Chinese Journal of Chemical Engineering 23 (2015) 1335–1339

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Chinese Journal of Chemical Engineering

journal homepage: www.elsevier.com/locate/CJChE

Catalysis, Kinetics and Reaction Engineering

Reaction kinetics of isopropyl palmitate synthesis

Lili Fu 1,2, Yinge Bai 3, Gaozhi Lü 4, Denggao Jiang 1,⁎
1
School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, China
2
Henan Province Product Quality Supervision and Inspection Center, Zhengzhou 450004, China
3
Institute of Process Engineering, Chinese Academy of Science, Beijing 100190, China
4
Henan EPRI Hitech Group Co., Ltd, Zhengzhou 450052, China

a r t i c l e i n f o a b s t r a c t

Article history: In this study, the kinetics of isopropyl palmitate synthesis including the reaction mechanism was studied based
Received 17 October 2014 on the two-step noncatalytic method. The liquid-phase diffusion effect on the reaction process was eliminated by
Received in revised form 18 April 2015 adjusting the stirring rate. The results showed that the two-step reaction followed a tetrahedral mechanism and
Accepted 27 April 2015
conformed to second-order reaction kinetics. Nucleophilic attack on the carbonyl carbon afforded an intermedi-
Available online 15 May 2015
ate, containing a tetrahedral carbon center. The intermediate ultimately decomposed by elimination of the leav-
Keywords:
ing group, affording isopropyl palmitate. The experimental data were analyzed at different temperatures by the
Isopropyl palmitate integral method. The kinetic equations of the each step were deduced, and the activation energy and frequency
Reaction kinetics factor were obtained. Experiments were performed to verify the feasibility of kinetic equations, and the result
Chemical reaction showed that the kinetic equations were reliable. This study could be very significant to both industrial application
Preparation and determining the continuous production of isopropyl palmitate.
Chloridization © 2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.
Palmitic acid

1. Introduction two-step noncatalytic method for the preparation of IPP [12,13].

Isopropyl palmitate (IPP) is one of the versatile chemical prod-
ucts and plays a significant role in personal products such as skin
creams, shampoo, conditioner, bath, and shower gels, because of
its good compatibility with the skin and high oil content of the
products, and no greasy feeling after use. Moreover, the branched
chain fatty acid esters can optimize the biodiesel properties such
as enhancing its lubrication to reduce friction caused by engine
components and reducing the pour point and cold filter plugging
point, thus could prolong the service life of the engine and improve
the low temperature fluidity [1,2]. As one of the branched chain
fatty acid ester, IPP is not only one of the components of the biodie-
sel group [3], but also could be used as additives to improve the
properties of biodiesel [4].
At present, IPP is generally prepared by the following methods:
it is synthesized from propylene and palmitic acid using sulfonic
acid type ion exchange resin as the catalyst, or synthesized from
palmitic acid and isopropanol using solid superacids or supported
solid acid as the catalyst [5–11]. The existing synthesis methods
have several disadvantages such as high cost, complex progress,
and low yield of the product; therefore, this study proposed a
⁎ Corresponding author.
E-mail address: jdg@zzu.edu.cn (D. Jiang).
The synthetic reaction consisted of a liquid phase system with no
catalyst, affording a high conversation rate with no side reaction.
Off-gas was recycled easily to synthesize the by-products. In this
study, IPP was synthesized from palmitic acid, thionyl chloride,
and isopropyl alcohol, and the reaction kinetics and kinetic model
were investigated, and all these data provided valuable and theo-
retical foundation for its scale-up and determination of the contin-
uous production technology.
2. Experimental
2.1. Reagents and instruments
2.1.1. Reagents
Analytical grade palmitic acid was purchased from Sinopharm
Chemical Reagent Co., Ltd. Thionyl chloride, isopropanol, palmitic
acid chloride, ethanol, sodium hydroxide, potassium hydroxide,
sodium bicarbonate, and potassium acid phthalate were purchased
from Tianjin Feng Chuan Chemical Reagent Technology Co., Ltd.
2.1.2. Instruments
Heat collection type magnetic stirrer DF-101S (Gongyi YingYu
instrument factory) was used for stirring. Electronic balance
TE6101-L (Sartorius AG) was used for weighing the samples. Gas

http://dx.doi.org/10.1016/j.cjche.2015.05.004
1004-9541/© 2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.
1336 L. Fu et al. / Chinese Journal of Chemical Engineering 23 (2015) 1335–1339

chromatographic analysis was performed using a GC900A high- 100

performance gas chromatograph (Shanghai Kechuang Chromato- -1
100 r· min
graph Instrument Co., Ltd). 98 -1
150 r· min

conversion of palmitoyl chloride/%

-1
96 200 r· min
2.2. Experimental -1
250 r· min
94
Under certain reaction conditions, IPP was prepared using the
following reactions:
92

CH3 ðCH2 Þ14 COOH þ SOCl2 →CH3 ðCH2 Þ14 COCl þ SO2 þ HCl ðaÞ 90

CH3 ðCH2 Þ14 COCl þ ðCH3 Þ2 CHOH→CH3 ðCH2 Þ14 COOCHðCH3 Þ2 þ HCl ðbÞ 88

86
Preliminary experiments showed that the stirring rate had a
certain effect on the conversation rate [14]. To evaluate the 84
liquid-phase diffusion, the two-step reaction was carried out at
different stirring rates of 100, 150, 200, 250 r·min− 1 while keeping 82
other conditions the same: n(thionyl chloride): n(palmitic acid) =
1.4, n(isopropanol):n(palmitoyl chloride) = 1.4, reaction temper- 80
ature 343 K. The results obtained were shown in Figs. 1 and 2, 20 40 60 80 100
when the stirring rate was 200 and 250 r·min − 1 , no significant reaction time/min
differences were found in the conversion of palmitic acid and
palmitoyl chloride. This indicated that the diffusion-controlled Fig. 2. Conversion of palmitoyl chloride vs. time for Reaction (b) at different stirring rates.
process was eliminated by selecting the appropriate stirring rate
to investigate the intrinsic kinetics of the two-step reaction.
Based on this result, the kinetic experiments in this work were all
performed at the stirring rate of 200 r·min− 1. tetrahedral carbon center, the reaction sequence is called tetrahedral
mechanism. The two-step reaction combining palmitic acid acylation
100 [18] and palmitoyl chloride alcoholysis [19,20] follows tetrahedral
100 r·min-1
98 mechanism.
150 r·min-1
200 r·min-1
96
conversion of palmitic acid/%

250 r·min-1 2.3.1. Acylation reaction mechanism [21]

94 First, palmitic acid and thionyl chloride react by nucleophilic acyl
substitution, forming chlorosulfonic acid anhydride as an intermediate,
92
which further reacts with chloride ion to afford palmitoyl chloride. R
90 stands for C15H31 in reactions (c), (d) and (e).
88

86 ðcÞ

84

82

80
20 40 60 80 100
reaction time/min
ðdÞ
Fig. 1. Conversion of palmitic acid vs. time for Reaction (a) at different stirring rates.

For the first-step acylation reaction, palmitic acid and thionyl

chloride were added to a three-neck round bottom flask equipped
with a magnetic stirrer under certain condition. A certain amount
of the reaction mixture was sampled at regular intervals, and the
conversion rate of palmitic acid was analyzed. For the second-step
alcoholysis reaction, the conversion rate of palmitoyl chloride was ðeÞ
analyzed similarly.

2.3. Reaction mechanism

Carboxylic acids and their derivatives contain carbonyl carbon in

their molecules, and they are susceptible to attack by nucleophiles, 2.3.2. Alcoholysis reaction mechanism [21]
forming intermediates [15–17]. The intermediates decompose by elim- Isopropyl alcohol reacts with palmitoyl chloride, forming a tet-
inating a leaving group. For the intermediate species containing a rahedral intermediate. Subsequent elimination of chloride from
 L. Fu et al. / Chinese Journal of Chemical Engineering 23 (2015) 1335–1339 1337

the tetrahedral intermediate affords IPP. R and R′ stand for –C15H31 Then, the natural logarithm of the Arrhenius equation leads to the
and –CH(CH3)2, respectively, in the following reactions: following Equation, showing a linear relationship between lnk and 1/T:

Ea
ln k ¼ − þ ln A: ð7Þ
RT
ðf Þ

Therefore, based on the slope and ordinate of the line, Ea and A can
be obtained.

3.2. Determination of reaction rate constants

The kinetic analysis of the two-step reaction was investigated. Based

ðgÞ on the assumption that β = n(thionyl chloride):n(palmitic acid) = 1.4
and β = n(isopropanol):n(palmitoyl chloride) = 1.4, the effect of reac-
tion temperature on the conversion for each step was studied. The
results are listed in Tables 1 and 2.

3. Reaction Kinetics Model

Table 1
Effects of temperatures on Reaction (a)
3.1. Expression of kinetics model [22]
Reaction temperature/K Conversion of palmitic acid/%
Theoretically, the kinetics of the tetrahedral mechanism reaction is 20 min 40 min 60 min 80 min 100 min
first-order reaction with respect to both the reactants; therefore, we
336 74.67 90.61 95.71 97.87 98.89
assumed that the two-step acylation and alcoholysis in this reaction 338 77.98 92.03 96.52 98.25 99.24
follow the second-order kinetics. 341 82.11 93.72 97.54 98.87 99.56
For a second-order reaction, the reaction rate is expressed by the 343 84.67 94.87 97.98 99.26 99.71
following Equation: 345 85.88 95.79 98.42 99.51 99.83

dcA
ð−r A Þ ¼ − ¼ kcA cB : ð1Þ
dt
Table 2
If cA0 = cB0, Eq. (1) could be deduced as follows: Effect of temperature on Reaction (b)

Reaction temperature/K Conversion of palmitoyl chloride/%

dcA 2
ð−r A Þ ¼ − ¼ kc2A ¼ kc2A0 ðl−xA Þ : ð2Þ
dt 20 min 40 min 60 min 80 min 100 min

336 77.68 90.25 96.04 97.91 99.07

In the following study, xA represents the conversion of palmitic acid 338 80.31 92.98 96.97 98.66 99.29
or palmitoyl chloride respectively. 341 83.80 94.74 98.23 99.23 99.71
343 85.96 95.42 98.58 99.53 99.82
Eqs. (1) and (2) were integrated to obtain the integrated rate
345 87.90 96.73 98.99 99.68 99.89
equation, showing the concentrations of reactants and products
with reaction time. For Eq. (2) the integral form is as follows:

xA The conversion in terms of ln[(β − xA)/β(1 − xA)] was calculated from

¼ kc A0 t ð3Þ
1−xA the data in Tables 1 and 2, and the relationship between ln[(β − xA)/
β(1 − xA)] and reaction time was plotted as shown in Figs. 3 and 4.
where β = c B0 /c A0 (β ≠ 1). Therefore, Eq. (1) can be deduced as
follow:

dcA
ð−r A Þ ¼ − ¼ kcA cB ¼ kc2A0 ð1−xA Þðβ−xA Þ: ð4Þ
dt

For Eq. (4), the integral equation is shown by Eq. (5).

β−xA
ln ¼ cA0 ðβ−1Þkt ðβ ≠ 1Þ ð5Þ
βð1−xA Þ

Therefore, according to the second-order rate law, a linear plot

should be obtained between the concentration vs. reaction time. If
the experimental data shows a linear relationship, the assumption
of the two-step reaction following a second-order kinetics model is
reasonable.
The Arrhenius equation associated with the relationship be-
tween reaction rate constants and reaction temperature is as
follows:

k ¼ Ae−Ea =RT : ð6Þ Fig. 3. Conversion of palmitic acid vs. time for Reaction (a).
1338 L. Fu et al. / Chinese Journal of Chemical Engineering 23 (2015) 1335–1339

Fig. 4. Conversion of palmitoyl chloride vs. time for Reaction (b). Fig. 5. Line A: lnk vs. 1/T of Reaction (a).

Each step of the reaction shows a linear relationship; therefore, the

assumption that the two-step reaction followed second-order kinetics is
reasonable.
Reaction rate constant (k) at the corresponding temperatures was
obtained from the slope of the line as shown in Figs. 3 and 4. The results
are listed in Tables 3 and 4.

Table 3
Value of k of Reaction (a) at the different temperatures

Temperature/K Equation k/L·mol−1·min−1 R2

336 y = 0.0329 x 0.03306 0.9993

338 y = 0.00361 x 0.03627 0.9990
341 y = 0.0415 x 0.04170 0.9992
343 y = 0.0458 x 0.04602 0.9995
345 y = 0.0507 x 0.05094 0.9985

Note: y was used for ln βðβ−x

1−xA Þ, x for t in the following study.
A

Fig. 6. Line B: lnk vs. 1/T of Reaction (b).

Table 4
3.4. Determination of reaction kinetics equations
Value of k of Reaction (b) at the different temperatures
According to Eqs. (1) and (6) and the values of Ea and A for each step,
Temperature/K Equation k/L · mol−1·min−1 R2
the kinetics equations of IPP synthesis are as follows:
336 y = 0.034 x 0.03489 0.9978
338 y = 0.038 x 0.03899 0.9975 Step 1:
341 y = 0.0459 x 0.0471 0.9992
343 y = 0.0508 x 0.05213 0.9989 dcPA 46103
345 y = 0.0561 x 0.05756 0.9984 −r PA ¼ − ¼ 4:63  105 e− RT cPA cTC : ð8Þ
dt

Step 2:

dcPC 54:15103
3.3. Determination of Ea and A for the reaction −r PC ¼ − ¼ 9:08  106 e− RT cPC cIPA : ð9Þ
dt

According to the Arrhenius Eq. (7), the plot of lnk vs. 1/T is
shown in Figs. 5 and 6. A line drawn at that abscissa represents 1/
T and ordinate lnk. Based on the slope and ordinate of the lines,
activation energy E a and frequency factor A for each step were
obtained.
The slopes of the Lines A and B were − 5532.46 and − 6513.18,
respectively. The ordinate of the Lines A and B were 13.045 and
16.022. The result of the calculation shows that the activation ener-
gy (Ea1) and frequency factor (A1) for step 1 acylation reaction are
46 kJ·mol− 1 and 4.63 × 105, respectively, and the activation energy
(E a2 ) and frequency factor (A 2 ) were 54.15 kJ·mol − 1 and
9.08 × 106 for Step 2 alcoholysis reaction.
In Eqs. (8) and (9), PA is the palmitic acid, TC is the thionyl
chloride, PC is the palmitoyl chloride, and IPC is the isopropanol.
The dynamic model of IPP synthesis was built and expressed in
Eqs. (8) and (9).
4. Verified Experiments
To verify the feasibility of kinetic equations, verified experiments
were performed. Based on the assumption that n(thionyl chloride):
n(palmitic acid) = 1.4, n(isopropanol): n(palmitoyl chloride) = 1.4,
 L. Fu et al. / Chinese Journal of Chemical Engineering 23 (2015) 1335–1339
the effect of the reaction time on the conversion for each step was stud-
ied at different temperatures. The results from the calculation according
to Eqs. (8) and (9) agreed well with the experimental values. Figs. 7 and
8 show the comparison, indicating that the dynamics equations are
reliable.
Fig. 7. Conversion of palmitic acid and the calculated results of kinetic equation.
Fig. 8. Conversion of palmitoyl chloride and the calculated results.
5. Conclusions
IPP was synthesized from palmitic acid, thionyl chloride, and
isopropanol by a two-step noncatalytic method. The results
showed that each step reaction obeys the tetrahedral mechanism
and follows a second-order reaction kinetic model. Based on the as-
sumption that the diffusion-controlled processes were eliminated
by selecting the appropriate stirring rate, intrinsic kinetics of the
two-step reaction was investigated. By analysis, calculation, and
induction of the relevant experiment data, the dynamic model of
IPP synthesis was built. The kinetic equations for the first and sec-
46103
ond steps were −r PA ¼ − dcdtPA ¼ 4:63  105 e− RT cPA cTC and −r PC ¼
6 −54:1510
3 2000.
− dcdtPC
¼ 9:08  10 e cPC cIPA , respectively. The activation en-
RT
ergies of first and second steps were 46 and 54.15 kJ·mol − 1 ,
1339
respectively. The frequency factors for the first and second steps
were 4.63 × 105 and 9.08 × 106, respectively. The result of the ver-
ified experiments showed that the kinetics equations are reliable.
This study is very significant for the industrial application and de-
termining the continuous production process of IPP synthesis.
Nomenclature
A1 frequency factor for Step 1 acylation reaction
A2 frequency factor for Step 2 alcoholysis reaction
Ea1 activation energy for Step 1 acylation reaction, kJ·mol−1
Ea2 activation energy for Step 2 alcoholysis reaction, kJ·mol−1
k rate constant, L·mol−1·min−1
R gas constant, J·mol−1·K−1
rPA reaction rate of palmitic acid, mol·L−1·min−1
rPC reaction rate of palmitoyl chloride, mol·L−1·min−1
T absolute temperature in kelvin, K
xA conversion of palmitic acid or palmitoyl chloride respectively, %
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