE cAcid cAlcohol − kH cEster cWater (2) 2t K +1 x − K

International Journal of Chemical Kinetics DOI 10.1002/kin.20845

 REACTION RATE PREDICTION OF ALIPHATIC MONOCARBOXYLIC ACIDS 191

If experimental parameters such as temperature, re- before use with anhydrous CuSO4 (Lachema, Czech
actants concentrations, and the amount of catalyst re- Republic) to minimize water content in reaction mix-
main the same, the esterification rate is dependent on tures. Inorganic chemicals such as H2 SO4 (96%),
the structure of the reacting acids and alcohols, espe- NaOH (titrimetric standard 5M), and CuSO4 anhy-
cially on their inductive, mesomeric, and steric effects. drous (Lachema, Czech Republic) were of analytical-
For acids and primary alcohols without mesomeric grade purity and were used as received.
effects, Taft suggested a two-parametric equation Solutions of reactants were prepared by weighing
[Eq. (14)]. The Taft equation is a semiempirical linear 0.2 mol of corresponding acid together with 0.98 g
free energy relationship used in contemporary physi- of anhydrous H2 SO4 . Weighed chemicals were quan-
cal organic chemistry for the study of reaction mecha- titatively transferred into a 100 mL volumetric flask
nisms [15–17] and for relative comparison of reaction (solution 1). Similarly, but without H2 SO4 , 0.2 mol
rates [18]. Usually the Taft equation has a general form of corresponding alcohol was weighed and trans-
of ferred into another 100 mL volumetric flask (solu-
tion 2). Finally, both solutions were filled to the mark
log kE = log kEo + ρ1 σ1 + δ ES (11) with pure dioxane. Equal volumes of the two solu-
tions were combined, giving a reaction mixture that
where σ 1 is the inductive (polar substituent) constant. contained reactants with a starting concentration of
It describes how a substituent will influence a reaction 1 mol·dm−3 and H2 SO4 as catalyst with a concentra-
rate with its inductive effect. Steric substituent con- tion of 0.005 mol·dm−3 .
stant Es quantifies the influence of steric effects on the Residual carboxylic acid concentration was deter-
reaction mechanism and its rate. Coefficients ρ 1 and δ mined by titration. On the basis of these results, the
are sensitivity factors for induction and steric effects. degree of conversion was calculated according to the
Taft proposed that under identical experimental condi- formula
tions, the steric and inductive sensitivity factors would
remain constant and would not influence the ratio of cACIDstarting − cACIDdetermined
x= (12)
reaction rates, allowing comparison of reaction rates cACIDstarting
relative to the standard value log kE0 , that is, reaction-
rate constant of reference species having parameters where cACIDstarting is the concentration of the acid at the
σ 1 and ES equal to zero [19]. beginning of esterification (in this work, 1 mol·dm−3 )
The aim of this study is an experimental deter- and cACIDdetermined is the residual acid concentration at
mination of sensitivity factors ρ 1 and δ in the Taft a given time point.
equation. It reports the relative esterification rates For the determination of equilibrium constants,
of aliphatic monocarboxylic acids with primary al- 10 mL of solution 1 and 10 mL of solution 2 were
cohols and demonstrates the calculation of reaction pipetted into ampoules. The ampoules were sealed and
rate constant for other esterification reactions under left to stand in a bath thermostated at 60◦ C for 10 days.
the same experimental conditions. Parameters σ 1 and Then, ampoules were opened and 1 mL was diluted for
ES are known for substituents of any primary alcohol titration with 30 mL water and this solution was titrated
and aliphatic monocarboxylic acid lacking mesomeric with 0.05 mol·dm−3 NaOH with phenolphthalein as the
effects. indicator; 0.2 mL was subtracted from the consump-
tion corresponding to catalyst content in the sample.
The measurements were repeated three times and the
EXPERIMENTAL degree of conversion was calculated.
For the determination of esterification rate con-
Formic acid, acetic acid (glacial anhydrous 100%), 1- stants, a 500 cm3 conical flask was immersed in a
propanoic (propionic) acid, 1-butanoic (butyric) acid, glass thermostat, stabilized a 60 ± 0.1◦ C. The reactor
2-methylpropanoic (isobutyric) acid, 1-pentanoic acid, was equipped with a magnetic stirrer and closed with a
3-methylbutanoic acid, 2,2-dimethylpropanoic acid, 1- plug, through which a long needle was introduced for
octanoic acid, 2-phenoxyacetic acid, 2-chloroacetic sampling the reaction mixture by syringe at chosen
acid, 2-bromacetic acid, 3-chloropropanoic acid, 2- time intervals to obtain 10–15 points of the kinetic
cyanoacetic acid propyl ester, methanol, ethanol, 1- curve.
propanol, 1-butanol, 1-pentanol, 2-methyl-1-propanol, The degree of conversion at each time point was de-
1-octanol, 2-phenoxyethanol, 2-chlorethanol, 2- termined titrimetrically during kinetic measurements.
methoxyethanol, 1,2-dihydroxyethan, and 1,4-dioxane The first run for each esterification reaction pair was
were of synthesis grade (Merck, Germany) were dried provisional to determine the optimal sampling times

International Journal of Chemical Kinetics DOI 10.1002/kin.20845

192 VOJTKO AND TOMČÍK

Table I Thermodynamic Equilibrium Constant (K) and Esterification Rate Constant (kE ) for Selected Aliphatic
Monocarboxylic Acids with 1-Propanol ES and σ 1 Taken from Ref. [20]
kE ·105 RSD ke kE ·105 Calculated
Acid Name ES σ1 K SDK dm3 ·mol−1 ·s−1 (%) dm3 ·mol−1 ·s−1 x∝
Formic acid +1.24 +0.02 4.19 0.80 44.0 5.0 32.7 0.67
Acetic acid 0.0 0.0 3.85 0.70 1.97 4.6 1.97 0.66
1-Propanoic acid –0.07 –0.01 3.70 0.70 1.60 3.1 1.67 0.66
1-Butanoic acid –0.36 –0.01 3.73 0.60 0.81 3.7 0.87 0.66
2-Methylpropanoic acid –0.47 –0.01 3.74 0.50 0.65 4.6 0.68 0.66
1-Pentanoic acid –0.39 –0.01 3.80 0.60 0.84 3.6 0.81 0.66
3-Methylbutanoic acid –0.93 –0.01 3.53 0.50 0.24 4.2 0.24 0.65
2,2-Dimethyl-pro-panoic acid –1.54 –0.01 4.22 0.70 0.067 4.5 0.06 0.67
1-Octanoic acid –0.40 –0.01 4.35 0.80 0.67 4.5 0.79 0.68
2-Phenoxyacetic acid –0.33 +0.40 2.83 0.05 1.44 2.8 1.15 0.63
2-Chloroacetic acid –0.24 +0.47 1.47 0.03 1.28 3.9 1.45 0.55
2-Bromoacetic acid –0.27 +0.47 1.34 0.03 1.13 3.5 1.36 0.54
2-Cyanoacetic acid –0.94 +0.57 3.01 0.05 0.33 3.0 0.32 0.63
2-Phenylacetic acid –0.38 +0.12 1.94 0.04 0.59 3.4 0.69 0.58
3-Chloropropanoic acid –0.90 +0.17 3.67 0.06 0.35 2.9 0.28 0.66

Table II Thermodynamic Equilibrium Constant (K) and Esterification Rate Constant (kE ) for Selected Primary
Alcohols with Acetic Acid ES and σ 1 Taken from Ref. [20]
kE ·105 RSD ke kE ·105 Calculated
Alcohol Name ES σ1 K SDK dm3 ·mol−1 ·s−1 (%) dm3 ·mol−1 ·s−1 x∝
Methanol +1.24 +0.02 3.95 0.7 4.79 6.3 4.36 0.67
Ethanol 0.0 0.0 3.85 0.7 2.18 7.4 2.18 0.66
1-Propanol –0.07 –0.01 3.85 0.6 1.97 6.1 2.16 0.66
1-Butanol –0.36 –0.01 3.62 0.6 1.94 4.1 1.81 0.67
2-Methyl-1-propanol –0.47 –0.01 3.20 0.5 1.59 5.0 1.69 0.64
1-Pentanol –0.39 –0.01 3.21 0.5 1.93 6.2 1.86 0.64
1-Octanol –0.40 –0.01 3.44 0.6 2.15 6.5 1.77 0.65
2-Methoxy-ethanol –0.19 +0.30 0.72 0.02 0.744 5.4 0.67 0.46
2-Chloroethanol –0.24 +0.47 0.19 0.003 0.278 3.6 0.30 0.33
2-Phenoxy- ethanol –0.33 +0.40 0.61 0.01 0.595 5.0 0.48 0.44
2-Dihydroxy-ethane +0.03 +0.25 0.966a 0.88
a
Calculated from dynamic measurements according to the formula k = 1 x
2t 1−x
at short times of the reaction when it is possible to consider
the direct reaction of second order.

corresponding to significant changes in the degree of The calculated degree of conversion was used di-
conversion. Generally, samples were taken every 5 min, rectly for the calculation of the equilibrium constants
and then the time sampling interval was extended to according to the formula
20 min. Each point on the kinetic curve was used to
calculate the corresponding rate constant. [ester][water] x2
K = = (13)
[acid][alcohol] (1 − x )2

RESULTS AND DISCUSSION The results are summarized in Tables I and II. Rel-
ative standard deviations do not exceed 8% for each
First, thermodynamic equilibrium esterification con- measurement.
stants of 15 aliphatic monocarboxylic acids with Thermodynamic equilibrium constant values were
propanol and 11 primary alcohols with acetic acid were used to calculate esterification rate constants accord-
determined. 1,4-Dioxane was used as the solvent be- ing to Eq. (10). It has been found that a discontinuous
cause it is inert and dissolves all components of the isothermal reactor equipped with a stirrer is very con-
reaction system to give a homogeneous solution. venient for creating a homogeneous environment for

International Journal of Chemical Kinetics DOI 10.1002/kin.20845

 REACTION RATE PREDICTION OF ALIPHATIC MONOCARBOXYLIC ACIDS 193

−6
−4.5

log kE(calculated)
log kE(calculated)

−5

−5.0

−4

−5.5

−5.5 −5.0 −4.5

−3 −4 −5 −6 log kE(experimental)
log kE(experimental)
Figure 2 Correlation between the experimentally obtained
Figure 1 Correlation between the experimentally obtained values of the esterification rate constants of acetic acid with
values of the esterification rate constants of 1-propanol with selected primary alcohols (log experimental kE ) and the values
selected aliphatic monocarboxylic acids (log experimental kE ) logcalculated kE calculated from Eq. (15).
and the values logcalculated kE calculated from Eq. (14).

primary alcohols and Taft equation for this reaction can

both polar (water) and less polar (esters) compounds be expressed as (with ethylacetate is as the reference
in 1,4-dioxane as a solvent. compound)
1-Propanol was used as a model alcohol to deter-
mine the dependence of the esterification rate on the 0experimental
log kE = log kEethylacetate − 1.55 σ1 + 0.27 ES (15)
structure of the 15 aliphatic monocarboxylic acids. The
standard least squares method was used to determine
where log kEethylacetate is equal to 2.18 × 10−5
0experimental
the dependence log kexperimental versus σ 1 and ES (with
parameter value from Anslyn and Dougherty [20]); the dm3 mol−1 s−1 . A plot of log kE(calculated) versus log
results can be described by Eq. (14) (with propyl ac- kE(experimental) was constructed (Fig. 2) and found to be
etate as the reference compound): linear with a slope of 0.96523 (SDSLOPE = 0.063, R2 =
0.981).
0experimental
log kE = log kEpropylacetate + 0.22 σ1 + 0.98 ES Correlation equations (14) and (15) are signifi-
cantly different. The most significant in esterification
(14) of 1-propanol with different acids is the steric effect,
connected with formation of protonated intermediate,
where log kEpropylacetate is equal to 1.97 × 10−5
0experimental
whereas in the process of esterification of acetic acid
dm3 mol−1 s−1 . The induction sensitivity factor of with primary alcohols, the crucial influence comes
ρ 1 = 0.22 shows that the reaction of 1-propanol with from inductive effects of the corresponding alcohol.
aliphatic monocarboxylic acids is mildly sensitive to Very negative induction sensitivity factor ρ 1 = –1.55 in
induction effects, whereas δ = 0.98 confirms a strong Eq. (15) indicates that the reaction of acetic acid with
steric influence on acid deprotonation. According to primary alcohols is accelerated by electron-donating
the Eq. (14), values of log kE(calculated) were calculated substituents that promote nucleophilic attack of the al-
for each propylester formation. A plot log kE(calculated) cohol on the protonated intermediate.
versus log kE(experimental) was found to be linear Using 1,4-dioxane as reaction medium enables esti-
(Fig. 1) with a slope of 0.96755 (SDSLOPE = 0.035, mates of the reaction-rate constant because it depends
R2 = 0.984) showing good correlation between exper- only on the structure of the reactants. Previous mea-
imental and calculated values of log kE . surements of structural influence on the esterification
Similarly, acetic acid was selected as model acid rates have always been carried out in different reac-
for the measurements of the esterification rates with 11 tion environments or at a high concentration of one

International Journal of Chemical Kinetics DOI 10.1002/kin.20845

194 VOJTKO AND TOMČÍK

Table III Predicted and Calculated Esterification Rate Constants for Another Ester to Verify Proposed Procedure.
Experimental Data Obtained from Second-Order Kinetic Equation at Low Degree of Conversion
kE(calc) ·105 kE(exp) ·105 (K = 1) kE(exp) ·105 (K = 4)
Ester Name Formula [dm3 ·mol−1 ·s−1 ] [dm3 ·mol−1 ·s−1 ] [dm3 ·mol−1 ·s−1 ]
1-Butylphenyacetate C12 H16 O2 0.45 0.42 0.42
Ethylbromacetate C4 H7 O2 Br 0.31 0.35 0.35
1-Penthyvalerate C10 H20 O2 0.67 0.65 0.65
2-Methyl-1-propyl-3-chlorpropionate C7 H13 O2 Cl 0.17 0.14 0.14

component, where the esterification-rate equation was calculated esterification reaction rate value is 1.97 ×
reduced to pseudo-first-order or the second-order equa- 10−6 dm3 ·mol−1 ·s−1 . This value is in relatively good
tion was used but reactions were not followed to equi- agreement with a value of 1.65 × 10−6 dm3 ·mol−1 ·s−1
librium. obtained experimentally. Similar to this, esterification
Knowing sensitivity factors for the two Taft param- rate constants of next four esters were predicted and
eters for both the acid and the alcohol allows one to verified experimentally at low degrees of conversion.
estimate the esterification rate for any primary alcohol The results are summarized in Table III. The good
reacting with any aliphatic monocarboxylic acid under agreement between predicted and experimental values
the same conditions at which rate constant of reference of rate constant was achieved.
species and their sensitivity factors were measured.
Because the reaction center is the same for any acid
CONCLUSIONS
and alcohol, the rate of esterification for any ester XY
(index X is related to alcohol and Y to acid) can be
A novel, simple, and reliable procedure for estimation
expressed as
of esterification rates was developed. The esterification
rate constants of aliphatic monocarboxylic acids with
log kXY = log kXA + 0.98EY + 0.22 σ1Y (16)
1-propanol and of primary alcohols with acetic acid
were measured under conditions of a nearly ideal so-
where
lution. It was observed that 1,4-dioxane is a suitable
solvent for these measurements because it is inert and
log kXA = log kEA + 0.27EX − 1.55 σ1X (17)
readily dissolves polar (acids, alcohols, and water) and
less polar (esters) species present in reaction mixture.
where kEA is reaction-rate constant of ethylacetate for-
For the quantification of relationship between struc-
mation and kXA is the reaction-rate constant of the
ture and reaction rate, a two-parameter Taft equation
corresponding acetate formation. Values of log kPA
was used, including inductive and steric effects. Be-
(reaction-rate constant of propylacetate formation) can
cause all rate measurements were made under equiv-
also be used for calculation but it should be recalcu-
alent experimental conditions (inert solvent, relatively
lated from value log kEA according to the equation
low concentrations of reactants, constant concentra-
tion of hydrogen ions, and constant temperature and
log kPA = log kEA +0.27ESPropanol −1.55 σ1 Propanol
volume), calculations using the second-order kinetic
= log kEA − 0.0034 (18) equation provided consistent reaction-rate constants.
On the basis of these results, it is possible to estimate
By combination of Eqs. (16), (17), and (18), a final reaction-rate constants that were not experimentally
equation for the calculation of rate constant is obtained: measured using only the known Taft steric and in-
duction constants for each reactant. This methodology
should also be applicable to other types of bimolecular
log kXY = (log kPA + 0.0034) + 0.98ESY chemical reactions.
+ 0.22 σ1Y + 0.27ESX − 1.55 σ1X (19)
APPENDIX: INTEGRATION OF KINETIC
The validity of this approach was verified on amyl EQUATION
isovalerate as an example. Amylisovalerate is an es-
ter of amyl alcohol (1-pentanol, ES = –0.39, σ 1 = Consider the general equilibrium chemical reaction
–0.01) and isovaleric acid (3-methylbutanoic acid,
ES = –0.93, σ 1 = –0.01). According to Eq. (19), the A+B↔R+S

International Journal of Chemical Kinetics DOI 10.1002/kin.20845

 REACTION RATE PREDICTION OF ALIPHATIC MONOCARBOXYLIC ACIDS 195

Definitions: = kE cB,0 dt
kE : reaction rate constant of forward reaction, 1
kH : reaction rate constant of backward reaction. dx = kE cB,0 dt
ax2 − bx + c
cA,0 − cA decomposition on partial fractions, assuming D =
x= − degree of conversion
cA,0 b2– 4ac > 0,
cA = cA,0 (1 − x ) 1 1
=√
ax 2 − bx + c b − 4ac
2
cB = cB,0 − cA,0 x
1 1
× √ − √
cR = cR,0 + cA,0 x x− b
− b 2 −4ac
x− b
+ b 2 −4ac
2a 2a 2a 2a
x
cS = cS,0 + cA,0 x 1 1 1
√ √ dx − √
kE b 2 − 4ac x− b
2a
− b 2 −4ac
2a
b2 − 4ac
K = 0
kH x t
1
The overall reaction rate can be expressed as × √ dx = cB,0 kE tdt
b 2 −4ac
x− b
2a
+ 2a
  0
√
0
1 b 2 −4ac
voverall = kE cA cB − kH cR cS = kE cA cB − cR cS 1 x− b
−
K √ ln 2a
√
2a
const = cB,0 kE t
b 2 − 4ac x − b
2a
+ b 2 −4ac
2a
assuming the following about the mentioned defini-
tions: for x(t = 0) = 0
√
dx   x− b
− b 2 −4ac
cA,0 = kE cA.0 (1 − x )(cB,0 − cA,0 x ) 2a
√
2a
const = 1
dt x− b
+ b 2 −4ac
 2a 2a
1
× − (cR,0 + cA,0 x )(cS,0 + cA,0 x )
K therefore
cA,0 dx √
b 2 − 4ac
b−
cA.0 (1 − x )(cB,0 − cA,0 x ) − 1
K
(cR,0 + cA,0 x )(cS,0 + cA,0 x ) const = √
b + b 2 − 4ac
= kE dt
for kE can be derived as
cA,0 dx
√
2
x 2 cA,0 − 1 2
cA,0 + x −cA,0 cB,0 − cA,0
2
b 2 −4ac
K
1 x− b
−
cA,0 dx kE = √ ln 2a
√
2a
× tc B,0 b 2 − 4ac x− b
+ b 2 −4ac
− K1 (cA,0 cS,0 + cA,0 cR,0 ) + cA,0 cB,0 − 1
c c
K R,0 S,0
2a 2a
√
= kE dt b − b 2 − 4ac
× √
b + b 2 − 4ac
dx
 
x 2 cA,0 1− 1
K
− x cB,0 + cA,0 + 1
K
(cS,0 + cR,0 ) respectively.
dx 1
× cR,0 cS,0 kE = √
+cB,0 − K1 cA,0 tc B,0 b 2 − 4ac
 √
√ √
= kE dt x b− b 2 − 4ac −
b+ b 2 −4ac
2a
b− b 2 − 4ac
× ln  √
dx √ b− b 2 −4ac √
  x b+ b 2 − 4ac − 2a
b+ b 2 − 4ac
cB,0 +cA,0 1 cS,0 +cR,0
x 2 ccA,0
B,0
1− 1
K
−x cB,0
+ K cB,0  √ 
1 x b − b 2 − 4ac − 2c
dx kE = √ ln  
× √
+1 − 1 cR,0 cS,0 tc B,0 b 2 − 4ac x b + b 2 − 4ac − 2c
K cA,0 cB,0

International Journal of Chemical Kinetics DOI 10.1002/kin.20845

 196 VOJTKO AND TOMČÍK

finally, 2. Isbell, T. A.; Carlson, K. D.; Abbott, T. P.; Phillips,

B. S.; Erhan, S. M.; Kleiman, R. Ind Crops Prod 1996,
 √ 
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1 2c − b − b 2 − 4ac x
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International Journal of Chemical Kinetics DOI 10.1002/kin.20845

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