Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
cnica, Departamento de Engenharia Qumica, Av. Prof. Luciano Gualberto, trav. 3, n. 380, CEP 05508-900 Sa~ o Paulo, Brazil
Universidade de Sa~ o Paulo, Escola Polite
polis, Brazil
Universidade Federal de Santa Catarina, Departamento de Engenharia Qumica e de Alimentos, Floriano
a r t i c l e in fo
abstract
Article history:
Received 14 August 2009
Received in revised form
14 March 2010
Accepted 19 March 2010
Available online 24 March 2010
A simple calorimetric method to estimate both kinetics and heat transfer coefcients using
temperature-versus-time data under non-adiabatic conditions is described for the reaction of
hydrolysis of acetic anhydride. The methodology is applied to three simple laboratory-scale reactors
in a very simple experimental setup that can be easily implemented. The quality of the experimental
results was veried by comparing them with literature values and with predicted values obtained by
energy balance. The comparison shows that the experimental kinetic parameters do not agree exactly
with those reported in the literature, but provide a good agreement between predicted and
experimental data of temperature and conversion. The differences observed between the activation
energy obtained and the values reported in the literature can be ascribed to differences in anhydride-towater ratios (anhydride concentrations).
& 2010 Elsevier Ltd. All rights reserved.
Keywords:
Acetic anhydride
Reaction calorimetry
Hydrolysis
Kinetics
Chemical reactors
Reaction engineering
Mathematical modeling
1. Introduction
O
H3C
O
O
CH3
CH3
CH3
H2O
CH3
C
O
H
elimination
CH3
CH3
0009-2509/$ - see front matter & 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2010.03.028
H2O
OH
O
H
CH3
H3C
H3C
CH3
C
O
H
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proton transfer
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2. Methodology
In the present work the kinetics of hydrolysis of acetic
anhydride was studied using simple isoperibolic calorimetry,
under non-isothermal conditions. The experiment is very simple,
employing only an arbitrary vessel (e.g., laboratory glassware)
and a digital thermocouple for measuring the variation of
temperature. Data treatment involves the use of mass and energy
balances to extract information regarding the kinetic parameters
of the reaction. As the reactor is not adiabatic, it is necessary to
include in the data treatment the determination of heat transfer
coefcient between the reactor and the surroundings .
2.1. Mass and energy balances
For a homogeneous reaction carried out in a liquid-phase,
constant-volume, non-adiabatic batch reactor, the mass and
energy balance equations, taking acetic anhydride (species A) as
the limiting reactant, are given by
NA0
dXA
rA V
dt
dTr
rA VDHUATr Tamb
6
dt
It is important to note that the value of (mCp)r in Eq. (6)
accounts for the heat capacity of the chemical components, as
well as for the contribution from heat capacities of the reactor
wall, stirrer, and components:
X
mj Cp,j
7
mCp r mCp reactor
mCp r
XA
V
NA0
CA
10
CW
11
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dTr
UATr Tamb
dt
12
rA
14
rA
CA CW
15
E1
R Tr
16
17
interior points
Tr tj 1 Tr tj1
dTr
2Dt
dt
t
18
last point
dTr
Tr tn2 4Tr tn1 Tr tn
dt t
2Dt
19
t0
Reactor
1
2
3
294.65
295.15
294.45
3. Experimental
The hydrolysis of acetic anhydride was carried out with excess of
water and in three different non-adiabatic vessels: (a) a cylindrical
plastic vessel (reactor 1), (b) a volumetric ask (reactor 2), and (c) a
thermal bottle or Dewar ask (reactor 3). Throughout the whole
Table 2
Reactants and reactors: volume and masses.
Volume (mL)
Deionized water
Acetic anhydride
Cylindrical plastic vessel
Volumetric ask
Thermal bottle
Magnetic stirrer
The integral of Eq. (13) was calculated for each interval of time
using the trapezoidal rule. Hence, the values of experimental
conversion were obtained from the nal time for complete
conversion of A backward to the starting time.
Knowing the value of UA, the rate of reaction of the limiting
reactant can be determined experimentally from the thermal
balance as follows:
Mass (g)
150
90
6.68
80.10
23.59
4.40
Table 4
Specic heat capacity of materials of reactors and stirrer.
Cp (J/g K)
Ref.
1.79
0.75
0.75
0.65
Ullmann (1985)
Ullmann (1985)
Ullmann (1985)
Westrum and Grnvold (1969)
Table 3
Constants for specic heat capacity of reactants and products.
A (J/mol K)
Water
Acetic anhydride
Acetic acid
92.053
71.831
18.944
B (J/mol K2)
C (J/mol K3)
2
3.995 10
8.888 10 1
1.0971
D (J/mol K4)
4
2.211 10
2.653 10 3
2.892 10 3
7
5.347 10
3.350 10 6
2.93 10 6
Ref.
Yaws (1999)
Yaws (1999)
Yaws (1999)
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W.H. Hirota et al. / Chemical Engineering Science 65 (2010) 38493858
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Table 6
Initial conversions.
Reactor
XA at t 0 (%)
1
2
3
6.33
4.94
5.72
Fig. 1. Graphical estimation of global heat transfer for the cooling region for:
(a) reactor 1, (b) reactor 2, and (c) reactor 3.
Table 5
Experimental heat transfer coefcient.
Reactor
UA (W/K)
1
2
3
0.424
0.280
0.0846
Fig. 2. Arrhenius plot for the data taken from: (a) reactor 1, (b) reactor 2, and
(c) reactor 3.
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20
Table 7
Experimental activation energy and ln(k0) values for the hydrolysis of acetic
anhydride.
Reactor
ln(k0) (L/mol s)
E (kJ/mol)
1
2
3
16.25
15.28
15.15
68.9
66.5
66.3
Table 8
Kinetic parameters for hydrolysis of acetic anhydride reported in the literature.
Ref.
Measuring techniques
E (kJ/mol)
n.r.
n.r.
Innite dilution
0.020.06
0.17
0.22
0.25
0.25
0.27
0.34
0.41
0.54
0.66
1.0
1.10
1.34
Equimolar concentration
Calorimetry
Titration
n.r.
Titration
Calorimetry
Calorimetry
Calorimetry
n.r.
Calorimetry
Conductivity
Conductivity
Conductivity
FTIR
Conductivity
Conductivity
n.r.
n.r
39.8
43.2
33.6
44.4
49.4
46.5
45.3
49.4
46.9
50.6
50.1
43.2
53.6
45.7
56.2
57.8
68.7
ln(k0)
Units of k0
7.80
s1
L/(mol s)
L/(mol s)
12.80
7.95
18.1
12.74
18.52
14.21
s1
L/(mol s)
s1
s1
s1
s1
15.48
7.66
20.45
s1
L/(mol s)
s1
9.93
7.53
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Table 9
Experimental activation energy and ln(k0) values for the hydrolysis of acetic
anhydride without mixing effects.
Reactor
ln(k0) (L/mol s)
E (kJ/mol)
1
2
3
17.57
16.65
16.19
73.74
70.14
69.12
100
E (kJ/mol)
80
60
literature data
40
present work
20
0
0
Fig. 3. Arrhenius plot for comparing the rate constant for the hydrolysis of acetic
anhydride obtained in this work with those reported in the literature: (a) reactor 1,
(b) reactor 2, and (c) reactor 3.
2
4
6
8
initial concentration of acetic anhydride (mol/L)
10
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other hand, Golding and Dussault (1978) also observed that the
effect of acetic acid on reaction rate reported in the literature has
been conicting.
Fig. 4 shows the variation of activation energy obtained by
different authors, as a function of the initial concentration of
acetic anhydride. It is quite evident that, for smaller
concentrations, activation energy increases with increasing
concentration of acetic anhydride. Our results, obtained for
relatively higher initial concentration of acetic anhydride, are
also included in this plot and follow reasonably well the trends of
changes of E with temperature.
Finally, in order to test the values obtained for the 3
parameters (U, k0, and E), they were used in the energy and mass
balances to simulate the evaluation of temperature and conversion. Figs. 5 and 6 show a comparison between the experimental
values of the reactor temperature (Fig. 5) and the conversion
(Fig. 6) with those predicted by the energy and mass balances
using the estimated values of UA and kinetic parameters (k0 and E)
for each case analyzed. For all cases, a good agreement between
experimental and predicted values was found despite values of
activation energy and frequency factor obtained being always
higher than those reported in literature.
5. Conclusions
This work shows that both kinetic parameters and heat
transfer coefcient of reactor contents can be easily determined
for hydrolysis of acetic anhydride using temperature-versus-time
data under non-adiabatic, isoperibolic conditions. The main
difference of this work in relation to other previously published
works in the literature is that the kinetic data were obtained
under non-adiabatic conditions, where the heat transfer coefcient must be known in order to determine these parameters. The
results shows that the estimates obtained for activation energy
and frequency factor of the hydrolysis of acetic anhydride are
apparently affected by excess of either reactant and, therefore, no
unique value of either ln(k0) or E could be taken. Despite the
observed differences between estimates of k0 and E and those
reported in the literature, experimental and predicted values of
temperature and conversion show good agreement.
As a nal comment, the simplicity of the experimental setup
and the calculations used in this investigation allows one to use
them as an experiment for undergraduate laboratories to
illustrate the application of the non-adiabatic calorimetric
method to infer state variables.
Notation
CA
CW
Cp
E
k
k0
(mCp)r
MW
NA0
NW0
R
( rA)
t0
tf
Tamb
Tr
UA
3857
V
total volume of reactants added to reactor, L
XA
conversion of component A
( DH) heat of hydrolysis of acetic anhydride, J/mol
r
density, g/L
Acknowledgements
The nancial supports from FAPESPFundac- a~ o de Amparo a
Pesquisa do Estado de Sa~ o Paulo, CNPqConselho Nacional
de Desenvolvimento Cientco e Tecnologico, and CAPES
Coordenac- a~ o de Aperfeic-oamento de Pessoal de Nvel Superior
are gratefully appreciated.
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