Describing the Reaction of the Hydrocarboxylation of 1-Hexene, Catalyzed by Co2(CO)8, in Marcelin–de Donde Kinetics

Article abstract of DOI:10.1134/S0036024420110321

Abstract: An equation is derived for calculating the rate coefficient of the 1-hexene hydrocarboxylation reaction in Marcelin–de Donde kinetics. The equation correctly describes experimental data in the range of concentrations of an unsaturated substrate,

Full text of DOI:10.1134/S0036024420110321

ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2020, Vol. 94, No. 11, pp. 2209–2211. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Fizicheskoi Khimii, 2020, Vol. 94, No. 11, pp. 1604–1607.
CHEMICAL KINETICS
AND CATALYSIS
Describing the Reaction of the Hydrocarboxylation of 1-Hexene,
Catalyzed by Co2(CO)8, in Marcelin–de Donde Kinetics
Yu. T. Vigranenkoa, A. V. de Vekkia,*, T. E. Krylovab, and E. V. Koluzhnikovaa
a St. Petersburg State Forestry University, St. Petersburg, 194021 Russia
bSt. Petersburg State University of Aerospace Instrumentation, St. Petersburg, 190000 Russia
*e-mail: gertsog5000@yandex.ru
Received January 26, 2020; revised January 26, 2020; accepted February 11, 2020
Abstract—An equation is derived for calculating the rate coefficient of the 1-hexene hydrocarboxylation reac-
tion in Marcelin–de Donde kinetics. The equation correctly describes experimental data in the range of con-
centrations of an unsaturated substrate, where the traditional Van’t Hoff–Arrhenius kinetics is of little use.
Keywords: Marcelin–de Donde kinetics, hydrocarboxylation, 1-hexene, dicobaltococarbonyl
DOI: 10.1134/S0036024420110321
INTRODUCTION
concentrations up to 0.5 mol/L, but as the concentra-
tion of [C6H12]0 rises from 0.5 to 3.46 mol/L, the order
of 1-hexene falls from 1 to 0.5. The observed variable
order indicates the law of acting masses is not obeyed.
It is therefore advisable to obtain additional informa-
tion about the reaction rates and compositions of the
liquid phase, including dissolved carbon monoxide, to
describe this area with kinetics of a more general form
without the concept of a reaction order.
In solving many problems of oil refining and petro-
chemistry related to calculations for reactors and opti-
mizing technological processes, an important role is
played by determining the time raw materials remain
in reactors (or the volumetric rate of their supply to the
reactor). These depend on the order of the reaction
and the magnitude of its rate constant. These concepts
are closely related to the law of mass action in Van’t
Hoff–Arrhenius kinetics, which is known to be strictly
obeyed only by strongly diluted solutions and ideal
gases, and under isothermal conditions. Failure to
obey the law of mass action creates additional difficul-
ties associated with calculating the periods raw mate-
rials remain in reactors. The error in determining it
thus grows if there is a variable reaction order for any
reagent. To eliminate this possibility, it is advisable to
EXPERIMENTAL
In this work, we used 1-hexene (chemically pure),
and acetone (pure) as the solvent. The purity of carbon
monoxide was 99.60 vol %, and the content of impu-
rities N2 was 0.06 vol %. No oxygen was present.
The reaction of hydrocarboxylation was studied in a
use kinetics of a more general form that preserves the 0.5 L ideal mixing reactor equipped with an electric fur-
main properties of the Van’t Hoff–Arrhenius kinetics. nace, a water cooling jacket, and a 0.01 L high-pressure
cutoff tank for sampling the liquid phase [3]. The unit
also included high pressure buffer tanks for hydrogen,
carbon monoxide, and CO–H2 synthesis gas, along
with a charging unit for unsaturated substrates. A high
rate of mixing (2800 rpm) ensured the proceeding of the
hydrocarboxylation reaction in the kinetic region.
Dicobaltoctacarbonyl Co2(CO)8 were obtained
from cobalt acetate and acetic anhydride in a shaking
autoclave, according to the procedure described in [4].
Dicobaltoctacarbonyl and water were loaded in the
reactor purged with argon, and then carbon monoxide
The reaction of the hydrocarboxylation of alkenes
is thus of great practical importance as an effective way
of synthesizing carboxylic acids from petrochemical
raw materials:
RCH=CH2 + CO + H2O → RCH2CH2COOH.
It is catalyzed by carbonyl complexes of transition
metals of group VIII of the Periodic Table, among
which the most active compounds are cobalt and pal-
ladium [1]. The kinetics of 1-hexene hydrocarboxyl-
ation in the presence of Co2(CO)8 was studied in [2],
where it was shown that this reaction is of the first was supplied up to a pressure of 8.0 MPa, and heating
order of magnitude for the catalyst and water in a wide and stirring were switched on. 1-Hexene was poured
range of variation of these parameters. The order for into the loading tank. Upon reaching the operating
alkene is also equal to unity in the region of its initial temperature, the 1-hexene was saturated with carbon
2209

2210
VIGRANENKO et al.
+
1
+
N
−
1
−
N
monoxide pumped from the loading vessel to the reac-
tor, bringing the pressure in it to 20.0 MPa. The
moment the 1-hexene was saturated with the carbon
monoxide was considered the beginning of the reac-
tion. Samples of the liquid and gas phases were taken
during our experiments. After reducing the flow of the
dissolved gases, the samples were weighed and sent for
chemical and gas chromatographic analysis. The con-
centration of cobalt in the samples of the liquid phase
was determined spectrophotometrically [5].
Gas chromatographic analysis of the products of 1-
hexene hydrocarboxylation was performed on an
LKhM-72 chromatograph equipped with a flame ion-
ization detector. The stationary phase was PEG-40M,
'
1
'
ν j A + … + ν j AN ꢀ ν j A + … + ν j AN,
1
corresponds to non-negative velocity coefficient k,
and the rate of the jth stage is written as
−
ν+jiμ(C)
ν jiμ(C)
RT
n
n


Wj(C) = kj
,
− exp 
i=1


 i=1

RT

where j = 1 … Q.
It can be shown that the widely used Van’t Hoff–
Arrhenius kinetics is a special case of Marcelin–de
Donde kinetics [7]. For the irreversible chemical reaction
'
' '
ν1A + … + νnAn ꢀ ν1A + … + νnAn
1
1
deposited on a solid Chromaton N-AW-DMCS car- the expression for the rate takes the form
rier (15 wt %). The 3 m × 3 mm column was made of
n
νiμA
RT
stainless steel. The initial temperature of the column
was 100°C, its final temperature was 220°C, and the
temperature was increased at a rate of 3 K/min. The
carrier gas was argon, the hydrogen flow rate was
60 mL/min, and the air flow rate was 85 mL/min. The
temperature of the detector was 170°C, and that of the
injector 150°C.
i
W = k exp
.

i=1
μA = μ(A0) + RT ln fA
Since
,
i
i
i
νiμ(A0)
n
n
i
W = k exp  exp ν ln f .
i
A
i
RT
i=1
i=1
Logarithmizing this expression, we arrive at the equa-
tion for calculating the rate coefficient of the irreversible
chemical reaction in the kinetics of Marcelin–de Donde:
RESULTS AND DISCUSSION
A class of simple kinetics now exists. According to
Feinberg [6], kinetics is referred to as simple if the total
mass and energy of the system are constant, the concen-
tration of all components that participate in the chemi-
cal reaction cannot be negative, and the function of the
full rate for a complex multi-stage reaction has the form
νiμ(A0)
RT
n
n
i
lnW = ln k + 
i=1
+ ν ln f .
i
A
i
i=1
Analysis of the equation shows that in order to calcu-
late the reaction rate coefficient, we must know the vol-
atility and standard chemical potentials of the initial
materials [8]. There are no works in the literature on
calculating the rate coefficients of irreversible catalytic
reactions from experimental data on heterophase liq-
uid–gas systems. We therefore calculated the rate coef-
ficient of the reaction of 1-hexene hydrocarboxylation.
The initial data for calculating the rate coefficient of the
reaction of 1-hexene hydrocarboxylation in the kinetics
of Marcelin–de Donde are presented in Table 1.
n
W (C) = ν W (C),
j j
j=1
where Wj(C) is the rate of the jth stage and νj is the stoi-
chiometric coefficient; i.e., it has the property of additiv-
ity. There is the so-called pseudopotential (C) =
μ
μ(C)/RT, where μ(C) is the chemical potential for which
scalar product μ(C)W(C) ≤ 0 (i.e., not positive).
The best known simple kinetics is the Marcelin–de
Analysis of the data in Table 1 shows that the solu-
Donde variety, in which each elementary stage of a bility of CO in liquid products falls from 18.5 to
complex reaction consisting of Q stages,
12.6 mol % as the conversion of 1-hexene grows from
Table 1. Rate and composition of products of the reaction of 1-hexene hydrocarboxylation
The composition of the liquid phase, mol %
Conversion
of C6H12, %
W,
ethanoic methyl ethyl
enante
aldehydes
mol/(L min)
1-hexene
water
acetone
CO
acids
ketone
0
7
15
22
33
44
0.0324
0.0291
0.0263
0.0237
0.0208
0.0181
6.4
6.0
5.2
5.0
4.6
4.2
—
—
—
—
0.1
0.1
0.2
—
—
—
0.1
0.1
0.2
35.5
35.7
35.4
35.1
34.7
34.2
39.6
40.6
42.1
43.4
44.9
46.1
18.5
17.2
16.4
15.3
13.5
12.6
0.5
0.9
1.4
2.1
2.5
Catalyst precursor (CO) , 160°C; pressure 29.4 MPa; [Co] = 0.059 g-atom/L; charge 37.0 g 1-hexene, 44.4 g H O.
2
8
2
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
Vol. 94
No. 11
2020

DESCRIBING THE REACTION OF THE HYDROCARBOXYLATION
2211
∞
2.20
2.15
2.10
2.05
2.00
the liquid phase; and
is the partial molar volume of
Vi
the dissolved gas at infinite dilution. The volatility of
water and 1-hexene was determined using the equa-
tion [9]
0 (P − P )
0
0
ꢀ
'
ln fi = ln fi (P = P ) + ln Xi + Vi
,
0
RT
where
0 and 0 are the volatility and partial molar
volume of the liquid component (water, 1-hexene) at
160°C and P = P , respectively. Value
0 calculated
ln fi
Vi
ln fi
0
using the Lee–Kesler equation [10]. The saturated
acetone vapor pressure was taken for P0 [11]. Henry
coefficient K(T, P0) for carbon monoxide and its par-
0
5
10
15
20
25
tial molar volume at infinite dilution
mined from the graph shown in Fig. 1.
were deter-
Vi
P − P0, МPа
Dependence lnW on
was linear-
ln f
fH O fCO
(
)
Fig. 1. Dependence of the solubility of carbon monoxide
C6H12
2
on pressure.
ized (Fig. 2), and the coefficient of the rate of the reac-
tion of 1-hexene hydrocarboxylation was calculated:
k = 1.89 × 1045 mol/(L min). The standard Gibbs
energies of water, carbon monoxide, and 1-hexene
were taken from [12] for the values of standard chemi-
lnW
−3.4
0
H2O
0
0
cal potentials
,
,
. The resulting value of
μ
μCO
μ
C6H12
the rate coefficient can be used in solving kinetic prob-
lems and calculating reactors.
−3.6
−3.8
−4.0
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27.6
27.8
ln( fC fCO fH )
O
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28.0
H
6
12
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∞ (P − P )
0
ꢀ
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'
ln fi = ln ki(T,P ) + ln Xi + Vi
,
0
(Butterworth-Heinemann, Boston, 1985).
RT
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'
where is the volatility of the dissolved gas in the gas
fi
phase; ki(T, P0) is the Henry coefficient at absolute
temperature T and the saturated vapor pressure of the
solvent; Xi is the molar fraction of the dissolved gas in
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RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 94 No. 11 2020