Kinetics of hydroformylation of 1-decene using carbon-supported ossified HRh(CO)(TPPTS)3 catalyst

Article abstract of DOI:10.1002/kin.21234

The kinetics of hydroformylation of 1-decene has been investigated using a carbon-supported ossified HRh(CO)(TPPTS)₃/Ba catalyst in a temperature range of 343–363?K. The effect of concentration of 1-decene, catalyst loading, partial pressure of H₂ and CO, and stirring speed on the reaction rate has been investigated. A first-order dependence was observed for catalyst concentration and hydrogen partial pressure. The rate showed a typical case of substrate inhibition for high 1-decene concentration. The rate varied with a linear dependence on P_CO up to a CO partial pressure of 5–6?MPa in contrast to the general trends; for most of the rhodium-phosphine catalyzed hydroformylation reactions, severe inhibition of rate is observed with an increase in CO pressure. A rate equation has been proposed, which was found to be in good agreement with the observed rate data within the limit of experimental errors. The kinetic parameters and activation energy values have been reported.

Full text of DOI:10.1002/kin.21234

Received: 11 July 2018
DOI: 10.1002/kin.21234
Revised: 1 November 2018
Accepted: 4 November 2018
A R T I C L E
Kinetics of hydroformylation of 1-decene using carbon-supported
ossified HRh(CO)(TPPTS)3 catalyst
Nitin S. Pagar1,2
Raj M. Deshpande1,3
1Homogeneous Catalysis Division, CSIR—
National Chemical Laboratory, Pune, India
Abstract
The kinetics of hydroformylation of 1-decene has been investigated using a carbon-
supported ossified HRh(CO)(TPPTS)3/Ba catalyst in a temperature range of 343–
363 K. The effect of concentration of 1-decene, catalyst loading, partial pressure of
H2 and CO, and stirring speed on the reaction rate has been investigated. A first-order
dependence was observed for catalyst concentration and hydrogen partial pressure.
The rate showed a typical case of substrate inhibition for high 1-decene concentration.
The rate varied with a linear dependence on P up to a CO partial pressure of 5–
6 MPa in contrast to the general trends; for mosCt Oof the rhodium-phosphine catalyzed
hydroformylation reactions, severe inhibition of rate is observed with an increase in
CO pressure. A rate equation has been proposed, which was found to be in good agree-
ment with the observed rate data within the limit of experimental errors. The kinetic
parameters and activation energy values have been reported.
2Post Graduate Department of Chemistry, Sir
Parashurambhau College, Pune, India
3SABIC Technology Centre, Bangalore, India
Correspondence
NitinS. Pagar, PostGraduateDepartmentof
Chemistry, SirParashurambhauCollege, Pune
411 030, India.
Email: nitin.pagar@spcollegepune.ac.in,
nspagar@gmail.com
Fundinginformation
Council of Scientific and IndustrialResearch
(CSIR), India, Grant/AwardNumber:
Task Force on Catalysis and Catalysts
(CMM0005.3)
K E Y W O R D S
1-decene, hydroformylation, kinetics, ossification, supported ossified
of the complex in the heterogenized phase, which ensures
that it does not leach into the noncatalyst liquid phase
1
INTRODUCTION
during the course of a reaction, while retaining the high
activity, selectivity, and original configuration of the cat-
alytic complex. Various attempts were made to heteroge-
nize some of the industrially relevant homogeneous catalysts
for application to different catalytic reactions including
hydroformylation. Although the techniques for heterogeniza-
tion onto solid supports viz anchored catalyst,6–11 polymer-
bound catalyst,12–16 encapsulated catalyst,17–19 supported liq-
uid phase catalyst, (SLPC)20–22 supported aqueous phase
catalyst (SAPC),23,24 supported ionic liquid phase catalyst
(SILP),25–27 biphasic catalysts using water-soluble metal
complexes of sulfonated,2–5 or fluorinated phosphines28–30
ligands, gave active catalysts; they were plagued with prob-
lems like leaching and deactivation of the catalysts. Although
these concepts have drawn interest, with the exception of
aqueous-biphasic catalysis no other approach has been found
to be commercially attractive, due to issues of catalyst leach-
ing, catalyst product separation, and poor activity. Even
application of aqueous biphasic catalysis is also restricted to
Homogeneous catalysis, using soluble metal complexes, pro-
vides selective synthetic routes under mild operating con-
ditions for many valuable chemicals from simple organic
precursors.1 Homogenous catalytic systems, however, have
intrinsic problems related to catalyst—product separation
and hence have limited industrial applications. Heterogeniza-
tion of metal complexes may provide a significant improve-
ment in this aspect. Different approaches, broadly classified
as “biphasic catalysis”2–5 and “solid-supported catalyst”.6–11
The prime requirement for these catalysts is the stability
Nomenclature: A, Concentration of H2 in toluene in equilibrium with gas
phase, kmol/m3; B, Concentration of CO in toluene in equilibrium with gas
phase, kmol/m3; C, Concentration of the catalyst, kmol/m3;
D, Concentration of the 1-decene, kmol/m3; k , Reaction rate constant,
1
m9/kmol3/s; K , Constant in Equation 3, m3/kmol; K , Constant in
2
3
Equation 3, m3/kmol; PCO, Partial pressure of carbon monoxide, MPa; ꢀH
,
2
Partial pressure of hydrogen, MPa; r, Rate of hydroformylation, kmol/m3/s;
R′Ai, Experimental rates; RAi, Predicted rates; t, Reaction time, min
Int J Chem Kinet. 2018;1–11.
wileyonlinelibrary.com/journal/kin
© 2018 Wiley Periodicals, Inc.
1

2
PAGAR AND DESHPANDE
the hydroformylation of propylene and butene due to lower
solubilities of higher olefins.31–33 Heterogenization by “ossi-
fication” has recently been proposed, wherein the immobiliza-
tion of water-soluble Rh and Pd/TPPTS complexes has been
achieved by precipitating it as an insoluble salt of Group 2
metals such as Ca, Sr, or Ba.34–36 Supported ossified cata-
lysts have been found to be active for the hydroformylation
of higher olefins and provide one of the most active and sta-
ble heterogenized complex catalyst.35 An investigation into
the kinetics of higher olefin hydroformylation would be thus
more relevant using such supported ossified catalyst.
2.2 Preparation of supported ossified catalyst
The supported ossified catalyst was synthesized from the
water-soluble metal complex HRh(CO)(TPPTS)3 by precip-
itation as its barium salt on a porous support. In a general
synthetic procedure, 20% aqueous Ba(NO3)2 (2 g, 8.51 mmol)
was combined with 10 g of support and refluxed for 4–5 h. The
mixture was subsequently dried, resulting in a barium nitrate
impregnated support.
1.5 grams of the above-prepared Ba(NO3)2 impregnated
support (carbon) was taken and added to an aqueous solution
of HRh(CO)(TPPTS)3 (131.5 mg, 0.07 mmol) and TPPTS
(240.5 mg, 0.42 mmol, (Rh:P = 1:6)) under argon flow. After
There are very few kinetic studies on hydroformylation
using solid-supported catalysts.37–47 The kinetics of hydro-
formylation of propylene,37,38 allyl alcohol,39 and 1-butene40
using SLPC, HRh(CO)(PPh3)3 was reported by Scholten and
co-workers. They have proposed the power law model based
on the observed trends. The kinetics of hydroformylation of
1-octene,41,42 linalool,43 and long-chain alkene44 was stud-
ied using SAPC. The trends reported were similar to those
observed in the homogeneous media except for the inhibition
observed at a higher olefin concentration. Similar observa-
tions were reported for the kinetics of hydroformylation of
1-hexene using the Rh/TPPTS complex exchanged on anion
exchange resin.45 Kinetics of hydroformylation of 1-hexene
using HRh(CO)(PPh3)3 encapsulated hexagonal mesoporous
silica46 and gas-phase propene hydroformylation over a SILP
rhodium catalyst also have shown similar trends.47
◦
4–5 h of stirring at ∼40 C, the mixture was filtered and
washed two to three times with cold and hot water, respec-
tively. The solid was further washed in a soxhlet apparatus for
12 h with water and toluene, respectively. This ensured that all
unreacted complex was removed. The catalyst was then dried
under vacuum (yield = 1.73 g).
2.3 Experimental setup
All the hydroformylation experiments were carried out in a
50-mL autoclave, supplied by Amar Engineers (India) and
was provided with arrangements for liquid and gas sampling,
automated temperature control, and a variable stirring speed.
The reactor was provided with a rupture disk as a safety mea-
sure. The maximum reactor operating pressure and tempera-
We report here a study on the kinetics of hydroformy-
lation using carbon-supported ossified catalyst. Such study
will also provide an understanding of the mechanism of
the reaction using ossified catalyst and the variation from
the reported mechanism using conventional homogeneous
HRh(CO)(PPh3)3 and HRh(CO)(TPPTS)3 catalysts.
◦
ture were 2000 psi and 250 C. The reduction of pressure in
the syngas reservoir in the course of the reaction was moni-
tored using a pressure transducer/recorder. Figure 1 shows a
schematic of the experimental setup.
2.4 Experimental procedure
In a typical experiment, the desired amounts of the catalyst,
olefin, and solvent were charged into the autoclave, and the
autoclave was closed. It was then flushed with nitrogen fol-
lowed by flushing with CO + H2 and heated up to the requisite
temperature. Subsequently, syngas with the requisite H2 and
Co ratio was filled in the reactor up to the reaction pressure.
A liquid sample was taken as the initial sample of the reactor
contents. The reaction was initiated by increasing the stirring
speed to the desired value. The syngas premix in a 1:1 CO:H2
ratio was fed continuously into the reactor to make up for the
gas consumption, which was intrinsically in a 1:1 ratio. This
was possible because the only products formed was aldehyde
(n: iso). This ensured that the ratio of CO: H2 in the reactor
was maintained, as present at the beginning of the reaction.
Analysis of the reaction products at the end of the reaction
also showed only aldehyde products. Since these reactions
were intended to understand the intrinsic kinetics, the reac-
tions times were short so that the liquid phase composition
did not vary much, and the data would represent the initial
2
EXPERIMENTAL
2.1 Materials
Rhodium trichloride (RhCl3⋅3H2O), obtained from Arora-
Matthey (Kolkata, India), was used as received without fur-
ther purification. 1-Decene (>99% pure) was obtained from
Aldrich (St. Louis, MO, USA). Barium nitrate and PPh3 were
procured from Loba Chemie (Mumbai, India). Freshly dis-
tilled toluene was used as the solvent. Hydrogen and car-
bon monoxide (>99.8%) were obtained from Indian Oxygen
(Mumbai, India) and Matheson Gas (Montgomeryville, PA,
USA), respectively, and used as received. The syngas mix-
ture (H2 + CO) in the desired ratio, typically 1:1 CO:H2, was
made as a premix from H2 and CO and stored in a reservoir.
The ligand triphenylphosphine trisulfonate (TPPTS)48 and its
rhodium complex, HRh(CO)(TPPTS)3, were prepared by fol-
lowing known literature procedures.23

PAGAR AND DESHPANDE
3
F I G U R E 1 A schematic of the reactor setup used for the hydroformylation reaction
reaction rate and ensure differential conditions. Analysis of
the liquid-phase composition for the initial and final samples
was conducted to ensure material balance, which was found
to be excellent. The rates of the hydroformylation reaction
observed in thus initial range were constant with a repro-
ducibility of 5–7%. This procedure was employed to study
the influence of the various reaction parameters on the rate of
hydroformylation, to assess the activity of the supported ossi-
fied catalysts for hydroformylation of 1-decene, and further
to study the kinetics of the reaction using carbon-supported
ossified catalyst.
and reproducibility of experiments. In these experiments, the
reactants consumed (1-decene, CO, and H2) and the prod-
ucts formed (undecanal, iso-C11 aldehyde) were compared.
A typical concentration time profile is shown in Figure 2.
The results showed a good agreement between the reactant
consumption and products formed; the results also confirmed
that the only products formed were the C11 aldehydes. Based
on these studies, the rate of aldehyde formation could be
represented by monitoring the consumption of syngas with
time.
3.1 Solubility data
2.5 Analytical methods
The solubility of CO and H2 in toluene was obtained exper-
imentally as per the reported procedure,49 and Henry's con-
stants for H2 and CO in toluene are presented in Table 1. These
values were used to calculate the concentrations of dissolved
CO and H2 in the toluene medium.
The reactants and products were analyzed quantitatively on
GC (HP 6890) over an HP-5 column (5% diphenyl and 95%
dimethylpolysiloxane stationary phase, 30 M × 320 ꢁm ×
0.25 ꢁm) An external standard method was used for this pur-
pose.. Calibration of the analysis was done using authentic
standards.
Table 2 lists the range of conditions studied for under-
standing the kinetics of 1-decene hydroformylation using the
carbon-supported ossified catalyst. As shown in Figure 3, the
initial rates of reaction were calculated from the gas consump-
tion data with respect to time. An initial induction period
was observed. This was found to vary with the temperature
and was 10, 20, and 30 min for the temperature of 363, 353,
and 343 K, respectively. The initial rates of reaction were
3
RESULTS AND DISCUSSION
The stoichiometric reaction for 1-decene hydroformylation is
given in Scheme 1. A few experiments were conducted for
a high conversion of 1-decene to confirm the mass balance
SCHEME 1 Hydroformylation of 1-decene

4
PAGAR AND DESHPANDE
0.5
0.4
0.3
0.2
0.1
0
1.85 kg/m3
3.7 kg/m3
5.55 kg/m3
7.4 kg/m3
1-Decene
0.14
0.12
0.10
0.08
0.06
0.04
0.02
0.00
n-aldehyde.
iso-aldehyde
isomerised olefin
CO or H absorbed
2
0
1
2
3
4
5
6
7
Time, h
0
1000
2000
3000
4000
Time, s
F I G U R E 2 Concentration–time profile for hydroformylation of
1-decene. Reaction conditions: catalyst, 3.7 kg/m3 (0.37 w/w % Rh);
F I G U R E 3 A plot of product formation versus time for different
1-decene, 0.39 kmol/m3; T, 353 K; stirring speed, 20 Hz; ꢀCO+H (1:1),
2
catalyst concentrations. Reaction conditions: 1-decene 0.39 kmol/m3;
4.14 MPa; total charge, 2.7 × 10 m3; solvent: toluene, time, 6.2 h
−5
T, 353 K; stirring speed, 20 Hz; ꢀCO−H (1:1), 4.14 MPa; total charge,
2
2.7 × 10 m3; solvent, toluene; time, 1 h
−5
TA B L E 1 Henry's constants for H2 and CO in toluene
Sr. no
T (K)
343
CO (m3 MPa/kmol)
H2 (m3 MPa/kmol)
TA B L E 3 Mass transfer parameters
1
2
3
11.70
11.53
11.24
28.10
26.80
25.73
Sr. no. Parameter
Criteria Value range
−4
353
1
2
3
Gas–liquid mass transfer
< 0.1
< 0.1
< 0.2
6.85 × 10 to
−3
363
resistance (훼 )
1.96 × 10
Liquid–solid mgalss transfer
2.85 × 10 to
−4
−5
resistance (훼 )
9.97 × 10
ls
TA B L E 2 Range of conditions used for the kinetic studies
−3
Intraparticle diffusion (휑)
8.2 × 10 to
Catalyst loading (kg/m3) 0.37 wt/wt % Rh
Concentration of 1-decene (kmol/m3)
Partial pressure of hydrogen (MPa)
Partial pressure of carbon monoxide (MPa)
Temperature (K)
1.85–7.4
−3
1. 62 × 10
0.098–0.78
0.68–5.41
0.34–9.65
343–363
(gas–liquid–solid, G-L-S) catalytic reaction, and hence it
is essential to check the various mass transfer effects in
such systems. The significance of gas–liquid mass transfer
resistance (훼 ), liquid–solid mass transfer resistance (훼 ),
Solvent
Toluene
gl
ls
Stirring speed (Hz)
16.6 – 24.1
and intraparticle diffusion (휑) was analyzed by comparing
the rate of reaction, Ri (kmol/m3/s), and the maximum
possible rate as per the criteria laid out by Ramachandran and
Chaudhari.50 The values for various mass transfer parameters
are presented in Table 3, which indicate that the reaction
operates in the kinetic regime.
Reaction volume (m3)
2.7 × 10
−5
calculated after correction for the induction period, as per the
Equation 1:
Slope of product formation vs. time plot
R =
(1)
3.3 Effect of stirring speed
Volume of liquid
The effect of stirring speed on the rate of reaction was stud-
ied to further confirm that the reaction operates in the kinetic
regime and did not under a mass transfer-controlled condition,
As seen in Figure 4, the rate of reaction was independent of
the stirring speed beyond, 1000 rpm (16.6 Hz), which clearly
indicates that the reaction occurs in the kinetic regime. There-
fore, a stirring speed of 1200 rpm (20 Hz) was used for all the
studies. This ensured that the data obtained were in the kinetic
regime.
The influence of the different parameters on the initial rate
of hydroformylation and the development of the kinetic model
are discussed in the following sections.
3.2 Mass transfer effects
The hydroformylation of 1-decene using the carbon-
supported ossified catalyst is a typical case of a three-phase

PAGAR AND DESHPANDE
5
ics. An increase in the concentration of catalyst will cause an
increase in the effective active catalyst concentration as seen
from the reported mechanism in Figure 6, thereby increas-
ing the rate of reaction and hence a first-order dependence is
observed.51
45
40
35
30
25
20
15
10
5
3.5 Effect of the 1-decene concentration
Figure 7 shows the effect of 1-decene concentration on the rate
of hydroformylation in the temperature range of 343–363 K.
The plot of rate versus 1-decene concentration passes through
the maxima. The rate was found to have a linear dependence
on 1-decene in the initial concentration range. At higher sub-
strate concentration, typical substrate inhibited kinetics was
observed. This could be due to the formation of diolefinic
species in equilibrium, which can reduce the concentra-
tion of active catalyst and thereby rate. Such observation
has been reported in kinetics of hydroformylation of olefins
using heterogeneous,41,42 homogeneous,52,53 and biphasic54
catalysts.
0
800
1000
1200
1400
Agitation speed, rpm
F I G U R E 4 A plot of rate of hydroformylation of 1-decene versus
stirring speed. Reaction conditions: catalyst, 3.7 kg/m3 (0.37 w/w %
Rh); 1-decene, 0.39 kmol/m3; T, 363 K; ꢀCO+H (1:1), 4.14 MPa; total
2
3.6 Effect of partial pressure of hydrogen
charge, 2.7 × 10 m3; solvent, toluene; time, 1 h
−5
As seen in Figure 8, the rate of reaction was found to show a
60
first-order dependence on ꢀH at a constant CO partial pres-
2
sure of 2.06 MPa. As per the hydroformylation mechanism
(Figure 6), the oxidative addition of H2 is the rate-determining
step. Hence, with increasing pressure of hydrogen the rate
enhancement is observed.
343 K
50
353 K
363 K
40
30
20
10
0
3.7 Effect of partial pressure of carbon
monoxide
Figure 9 shows the effect of P on the rate of hydroformy-
lation of 1-decene at a 2.07 CMO Pa H2 partial pressure. A
plot of rate versus CO partial pressure passes through max-
imum. In the initial pressure range, the rate was found to
be first order with respect to P and inversely dependent
on P at higher CO pressuresC.OAs per the mechanism of
rhodiCuOm-catalyzed hydroformylation, using triphenyl phos-
phine trisulfonate ligand (Figure 6), the inhibition with CO
occurs due to the formation of inactive di and tricarbonyl acyl
rhodium species such as [RCH2CH2CORh(CO)2(TPPTS)2]
and[RCH2CH2CORh(CO)3(TPPTS)]. In general, the inhibi-
0
2
4
6
8
Catalyst loading, kg/m3
F I G U R E 5 A plot of rate versus catalyst loading in
hydroformylation of 1-decene. Reaction conditions: 1-decene,
0.39 kmol/m3; T, 343–363 K; stirring speed, 20 Hz; ꢀCO+H (1:1), 4.14
2
MPa; total charge, 2.7 × 10 m3; solvent, toluene; time, 1 h
tion with P is observed in the range of 0.3–0.5 MPa.55–57
−5
CO
In the case of the supported ossified catalysts, the inhibition is
observed at relatively higher PCO, which could be due to the
presence of excess TPPTSBa3/2 ligand on the support. This
makes the phosphine easily available for binding the metal
center and prevents the formation of inactive dicarbonyl and
tricarbonyl species at lower CO pressures. It is well known
that in case of phosphine-modified rhodium systems the max-
imum rate with P is highly dependent upon the Rh: PPh3
ratio. At a higherCrOatio, the maximum is observed at higher
3.4 Effect of catalyst loading
The effect of catalyst loading on the rate of hydroformyla-
tion of 1-decene was studied in the temperature range of 343–
363 K, 1-decene concentration of 0.39 kmol/m3, and a total
pressure of CO + H2 = 4.14 MPa (CO/H2 = 1). The results are
shown in Figure 5. The rate was found to be linearly dependent
on the catalyst concentration, indicating a first-order kinet-

6
PAGAR AND DESHPANDE
HRh(CO)(TPPTS)3
(OH)Rh(CO)(TPPTS)2
R-CH2CH2CHO
CH3
-TPPTS
H2
OH2
CO
R-CH-CHO
HRh(CO)(TPPTS)2
HRh(CO)2(TPPTS)2
R-CH=CH2
(H )
2
(RCH2CH2CO)Rh(CO)(TPPTS)2
CH3
(RCHCO)Rh(CO)(TPPTS)
(H2)
2
R-CH=CH2
HRh(CO)2(TPPTS)2
H2
(RCH2CH2CO)Rh(CO)(TPPTS)2
CH3
RCH2CH2Rh(CO)2(TPPTS)2
CH3
RCHRh(CO)2(TPPTS)2
(RCHCO)Rh(CO)(TPPTS)2
CO
CO
(RCH2CH2CO)Rh(CO)2(TPPTS)2
CH3
(RCHCO)Rh(CO)2(TPPTS)2
CO
CO
TPPTS
TPPTS
(RCH2CH2CO)Rh(CO)3(TPPTS)
CH3
(RCH2CH2CO)Rh(CO)3(TPPTS)
F I G U R E 6 Mechanism for hydroformylation using HRhCO(TPPTS)3 catalyst
58 The Rh:P ratio used in this work is 1:6, and hence such
catalyzed hydroformylation, using a triphenyl phosphine lig-
and, where inhibition with CO occurs at a much lower pres-
sure range.59–62
P
.
CO
an observation is likely.
The role of carbon support on adsorption of H2 and CO
gases may also contribute to the observed trend. It was
observed experimentally that the solubility of both the gases
is slightly higher in the presence of carbon-supported ossi-
fied catalyst (may be due to adsorption of gases on carbon) as
compared to the solubility in a solvent alone. Because of the
higher availability of the H2 on the catalyst surface, the forma-
tion of inhibiting species may take place at a higher PCO. The
inhibition is more pronounced at 363 K, whereas it is barely
observed at the lower temperature of 343 K. This observation
is in contrast to the trends reported in homogeneous rhodium-
During the course of this study, it was also observed that
the n/i ratio was not strongly influenced by the concentration
of the parameter studied. The n/i ratio varied in the range of
2.4–3.0 for all the parameters investigated.
3.8 Kinetic models
An empirical approach was employed for developing the
kinetic rate equation. The independence of the rate on stir-
ring speed and also the analysis of the different mass transfer

PAGAR AND DESHPANDE
7
60
50
40
30
20
10
0
343 K
353 K
363 K
343 K
353 K
363 K
40
35
30
25
20
15
10
5
0
0
0.2
0.4
0.6
0.8
0
2
4
6
8
1-Decene concentration, kmol/m3
PCO, MPa
F I G U R E 7 A plot of rate versus 1-decene concentration effect in
the hydroformylation of 1-decene. Reaction conditions: catalyst,
3.7 kg/m3 (0.37 w/w % Rh); T, 343–363 K; stirring speed, 20 Hz;
F I G U R E 9 A plot of rate versus P for the hydroformylation of
CO
1-decene. Reaction conditions: catalyst, 3.7 kg/m3 (0.37 w/w % Rh);
−5
1-decene, 0.39 kmol/m3; T, 343–363 K; stirring speed, 20 Hz; ꢀH
:
ꢀCO+H (1:1), 4.14 MPa; total charge, 2.7 × 10 m3; solvent, toluene;
2
2
−5
2.07 MPa; total charge, 2.7 × 10 m3; solvent: toluene; time, 1
time: 1 h
343 K
80
best fit was based on the least minimum error between the
predicted and experimental rates as shown in Equation 2:
353 K
70
363 K
푛
∑
[
]
2
Φ =
푅퐴푖 − 푅′퐴푖
(2)
60
50
40
30
20
10
0
푖=1
where Φ, which represents the sum of the squares of the differ-
ence between the observed and predicted rates, is the objective
function to be minimized (Φmin); n is the number of experi-
mental data, whereas RAi and R′ are the predicted and exper-
imental rates, respectively. TablAei 4 also shows the values of
the rate parameters and Φ
.
The following criteria mwienre used to discriminate the rate
models: (i) thermodynamic viability, (ii) activation energy
values, and (iii) the error (Φmin) between the experimental and
predicted rates, i.e. the fitting of the equation. Rate models II
and III showed inconsistency of the equilibrium constants and
also had high activation energy and were not considered fur-
ther. Since negative values of rate parameters were not possi-
ble, Model V was rejected. The Φmin value for model IV was
higher than that for model I. Hence, model I (Equation 3) was
considered the best model to represent the kinetics of hydro-
formylation of 1-decene in the presence of a carbon-supported
ossified catalyst:
0
2
4
6
PH2, MPa
F I G U R E 8 A plot of rate versus ꢀH for the hydroformylation of
2
1-decene. Reaction conditions: catalyst, 3.7 kg/m3 (0.37 w/w % Rh);
1-decene, 0.39 kmol/m3; T, 343–363 K; stirring speed, 20 Hz; P
,
CO
−5
2.07 MPa; total charge, 2.7 × 10 m3; solvent, toluene; time: 1 h
resistances (Table 3) indicated that the data were indeed rep-
resenting the true chemical reaction, free of any mass transfer
resistances. The initial rate data could thus be used to evaluate
the intrinsic kinetic parameters.
푘1퐴퐵퐶퐷
(1+퐾2퐷)2(1+퐾3퐵)2
푟 =
(3)
Several rate equations based on the observed rate depen-
dencies were proposed as shown in Table 4. A nonlinear
regression analysis (Marquardt method) was used to fit the
data, and the different kinetic parameters were evaluated. The
In this equation, k is the intrinsic rate constant
(m9/kmol3/s), whereas the different concentrations are
represented as follows:

8
PAGAR AND DESHPANDE
TA B L E 4 Values of kinetic parameters at different temperatures
Model
Rate model
T (K)
k1
K2
K3
9.58 × 10
ꢀmin
푘1퐴퐵퐶퐷
(1+퐾2퐷)2(1+퐾3퐵)2
−3
−1
−12
I
푟 =
343
3.14 × 10
3.95
8.76 × 10
−3
−1
−11
353
363
343
5.92 × 10
1.16 × 10
4.97
5.90
9.46 × 10
9.24 × 10
3.60 × 10
1.54 × 10
8.12 × 10
−2
−1
−10
푘1퐴퐵퐶퐷
−3
−12
II
푟 =
푟 =
푟 =
1.43 × 10
1.76 × 101
2.95
(1+퐾2퐷2)(1+퐾3퐵2)
−4
−2
−9
−9
353
3.27 × 104
4.90 × 108
9.17 × 10
1.20 × 10
363
4.49
3.40 × 104
1.82 × 10
5.24 × 10
푘1퐴퐵퐶퐷
(1+퐾2퐷)(1+퐾3퐵)
−2
−11
III
IV
343
1.51 × 10
7.23 × 101
2.64
1.13 × 10
−2
−1
−11
−10
353
2.88 × 10
7.35 × 101
2.61
4.60 × 10
363
5.17 × 10
6.95 × 102
2.52
2.06 × 10
푘1퐴퐵퐶퐷
(1+퐾2퐷)2(1+퐾3퐵)
−3
−12
343
3.42 × 10
6.29 × 10
3.98
2.72
2.64
9.78 × 10
−3
−11
353
363
343
3.93
3.91
1.90
4.00 × 10
2.31 × 10
9.57 × 10
5.67 × 102
3.65 × 105
−9
푘1퐴퐵퐶퐷
(1+퐾2퐷)3(1+퐾3퐵)3
−3
−1
−12
V
푟 =
2.52 × 10
1.26 × 103
5.84 × 10
−1
−9
353
363
3.82 × 103
–1.47 × 10
5.62 × 10
6.08 × 10
1.68 × 10
−3
−1
−10
9.42 × 10
1.91
80
-3
-4
-5
-6
-7
-8
70
60
50
40
30
20
10
0
2.7
2.75
2.8
2.85
2.9
2.95
0
20
40
60
80
1/T × 103, K-1
Experimental rates, × 106 kmol/m3/s
F I G U R E 1 1 Temperature dependence of rate constant
F I G U R E 1 0 Comparison of experimental rates and rates
predicted using model I
the Arrhenius plot shown in Figure 11. The rate parameters
A: concentration of H2 in toluene, kmol/m3,
B: concentration of CO in toluene, kmol/m3,
C: concentration of catalyst, kmol/m3, and
D: 1-decene concentration, kmol/m3.
K and K show opposite trends. Both K and K are in fact
3
2
3
lu2mped parameters, which describe the overall trends and not
individual equilibrium constants. Such a behavior is thus, pos-
sible.
The rate parameters for Equation 3 for all the temperature are
The validity of the proposed model I was cross-checked by
plotting the experimental and observed rates at varying con-
centrations of the variables for all temperatures (Figure 12).
The model was found to predict the trends in good agreement
with experimental observations.
presented in Table 4 (entry 1).
Figure 10 shows good agreement between the experimen-
tal and predicted rates, with an average deviation of 5%.
The activation energy was evaluated as 67.94 kJ/mol from

PAGAR AND DESHPANDE
9
363 K Experimental
363 K Experimental
353 K Experimental
343 K Experimental
predicted
4
3.5
3
Cata
Sub
353 K Experimental
6
5
4
3
2
1
0
343 K Experimental
Predicted
2.5
2
1.5
1
0.5
0
0
2
4
6
8
0
0.2
0.4
0.6
0.8
1
3
1-Decene concentration, kmol/m3
Catalyst concentration, kmol/m
363 K Experimental
353 Experimental
343 Experimental
Predicted
363 K Experimental
353 K Experimental
343 K Experimental
Predicted
6
8
7
6
5
4
3
2
1
0
5
4
3
2
1
0
0
0.2
0.4
0.6
0.8
0
0.05
0.1
0.15
0.2
0.25
H2 concentration, kmol/m3
CO concentration, kmol/m3
F I G U R E 1 2 Validation of the proposed rate model for various reaction parameters
to that observed in homogeneous and biphasic media. A rate
equation has been proposed based on the observed data, which
is in full agreement with the experimental rates obtained. The
activation energy was calculated to be 67.94 kJ/mol.
4
CONCLUSIONS
The ossified HRh(CO)(TPPTS)3 catalyst supported on carbon
was found to be the best considering the stability of the cat-
alyst as compared to that ossified catalyst on other supports.
The detailed analysis of the various mass transfer effects in the
G–L–S system was evaluated. The kinetics of 1-decene hydro-
formylation using the carbon-supported ossified catalyst in
toluene has been investigated in a temperature range of 343–
363 K. The rate was found to be first order with respect to cat-
alyst and partial pressure of hydrogen. The plots of rate versus
1-decene concentration as well as P passed through max-
ima and show typical substrate inhibiCtiOon at higher concentra-
tions. In the lower concentration range, the rate was found to
be first order with respect to ligand and P
ACKNOWLEDGMENTS
Research fellowship provided by CSIR India to NSP is
acknowledged. The funding provided by the Task Force on
Catalysis from the CSIR (CMM0005.3) is also acknowledged.
ORCID
Nitin S. Pagar
https://orcid.org/0000-0002-3141-3356
This kinetics using the carbon-supporteCdOo.ssified catalyst is
different from kinetics observed in homogeneous and bipha-
sic catalysis with respect to the substrate concentration effect,
which shows the substrate inhibition effect at a higher sub-
strate concentration. An unusual observation for this catalyst
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How to cite this article: Pagar NS, Deshpande RM.
Kinetics of hydroformylation of 1-decene using car-
bon supported ossified HRh(CO)(TPPTS)3 catalyst.
Int J Chem Kinet. 2018;1–11. https://doi.org/10.1002/
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