Hydrolysis kinetics of 2-cyanopyridine, 3-cyanopyridine, and 4-cyanopyridine in high-temperature water

Article abstract of DOI:10.1002/kin.20707

We report herein the kinetic studies on hydrolysis of three cyanopyridines in high-temperature water. 3-Cyanopyridine, 4-cyanopyridine and 2-cyanopyridine underwent consecutive hydrolysis to the corresponding pyridinecarboxamides and picolinic acids. Further decarboxylation to pyridine was observed for 2-cyanopyridine hydrolysis. Experiments at different initial reactant concentrations revealed that these compounds exhibited the first-order kinetics. Experiments at different temperatures showed that the first-order rate constants displayed an Arrhenius behavior with activation energies of 74.3, 40.3, and 83.7 kJ mol^-1 for 3-cyanopyridine, 4-cyanopyridine, 2-cyanopyridine, respectively. The activation energies obtained for 3-pyridinecarboxamide, 4-pyridinecarboxamide and 2-pyridinecarboxamide hydrolysis are 80.1, 32.7, and 70.5 kJ mol^-1, respectively. The effect of substituent position on activation energies for cyanopyridine and pyridinecarboxamide hydrolysis is ortho a meta > para.

Full text of DOI:10.1002/kin.20707

Hydrolysis Kinetics of
2
3
4
-Cyanopyridine,
-Cyanopyridine, and
-Cyanopyridine in
High-Temperature Water
JIE FU, HAOMING REN, CHAOJUN SHI, XIUYANG LU
Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, People’s Republic of China
Received 26 September 2011; revised 21 November 2011; accepted 25 November 2011
DOI 10.1002/kin.20707
Published online in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: We report herein the kinetic studies on hydrolysis of three cyanopyridines in high-
temperature water. 3-Cyanopyridine, 4-cyanopyridine and 2-cyanopyridine underwent con-
secutive hydrolysis to the corresponding pyridinecarboxamides and picolinic acids. Further
decarboxylation to pyridine was observed for 2-cyanopyridine hydrolysis. Experiments at dif-
ferent initial reactant concentrations revealed that these compounds exhibited the first-order
kinetics. Experiments at different temperatures showed that the first-order rate constants
−1
displayed an Arrhenius behavior with activation energies of 74.3, 40.3, and 83.7 kJ mol
for 3-cyanopyridine, 4-cyanopyridine, 2-cyanopyridine, respectively. The activation energies
obtained for 3-pyridinecarboxamide, 4-pyridinecarboxamide and 2-pyridinecarboxamide hy-
−1
drolysis are 80.1, 32.7, and 70.5 kJ mol , respectively. The effect of substituent position on
activation energies for cyanopyridine and pyridinecarboxamide hydrolysis is ortho ≈ meta >
para. ꢀC 2012 Wiley Periodicals, Inc. Int J Chem Kinet 1–8, 2012
INTRODUCTION
small organic compounds, and higher ion product. All
of these properties are temperature dependent and can
be manipulated to optimize the reaction environment
[1]. Therefore, HTW can support ionic, polar nonionic,
and free-radical reactions. The relative rates of these
different classes of reactions can be very sensitive to
the reaction conditions. The state-sensitive nature of
the solvent properties can give rise to marked tem-
perature and density effects on the reaction kinetics,
as observed experimentally for numerous reactions in
HTW [2].
High-temperature water (HTW), defined as liquid wa-
◦
ter above 180 C, is a green medium for chemical reac-
tions. Compared with water at room temperature, HTW
features lower dielectric constant, better solubility for
Correspondence to: X. Lu; e-mail: luxiuyang@zju.edu.cn.
Contract grant sponsor: National Natural Science Foundation of
China.
Contract grant number: 20976160.
Contract grant sponsor: Zhejiang Provincial Natural Science
Foundation of China.
Nitriles were focused on because of their exis-
tence in industrial waste streams and in the product
spectra from the reaction of aliphatic NO2 containing
Contract grant number: R4080110.
ꢀ
c 2012 Wiley Periodicals, Inc.

2
FU ET AL.
compounds in HTW [3]. A better understanding of the
behavior of nitriles in HTW would assist the attempts
to use HTW for waste cleanup. In addition, hydroly-
sis of nitriles is one of the best approaches to prepare
amides or carboxylic acids. Traditionally, hydrolysis of
nitriles to the corresponding amides or carboxylic acids
is carried out in water with a strong acid or base catalyst
reaction are obtained. The results provide insight into
the effect of substituent position and heterocyclic N on
hydrolysis of heterocyclic nitriles and amides.
EXPERIMENTAL
Materials
[4–6]. These base- or acid-catalyzed reactions have cer-
3-Cyanopyridine (99%) was obtained from Shang-
tain disadvantages such as undesired by-products, salt
yield from additional neutralization, and environmen-
tal pollutions. HTW provides a green strategy without
strong acid or base catalyst for amide or carboxylic
acid production. Hence, it is important to understand
the kinetics and mechanisms for the hydrolysis of ni-
triles in HTW.
There is a modest body of literature on hydrolysis of
various kinds of nitriles in HTW, but it centers primar-
ily on aromatic nitriles, aliphatic nitriles, and dinitriles
hai Bangcheng Chemical Co., Ltd. (Shanghai, Peo-
ple’s Republic of China). 4-Cyanopyridine (99%),
2-cyanopyridine (99%), and 4-pyridinecarboxamide
(98%) were obtained from ACROS Organics (Geel,
Belgium). 3-Pyridinecarboxamide (99.5%) and 3-
picolinic acid (99.5%) were obtained from Chengdu
Kelong Chemical Co., Ltd. (Sichuan, People’s Repub-
lic of China). 2-Pyridinecarboxamide (99%) was ob-
tained from TCI Chemical Co., Ltd. (Shanghai, Peo-
ple’s Republic of China). 4-Picolinic acid (99%) was
obtained from Sinopharm Chemical Reagent Co., Ltd.
[
3,7–13]. The literature on hydrolysis of heterocyclic
nitriles in HTW is much more sparse. The kinetics of
-cyanopyridine was investigated in our previous arti-
cle [14]. The activation energies for the hydrolysis of
-cyanopyridine and 3-pyridinecarboxamide were ob-
(
Shanghai, People’s Republic of China). 2-Picolinic
acid (99%) was obtained from J & K Chemical, Ltd.
Beijing, People’s Republic of China). They are all of
3
(
3
analytical reagent grade and were used as received.
Deionized water was prepared in-house.
tained. However, the kinetics of the consecutive hydrol-
ysis of 3-cyanopyridine in our previous work required
additional experiments using 3-pyridinecarboxamide
as a reactant, which is time consuming and needs to
be improved. Moreover, the position of the nitrile sub-
stituent will probably affect the reaction activity of
cyanopyridine. The research on the position effect will
help us to have a better understanding on the hydrolysis
of heterocyclic nitriles in HTW.
Reactors
The reactor is made up of 316-L stainless steel, which
mainly consists of a high-pressure autoclave (500-mL
volume), a plunger pump, a mechanical impeller, and
a sampling line. The schematic diagram is available
in our previous publication [15]. The sampling line
includes a high-pressure valve and a cooler. The appa-
ratus exhibits the following capabilities: temperature
In this article, to further advance understanding of
hydrothermal hydrolysis of heterocyclic nitrile, three
compounds were selected for study: 3-cyanopyridine,
◦
up to 320 C, pressure up to 20 MPa, good temperature
◦
control of ± 1 C and on-line sampling. The reactor and
4-cyanopyridine, and 2-cyanopyridine. These com-
furnace were made by Dalian Kemao Experimental
Equipment Co., Ltd. (Liaoning, People’s Republic of
China).
pounds are the N-heterocyclic analogs of benzonitrile,
and each compound has a nitrile substituent attached
to 3-, 4-, and 2-carbon, respectively. These compounds
can be used to examine effect of the heterocyclic N
atom and nitrile substituent position on the nitrile hy-
drolysis. Figure 1 shows the reaction pathways for hy-
drolysis of the three cyanopyridines (2-picolinic acid
can be subsequently decarboxylated). The model on the
consecutive reactions is established without additional
experiments using pyridinecarboxamide or picolinic
acid as a reactant, and the activation energies for each
Experimental Procedure
The reactor was degassed with a vacuum pump and
then filled with high-purity nitrogen. Three hundred
milliliter of degassed deionized water was added to the
reactor through the valve by using a plunger pump. Af-
ter the temperature inside the reactor had reached the
desired reaction temperature, 60 mL reactant solution
Figure 1 Reaction pathway for hydrolysis of cyanopyridines.
International Journal of Chemical Kinetics DOI 10.1002/kin.20707

HYDROLYSIS KINETICS OF CYANOPYRIDINES IN HIGH-TEMPERATURE WATER
3
(in water) was quickly injected by the plunger pump
through the valve and the line was rinsed with 20 mL of
deionized water. After adding this material, the reactor
returned to the reaction temperature within a few min-
utes. The system pressure was maintained at 8 MPa by
high-pressure nitrogen from a cylinder. Finally, sam-
ples were collected at certain reaction times. The reac-
tion mixture was constantly agitated at 400 rpm using
a mechanical impeller throughout the duration of the
reaction.
Sampling and Analysis
Two to three milliliter samples were collected after
Figure 2 Temporal variation of 4-cyanopyridine conver-
sions at 220 C and different initial concentrations.
◦
1–2 mL of solution had first been vented to purge
the sample line. The liquid sample was quantita-
tively analyzed by HPLC (Agilent 1100; Santa Clara,
CA, USA) with a UV detector by an external ref-
erence method. The HPLC column was KNAUER-
C18 (4 mm ID × 250 mm) (Berlin, Germany). For
trations of 4-cyanopyridine were 0.5, 0.75, 1.0, 1.5,
and 2.0 g/L. The conversion rates were similar at dif-
ferent concentrations, which signal first-order kinetics
for the hydrolysis reactions. Similar results were ob-
tained for effect of concentration on 3-cyanopyridine
and 2-cyanopyridine hydrolysis.
3-cyanopyridine, the mobile phase was 5 g/L of
H3PO4 solution:methanol:acetonitrile = 47:50:3 flow-
ing at 0.6 mL/min; the column temperature was
Effect of Temperature on Hydrolysis of
◦
3
5 C; the injection volume was 5 μL; and the mi-
3
-Cyanopyridine
crowave length of detector was 210 nm. For 4-
cyanopyridine, the mobile phase was 3 g/L of H3PO4
Figure 3 shows the effect of temperature on the hydrol-
ysis of 3-cyanopyridine. The reactions were carried out
solution:methanol:acetonitrile = 70:15:15 flowing at
◦
◦
at temperatures of 210, 220, 230, 240, and 250 C and
0
.6 mL/min; the column temperature was 35 C; the
an initial 3-cyanopyridine concentration of 0.5 g/L. The
reaction pressure was 8 MPa. Nearly complete conver-
sion of 3-cyanopyridine occurred after about 150 min
injection volume was 5 μL; and the microwave length
of the detector was 268 nm. For 2-cyanopyridine, the
mobile phase was 5 g/L of H3PO4 and 2 g/L triethy-
lamine solution:methanol:acetonitrile = 75:20:5 flow-
◦
◦
at 250 C. At 210 C, on the other hand, the conversion
was only 86% after 240 min. 3-Pyridinecarboxamide
and 3-picolinic acid were the only products observed.
The yield variation of 3-pyridinecarboxamide shows
a clear trend of an intermediate product: at the begin-
ning; it increased with the elapsing of the reaction time,
then decreased after reaching a maxima. The maximum
yield at each temperature was 70–80%. The yield of
◦
ing at 0.4 mL/min; the column temperature was 35 C;
the injection volume was 10 μL; and the microwave
length of the detector was 268 nm. Peaks were identi-
fied by comparison of their retention times with those
of standard solutions of pure compounds, and identities
were confirmed by GC/MS (Agilent 6890/5973).
Product yields were calculated as the number of
moles of product recovered divided by the initial num-
ber of moles of cyanopyridine loaded into the reactor.
The mole balances were calculated as the total number
of moles of products and cyanopyridine recovered di-
vided by the initial number of moles of cyanopyridine
loaded into the reactor.
3-picolinic acid always increased with the elapsing of
the reaction time at each temperature. The curves in
Fig. 3 are calculated from the first order consecutive
reaction model and will be described later in this arti-
cle. The mole balances at each temperature are shown
in Fig. 3d. The mole balance was always around 95–
105%.
RESULTS AND DISCUSSION
Effect of Temperature on Hydrolysis of
-Cyanopyridine
4
Effect of Concentration on Hydrolysis of
Cyanopyridine
Figure 4 shows the effect of temperature on the hydrol-
ysis of 4-cyanopyridine. The reactions were conducted
at 190, 205, 220, 235, and 250 C and an initial 4-
◦
Figure 2 shows the effect of initial concentration on
◦
the hydrolysis of 4-cyanopyridine at 220 C. The reac-
cyanopyridine concentration of 0.5 g/L. The reaction
◦
tion pressure was maintained at 8 MPa. The concen-
pressure was 8 MPa. At 250 C, 3-cyanopyridine was
International Journal of Chemical Kinetics DOI 10.1002/kin.20707

4
FU ET AL.
Figure 3 Temporal variation of 3-cyanopyridine conversion, yields to 3-pyridinecarboxamide and 3-picolinic acid, and mole
balance at different temperatures: (a) conversion of 3-cyanopyridine, (b) yield of 3-pyridinecarboxamide, (c) yield of 3-picolinic
acid, and (d) mole balance.
◦
nearly consumed within 90 min and the conversion
was 78% at 190 C for 90 min. The effect of temper-
ducted at 210, 220, 230, 240, and 250 C and an initial
2-cyanopyridine concentration of 0.5 g/L. The reac-
tion pressure was 8 MPa. Nearly complete conver-
sion of 4-cyanopyridine occurred after about 30 min
◦
ature on 3-cyanopyridine seems not to be very sig-
nificant. 4-Pyridinecarboxamide and 4-picolinic acid
were the only products observed. Their yields at each
temperature are shown in Figs. 4b and 4c. Same as
in 3-pyridinecarboxamide, the yield variation of 4-
pyridinecarboxamide shows a clear trend of the in-
termediate product. The maximum yield at each tem-
perature was about 65%. The yield of 4-picolinic acid
always increased with elapsing of the reaction time
at each temperature. The smooth curves were again
obtained from a first-order kinetic model that will be
discussed in the next section. The mole balances at each
temperature are shown in Fig. 4d. The mole balance
was always around 90–105%.
◦
◦
at 250 C. At 210 C, on the other hand, the conversion
was only 88% after 90 min. Differing from the products
of 3-cyanopyridine and 4-cyanopyridine, pyridine was
observed as a product besides 2-pyridinecarboxamide
and 2-picolinic acid, which suggests decarboxylation
occurred in the reaction system. The yield variation
of 2-pyridinecarboxamide also shows a clear trend of
the intermediate product. The maximum yield at each
temperature was around 80%. The yield of 2-picolinic
acid was relatively low. Eleven percent was the high-
est yield achieved for 2-picolinic acid within 90 min.
The yield of pyridine kept increasing with elapsing
of the reaction time at each temperature. The smooth
curves were again obtained from a first-order kinet-
ics model that will be discussed in the next section.
The mole balances at each temperature are shown in
Fig. 5e. Most of them were around 90–110%. Some
Effect of Temperature on Hydrolysis of
2
-Cyanopyridine
Figure 5 shows the effect of temperature on the hy-
drolysis of 2-cyanopyridine. The reactions were con-
◦
points for the mole balance at 240 and 250 C were
International Journal of Chemical Kinetics DOI 10.1002/kin.20707

HYDROLYSIS KINETICS OF CYANOPYRIDINES IN HIGH-TEMPERATURE WATER
5
Figure 4 Temporal variation of 4-cyanopyridine conversion, yields to 4-pyridinecarboxamide and 4-picolinic acid, and mole
balance at different temperatures: (a) conversion of 4-cyanopyridine, (b) yield of 4-pyridinecarboxamide, (c) yield of 4-picolinic
acid, and (d) mole balance.
below 90%, which was probably due to the experi-
mental errors.
is the concentration of carboxylic acids. k1 is the rate
constant for cyanopyridine hydrolysis to amide, k2 is
the rate constant for amide hydrolysis to carboxylic
acid.
For 2-cyanopyridine, the equations for the con-
sumption of 2-cyanopyridine and production of 2-
pyridinecarboxamide are the same as Eqs. (1) and (2).
The equations for the production of 2-picolinic acid
and pyridine are as follows:
Kinetics of Hydrolysis
Figure 1 shows the reaction pathways for the three
cyanopyridines. 3-Cyanopyridine and 4-cyanopyridine
underwent consecutive hydrolysis in HTW. The rate
equation for each reaction was assumed to be first order
in the concentration (C) of each species in the reaction.
The mole balance equations for each of the species are
as follows:
dCC
−
−
= k2CB − k3CC
= k3CC
(4)
(5)
dt
dCD
dt
dCA
−
= k1CA
(1)
(2)
(3)
dt
dCB
dt
where CD is the concentration of pyridine and k3 is the
rate constant for 2-picolinic acid decarboxylation.
We compiled the above equations into Scientist
from MicroMath (Scientist Software, St. Louis, MO,
USA) and fitted the concentrations for each of the
species versus time data at each temperature. The soft-
ware solved the governing differential equations for a
=
k1CA − k2CB
dCC
dt
−
= k2CB
where CA refers to the concentration of cyanopy-
ridines, CB is the concentration of amides, and CC
International Journal of Chemical Kinetics DOI 10.1002/kin.20707

6
FU ET AL.
Figure 5 Temporal variation of 2-cyanopyridine conversion, yields to 2-pyridinecarboxamide, 2-picolinic acid and pyridine,
and mole balance at different temperatures: (a) conversion of 2-cyanopyridine, (b) yield of 2-pyridinecarboxamide, (c) yield of
2-picolinic acid, (d) yield of pyridine, and (e) mole balance.
batch reactor and simultaneously estimated the value of
the rate constant by minimizing the sum of the squared
differences between the experimental and calculated
concentration for each of the species.
The curves in Figs. 3–5 show that the reactant con-
version and product yields calculated using the model
reasonably represent the experimental data for most
steps of consecutive hydrolysis of the three cyanopy-
ridines at all temperatures. This data fitting provided
estimates for the rate constants at each temperature.
The results of this parameter estimation are presented
in Table I. The uncertainties shown are the standard de-
viations in the rate constants as determined by the pa-
rameter estimation software. The standard deviations
International Journal of Chemical Kinetics DOI 10.1002/kin.20707

HYDROLYSIS KINETICS OF CYANOPYRIDINES IN HIGH-TEMPERATURE WATER
7
Table I Hydrolysis (Decarboxylation) Rate Constants (×10− min ) for Cyanopyridines, Pyridinecarboxamides, and
3
−1
Picolinic Acid
3
-
3-
4-
4-
2-
2-
2-Picolinic
Acid
◦
T ( C)
Cyanopyridine Pyridinecarboxamide Cyanopyridine Pyridinecarboxamide Cyanopyridine Pyridinecarboxamide
1
2
2
2
2
2
2
2
90
05
10
20
30
35
40
50
19.8 ± 0.9
33.9 ± 2.2
3.2 ± 0.4
3.92 ± 0.37
7.42 ± 0.08
10.6 ± 0.2
16.0 ± 1.4
0.837 ± 0.061
1.43 ± 0.07
2.00 ± 0.69
31.6 ± 0.8
47.8 ± 1.8
73.2 ± 3.3
3.58 ± 0.32
2.86 ± 0.39
5.17 ± 0.34
17.3 ± 4.0
37.9 ± 12.5
45.5 ± 7.3
38.2 ± 1.8
45.8 ± 1.9
4.75 ± 0.41
6.63 ± 0.31
20.7 ± 1.5
31.2 ± 0.7
74.3 ± 2.7
2.6 ± 1.0
4.17 ± 0.11
80.1 ± 5.1
109 ± 6
152 ± 8
7.90 ± 0.58
11.6 ± 0.6
70.5 ± 16.5
136 ± 49
95.6 ± 116.4
194 ± 41
76.4 ± 8.5
40.3 ± 5.9
8.45 ± 0.49
32.7 ± 2.6
Ea (kJ/mol)
83.7 ± 1.4
of rate constants given in the table are all satisfactory
except the values for 2-picolinic acid decarboxylation.
Fortunately, we have focused on the consecutive hy-
drolysis of cyanopyridines.
The variation of the rate constants with tempera-
ture followed the Arrhenius equation. The Arrhenius
parameters were determined by linear regression of
ln k versus 1/T . The Arrhenuis parameters were A
ridine and pyridinecarboxamide hydrolysis is ortho ≈
◦
meta > para. At 220 C, the rate constants of cyanopy-
ridine hydrolysis have the sequence of ortho > para >
meta, and the rate constant sequence for pyridinecar-
boxamide hydrolysis is para > ortho > meta. How-
ever, both the rate constants for ortho-cyanopyridine
◦
and pyridinecarboxamide are highest at 250 C, be-
cause of the high activation energy. Moreover, differ-
ing from 3-cyanopyridine and 4-cyanopyridine, the 2-
cyanopyridine reaction system yielded a large amount
of pyridine, which indicates not only orthocyanopyri-
dine and pyridinecarboxamide have lower hydrother-
mal stability but also orthopicolinic acid does. It is
probably caused by the short distance between the
substituents and heterocyclic N atom. Overall, or-
thocyanopyridine, pyridinecarboxamide, and picolinic
acid are more active than meta- and paraposition
cyanopyridines, pyridinecarboxamides, and picolinic
acids.
−
1
5.90 ± 0.28
−1
5.61 ± 0.53
(
3
min ) = 10
, Ea = 74.3 ± 2.7 kJ mol for
−1
-cyanopyridine hydrolysis; A (min ) = 10
,
−1
Ea = 80.1 ± 5.1 kJ mol for 3-pyridinecarboxamide
−
1
2.87 ± 0.62
hydrolysis; A (min ) = 10
, Ea = 40.3 ±
−1
5
(
.9 kJ mol
for 4-cyanopyridine hydrolysis; A
−
1
1.17 ± 0.28
−1
min ) = 10
, Ea = 32.7 ± 2.6 kJ mol
1
−
for 4-pyridinecarboxamide hydrolysis; A (min ) =
7
.55 ± 0.15
−1
1
0
, Ea = 83.7 ± 1.4 kJ mol
for 2-
−1
5.06 ± 1.72
cyanopyridine hydrolysis; A (min ) = 10
, Ea
−
1
=
70.5 ± 16.5 kJ mol for 2-pyridinecarboxamide hy-
−1
19.1 ± 4.2
drolysis; A (min ) = 10
, Ea = 194 ± 41 kJ
−1
mol for 2-picolinic acid decarboxylation.
CONCLUSION
Effect of Substituent Position on Hydrolysis
◦
At 300 C and 8.7 MPa pressure, benzonitrile can
2-Cyanopyridine, 3-cyanopyridine and 4-cyanopyri-
dine undergo consecutive hydrolysis on the timescale
of hours in liquid water at temperatures around
be almost consumed for 225 min [3]. Based on our
results, complete consumption takes about 150, 90,
and 30 min for 3-cyanopyridine, 4-cyanopyridine,
◦
200 C. For 3-cyanopyridine and 4-cyanopyridine,
◦
and 2-cyanopyridine, respectively, at 250 C and 8
their corresponding pyridinecarboxamides and picol-
inic acids are products observed. 2-Cyanopyridine
yielded 2-pyridinecarboxamide, 2-picolinic acid, and
pyridine as the observed products. All cyanopy-
ridines exhibited consecutive first-order kinetics. The
activation energies were determined to be 74.3,
MPa pressure, which indicates that the heterocyclic
N atom can lower the hydrothermal stability of ben-
zonitrile. In Table I, the activation energies for 3-
cyanopyridine and 2-cyanopyridine hydrolysis are
quite similar, but much higher than the activation
energy of 4-cyanopyridine hydrolysis. Similar re-
sults can be found in pyridinecarboxamide hydroly-
sis: The activation energies for 3-pyridinecarboxamide
and 2-pyridinecarboxamide hydrolysis are similar,
but much higher than the activation energy of 4-
pyridinecarboxamide hydrolysis. The effect of sub-
stituent position on activation energies for cyanopy-
−1
40.3, 83.7, 80.1, 32.7, and 70.5 kJ mol
for 3-
cyanopyridine, 4-cyanopyridine, 2-cyanopyridine, 3-
pyridinecarboxamide, 4-pyridinecarboxamide, and 2-
pyridinecarboxamide hydrolysis, respectively. The
effect of substituent position on activation energies
for cyanopyridine and pyridinecarboxamide hydrol-
ysis is ortho ≈ meta > para. Ortho-cyanopyridine,
International Journal of Chemical Kinetics DOI 10.1002/kin.20707

8
FU ET AL.
pyridinecarboxamide, and picolinic acid are more
active than meta- and paraposition cyanopyridines,
pyridinecarboxamides, and picolinic acids.
7. Kr a¨ mer, A.; Mittelst a¨ dt S.; Vogel, H. Chem Eng Technol
1999, 22, 494–500.
8
. Venardou, E.; Garcia-Verdugo, E.; Barlow, S. J.;
Gorbaty, Y. E.; Poliakoff, M. Vib Spectrosc 2004, 35,
1
03–109.
BIBLIOGRAPHY
9
. Harrell, C. L.; Moscariello, J. S.; Klein, M. T. J Supercrit
Fluids 1999, 14, 219–224.
1
2
3
4
5
6
. Fu, J.; Savage, P. E.; Lu X. Ind Eng Chem Res 2009, 48,
0467–10471.
. Akiya, N.; Savage, P. E. Chem Rev 2002, 102, 2725–
750.
. Izzo, B.; Harrell, C. L.; Klein, M. T. AIChE J 1997, 43,
048–2058.
. Krieble, V. K.; Noll, C. I. J Am Chem Soc 1939, 61,
60–563.
. Wiegand, G. H.; Tremelling, M. J Org Chem 1972, 37,
14–916.
. Hall, J. H.; Gisler, M. J Org Chem 1976, 41, 3769–
770.
10. Tewari, Y. B.; Goldberg, R. N. J Chem Thermodyn 2005,
37, 720–728.
11. Duan P.; Wang, Y.; Yang, Y.; Dai, L. J Solution Chem
2009, 38, 241–258.
12. Duan, P.; Wang, X.; Dai, L. Chem Eng Technol 2007,
30, 265–269.
13. Sarlea, M.; Kohl, S.; Blickhan, N.; Vogel, H.
ChemSusChem 2010, 3, 85–90.
14. Shi, C.; Lu, X. J Zhejiang Uni (Eng Sci) 2009, 43, 1692–
1696.
15. Lu, X.; Li, Z.; Gao, F. Ind Eng Chem Res 2006, 45,
4145–4149.
1
2
2
5
9
3
International Journal of Chemical Kinetics DOI 10.1002/kin.20707