Pergamon Chemical Engineering Science, Vol. 51, No. 20, pp.

4681 4692, 1996

Copyright 1996 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
Plh S0009-2509(96)00306-5 0009 2509/96 $15.00 + 0.00

APPLICATIONS OF TEMPERATURE SCANNING IN KINETIC

INVESTIGATIONS: THE HYDROLYSIS OF ACETIC
ANHYDRIDE

S. P. ASPREY, B. W. WOJCIECHOWSKI,* N. M. RICE and A. DORCAS

Queen's University, Kingston, Ontario, Canada K7L 3N6

(Received 28 May 1995; accepted 29 March 1996)

Abstract--Tbe temperature scanning methods described here are widely applicable. They can be used in
kinetic investigations on many other liquid-phase reactions with similar chemical kinetics: for example, the
hydrolysis reactions of alkyl halides and esters, including both acid- and base-catalyzed reactions. In more
complicated cases the temperature scanning methods require more sophisticated data handling procedures
but they continue to yield the correct overall (net) rates of reaction. We leave such cases for future
consideration and confine ourselves to this simple system where diffusion and heat transfer rates are clearly
unimportant. Copyright 1996 Elsevier Science Ltd

Keywords: Temperature scanning, hydrolysis, acetic anhydride, kinetics.

INTRODUCTION Hanesian (1993) also used temperature as a measure

F o r many years, the kinetics of the hydrolysis of acetic
anhydride have been studied using conventional
steady-state methods, with references going back as
far as 1906 (Lumiere and Barbier, 1906). In most of the
studies reported, a plug-flow or batch reactor is oper-
ated isothermally at several pre-selected temper-
atures. A variety of methods of product analysis, some
very tedious, have been used for measuring the extent
of conversion at selected times during the reaction. In
most studies the reaction had to be stopped in some
fashion for the analysis to be performed. More re-
cently, Glasser and Williams (1971) suggested that
continuous measuring techniques such as pH, infrared
spectroscopy, and conductivity, as well as temper-
ature measurements, present possible analysis tech-
niques for real-time monitoring of conversion. The
operation of a TSR relies on such continuous
monitoring of output conditions. A TSR must have its
conversion measured by methods which are rapid in
comparison with the rate of reaction or, for that
matter, in comparison to the rate of temperature
scanning.
In an attempt to simplify and make continuous the
required concentration measurements, Glasser and
Williams (1971) proposed using the temperature of the
reacting system as an indication of the extent of the
reaction. Using this technique to calculate the extent
of conversion, kinetic parameters were obtained by
a regression analysis of the temperature-time curves
logged during the experiment, using differential equa-
tions describing the reaction/reactor system, includ-
ing all heat flows. More recently, Shatynski and
*Corresponding author.
4681
of the hydrolysis reaction. They attempted to avoid
some of the calculational complexities inherent in
Glasser's experiment by maintaining adiabaticity and
operating at steady-state conditions.
Extracting reaction rates in the regime where tem-
perature and conversion change simultaneously
seems to have eluded previous authors. Instead, two
well-known extremes of operating conditions are ex-
ploited to the exclusion of all others: (1) isothermal
conditions, where the heat transfer coefficients are
large and the reaction temperature is well controlled
by appropriate heaters/coolers; and (2) adiabatic con-
ditions, where heat transfer coefficients are small or
the driving force for heat transfer is kept to a min-
imum and temperature rise is a measure of conver-
sion. As discussed in earlier publications by Woj-
ciechowski (1992) and Wojciechowski and Rice
(1993), temperature-scanning techniques allow the use
of these as well as all intermediate conditions to ex-
tract valid rate data from the unexplored regimes
between zero and infinite heat transfer to and from the
reactor. In temperature scanning reactors, the feed
temperature is deliberately ramped without waiting
for steady-state conditions, and heat transfer between
the reactor and its surroundings is finite.
In a conventional isothermal experiment, each tem-
perature chosen yields a single point on an Arrhenius
plot. Using isothermal techniques, an Arrhenius plot
normally contains five or less (usually three) points
through which a straight line is 'fitted' and the activa-
tion energy of the reaction is calculated from its slope.
In sharp contrast to this, by ramping the temperature
of the feed to a TS reactor, we can obtain many
isothermal rates from one run; in essence, an arbitrar-
ily large number of rates can be extracted from one
4682 S. P. ASPREYet al.
run using the temperature-scanning techniques de- Elimination
scribed below.
Temperature Rampin9 is a well established tech- O- O/CH3 O
O- CH3
nique in, for example, Temperature Programmed Re-
duction/Oxidation/Desorption/etc. While these tech- I~ C H 3 - - C + \c /
niques may be used for quantitative measurements,
they are almost always used for qualitative investiga- If
tions. We know of no methods of quantifying the / I o /o + O
reaction rates on the basis of ramped runs for the
case when steady state is not achieved, as is the
case with the general application of our methods in Proton Transfer
the operation of a Temperature Scannino Reactor.
The TSR methodology in its broader aspects is there-
fore a new and distinct method of acquiring kinetic
\ \
CH 3~ C CH 3 C
data.
/ ' / + H+
This is our first presentation of experimental results
O+ O
based on the TS methodology. As such it deals with /
a very simple system; no volume expansion, slow .// H
H
ramping rates and kinetics known to be pseudo-first-
order in the reactant. More complicated systems can
also be studied in this way, but the necessary math- Step one, the addition reaction, is the rate-controlling
ematical tools and data handling routines are more process.
complex than those needed for this system and we
leave them for later. Nevertheless, the methods used The kinetics of the reaction
here are not confined to the hydrolysis of acetic an- Since step one is rate controlling, the rate of the
hydride and will be applicable to a wide range of hydrolysis reaction can be written as
liquid-phase reactions. In that sense they present an -- d [Ac20]
instance of a more general case. = k' [Ac20] [H20]. (1)
dt
However, under conditions where there is an excess of
THEORY water, pseudo-first-order reaction conditions can be
The hydrolysis reaction assumed. The expression now simplifies to
The chemistry of the reaction. In order to make the
issues clear we begin by reporting what is known -d[Ac20]
k' [Ac20] (2)
about this reaction. The overall hydrolysis of acetic dt
anhydride reaction can be represented in the follow- or,
ing way using abbreviated notation:
-dG
= kCA (3)
dt
Ac20 + H 2 0 ~ 2 AcOH.
where k is the observed rate constant (in units of
The mechanisms of the hydrolysis of carboxylic acid time - t ) for the pseudo-first-order hydrolysis. The
derivatives are well documented. It is well known that pseudo-first-order rate constant k is therefore com-
the reaction proceeds via a substitution, in which an posed of a true second-order rate constant k' multi-
attacking nucleophile replaces a substituent group on plied by the concentration of water in the reactant
the central carbon. This is not a classical SN1 or SN2 mixture
substitution reaction that one might expect; rather, k = k' [H20]. (3a)
the rate controlling step is a simple addition reaction
(March, 1995). The overall reaction mechanism pro- Any 'dilution' of the water by increased concentra-
ceeds via three irreversible steps: addition, elimina- tions of acetic anhydride or by the addition of an
tion, and proton transfer to the solvent (Candruff, inactive component will show up in the first-order
1978). rate constant as a change in the frequency factor
k = Ae -r/Rr = A ' [ H 2 0 ] e -~mr (3b)
Addition where A = A' [H20].
O- / CH3
By integrating eq. (3), we obtain,
CH 3
C"3
[CA] = [CA]o exp ( - k t ) . (4)
o~CNo/C(o +H20 . 2CH3&/%C
Dissociation of the acetic acid occurs as it is formed
and can be represented by,
Kq
H AcOH ~ AcO- + H + (5)
 Temperature scanning applications
where the equilibrium constant can be written as
[ A c O - ] [H +] [H+]:
Keq - [AcOH] [AcOH] " (6)
M E T H O D S O F M E A S U R I N G C O N V E R S I O N IN STUDIES O F
ACETIC A N H Y D R I D E HYDROLYSIS
An historic perspective
To highlight the efficacy of our temperature scan-
ning methods and of the use of conductivity to
measure the extent of reaction we recite the methods
previously used in studies of acetic anhydride hy-
drolysis, as well as in many similar reactions.
Classical methods for the determination of liquid-
phase reaction rates have depended upon the
measurement of concentration at discrete time inter-
vals. This requires either some way of stopping the
reaction at a specific time, or a means of taking
measurements rapidly with respect to the rate of the
reaction.
In a study of the kinetics of this hydrolysis reaction,
Cleland and Wilhelm (1956) used both a batch and
a plug-flow reactor. In their work using the batch
reactor, measurement of conversion required that at
various times a small sample of liquid be removed
from the reacting system. The sample is introduced
into a flask containing about 15 times the amount of
saturated aniline-water needed to react completely
with the unconverted acetic anhydride in the sample.
The reaction proceeds very rapidly in comparison to
the hydrolysis reaction itself and forms acetanilide.
The solution is then back-titrated with caustic soda
using phenophthalein as the indicator.
In the P F R configuration, the fraction of acetic
anhydride converted in the reactor was determined
from measurements of the inlet and outlet concentra-
tions. Sampling consisted of 'catching' one sample of
the flowing stream in a flask containing the aniline
and a second in an empty flask, and allowing this
second sample to hydrolyse completely. In order to
establish the fraction of anhydride converted in the
first sample, which had been treated with aniline and
titrated immediately the second sample was titrated to
determine the amount of anhydride present at zero
conversion.
More recently, Glasser and Williams (1971) used
temperature as a continuous meter-readable indica-
tion of the extent of reaction in a batch reactor. The
reported temperature increase was approximately 1C
over the course of the reaction. In order to follow the
progress of the reaction, very sensitive temperature
measurements were necessary. Once the temperature
data were collected, Glasser and Williams (1971) fitted
these to differential equations describing the mass and
energy balances of the system, including all heat trans-
fer terms, in turn determined in a separate set of runs
which established the heat transfer properties of the
reactor. Ignoring for the moment the fact that ex-
tremely accurate temperature measurement must be
made, deviation from isothermal conditions rendered
4683
simple techniques of data interpretation useless. In-
stead, kinetic parameters were obtained by a regres-
sion analysis of the experimental temperature-time
curves on the simultaneous differential equations de-
scribing the reaction system. The excellent results
finally obtained in 1971 are a testimonial to the care-
ful experimental and computational techniques em-
ployed.
Shatynski and Hanesian (1993), who also used tem-
perature as a measure of the hydrolysis reaction, while
maintaining adiabatic conditions, were wise to
operate under much simpler steady-state conditions.
Nevertheless, the complexity of the methods used in
such work, both experimental and computational, is
impressive.
Other continuous measuring techniques may be
used, including pH, infrared spectra(FT-IR), etc. As
long as the measurement technique is relatively fast
compared to the rate of the reaction under study, any
of these methods can be used to obtain conversion
data usable by the Temperature Scanning Reactor.
The conductivity method
Due to ion formation from the dissociation of the
acetic acid formed by the hydrolysis of acetic an-
hydride, this reaction can be monitored using an elec-
trical conductivity meter. As the reaction progresses,
ionic species are produced by the dissociation of the
acetic acid, whose concentration increases as a result
of the hydrolysis reaction. As a result, the electrical
conductivity of the solution will change with the con-
version of acetic anhydride, but not directly.
The product ions on the right-hand side of eq. (5)
are the conducting species. At low concentrations
their capacity to carry charges, and hence the con-
ductivity of the solution, varies linearly with the con-
centration of these ions. By writing conductivity as
a linear function of proton concentration, we have
L, = q~[H +] +Lo (7)
where Lo is the initial conductivity at time t = 0,
where no H + ions beyond those present in distilled
water are present in the solution; Lt the conductivity
at time t during the course of the reaction when H
ions due to the ionization of the acetic acid are also
present; ~b the unknown constant relating conductiv-
ity to concentration.
Using eq. (6), we can rewrite eq. (7) as
L, = q~/Keq[AcOH] + Lo (8)
moreover,
L, = ~bx/2Keq{[Ac20]o - [Ac20]} + Lo (9)
and when [Ac20] = 0, at the end of the reaction,
L~ = q~x/2Keq[Ac20]0 + Lo. (10)
To our knowledge this is the first time that conductiv-
ity measurement has been reported as a means of
following the conversion of acetic anhydride. This
4684 S. P. ASPREYet al.
method may well be of broader applicability in
L= Plotted as a Function of Temperature
temperature scanning experiments in other systems
involving ionic products or reactants. 0.96

KINETICS
0.94

Kinetics in a plug-flow reactor or a batch reactor

0.92
Using eqs (8)-(10) and eq. (4), we have

Lt Lo 0.90
/ [Ac20] _ x/1 _ e x p ( - k t )
Loo - L0 1 [Ac20]o J
0.88

=/1 CA .. ' /
CAo -- V/~a (11) 0.86

where L~o denotes the conductivity at in/inite time 0.84

when all the acetic anhydride has reacted to produce
acetic acid. This measurement is most easily obtained 0.82
in situ by filling the plug-flow reactor with reactants [ i i r i i I i
312 314 316 318 320 322 324 326 328 330
and turning the flow rate down to zero. After the Temperature (K)
mixture within the reactor has reacted to completion,
one measures the highest conductivity observed dur- Fig. l. L~ plotted as a function of temperature of the reac-
ing the transient when flow is resumed. Alternatively, ting fluid. A linear regression line shows the relation used in
one can set aside a sample of the feed in a flask and the calculations. Notice the obvious clustering of points
measure its conductivity after the reaction goes to around the trend line. This scatter is due to digital dithering.
The outliers which fall outside the range of dither are due to
completion. The latter method can introduce errors if air bubbles passing over the conductivity probe.
the conductivity meter used at the reactor output is
not well-correlated with the one used to measure
conductivity in the flask. tion was put forward by Wojciechowski and Rice
From the equations given above, it is evident that (1996),
a plot of

in [ _ ~ln I ( L ~ - L ) 2 - ( L t - L o ) 2 ] ] vs 1 - k C A = CAo X + dX (13)

T
(12)
is an Arrhenius plot with slope equal to ( - Ea/R). The
pre-exponential factor is given by the y-intercept of
such a plot and therefore ln(A) is read offthe graph at
l I T = 0. Notice that in the case of the batch reactor,
t represents clock time, whereas in the plug-flow reac-
tor, t represents space time (z).
Since conductivity in a given solution is a function
of temperature, Lo and Lo~ must be known at all
temperatures scanned in an experiment in order for
the above function to be correctly evaluated at each
temperature. This was accomplished by measuring 10
values of each of Lo and Lo~ over the temperature
range of interest (25-55C), and using a linear regres-
sion to obtain a functional form for the two conduc-
tivities. An alternative method is shown in Fig. 1
which shows a plot of Lo~ obtained by measuring the
conductivity of a completely reacted sample in
a beaker undergoing temperature ramping.
Kinetics in a TS-CSTR
Equation (11) can also be used to interpret data
from the CSTR in the following way. In the CSTR, we
must take into account the unsteady-state reaction
conditions as temperature is ramped. The following
design equation accounting for this transient condi-
Go-dr-
Dividing both sides by CA and substituting X = 1 -
CA/CAo and ~ = V/vo (V is the reactor volume, while
Vo is the volumetric feed rate), we get
k= (l-X) X +~- (14)
where t in this case is the 'clock time' during the
process of temperature ramping.
From eq. (11) we know that,
Lt - Lo ~2
x = \~ - Eoj (15)
and thus, in principle, k may be directly calculated
from conductivity measurements by substituting
eq. (15) into eq. (14). However, the calculation of the
derivative dX/dt cannot be done in real-time in a real
CSTR due to 'noise' in the measurement of Lt and
consequently in the calculated values of X. This prob-
lem is evident in Fig. 2 where the original Lt data from
our TS-CSTR is shown as a function of time. Figure 3
shows the consequent noise in conversion vs time.
Slopes taken from such data amplify this noise and
are not acceptable for our calculation. To deal with
this we resort to filtering the data in a manner we will
describe later.
 Temperature scanning applications 4685

Conductivity as a Function of Clock Time for the TS-CSTR circulator, which includes a cooling capability to
speed up cooling at the end of a run as well as
0.8 electrical heaters.
At the reactor exit, a Cole-Parmer conductivity
0.7- probe was inserted into the effluent, with the active
probe-end submersed in the temperature-controlled

/
0.6-
water bath to ensure that the analysis is done at the
reaction temperature at each instant during the

/
ramping process. The probe was read with a Cole-
.-J" 0.5-
Palmer temperature-compensated conductivity meter
model no. 19100-00, whose digital output was connec-
0.4-
ted to a 386/SX PC. An Omega pre-heater was used to
/ preheat the incoming distilled water feed, and was
0.3- controlled with a digital Omega PID temperature
controller with adjustable set-point. Pumping of re-
0.2 I I i i I i I l actants through the reactor was accomplished with
100 200 300 400 500 600 700 800 900 a positive displacement rotary pump, which main-
Time(s) tained a constant water-to-acetic anhydride ratio of
approximately 10: 1. Mounted directly downstream
Fig. 2. Raw conductivity data taken as a function of clock-
time for the TS-CSTR. Some noise can be seen in the read- of the conductivity probe was a J-type thermocouple,
ings, which would be amplified through the derivative. The connected to a digital Omega temperature read-out,
small scatter is due to digital resolution while the outlier with its output connected to the same 386/SX PC.
points are caused by air bubbles passing through the reactor Communication of both the temperature read-out
system. and the conductivity meter with the data logging
software was through a Keithley-MetraByte DAS-8
Raw Conversion in the TS-CSTR PC board. No amplification of thermocouple outputs
was necessary at the PC level, as the temperature
0.40 read-out used provides the required amplification
automatically.
For data acquisition, ViewDac software was used.
0.35 -
This package allows real-time graphs to be con-

0.30 -
/ structed from the data and from various quantities
calculated from the data. All data collected were
/
/ written to a floppy disk, each entry of temperature
0.25 - / and conductivity being tagged with a 'clock time'
X

0.20 -
/ identifier. Figure 4 shows the experimental setup.
At the low temperature ramping rate used here, the
/
/ output stream at the reactor exit presents material
0.15 -

0.10 - /
/ which has spent time in the reactor at essentially
isothermal conditions. Since the reaction is first order,
one can calculate the rate constant (k) from the PFR,
batch or CSTR data for each data point collected. The
rate constants calculated in this way from PFR and
0.05 i I I I I I I i
BR data can be displayed in real-time on the com-
0 100 200 300 400 500 500 700 800 900
puter monitor.
Time (s) Figures 4 and 5 show the configurations for both
the plug flow reactor and the CSTR reactor. The
Fig. 3. Raw conversion in the TS-CSTR taken as a function
of clock-time. Notice the amplification of the 'noise' when CSTR configuration could also be used for batch
raw data containing noise shown in the Fig. 2 is treated using studies by simply loading the reactor and shutting off
eq. (14). the flow.

E X P E R I M E N T A L APPARATUS EXPERIMENTAL P R O C E D U R E
In the case of the plug-flow reactor, the reaction With the reactor at room temperature (25C), the
was carried out in a -in. OD polyvinyl tube, placed pump started the distilled water flowing and allowed
in a controlled-temperature water bath. The CSTR any air-bubbles to escape the reactor system and to be
and batch reactors consisted of a glass vessel with purged from the meter electrodes. At this point, the
a volume of 1.441 placed in the same water bath. conductivity, L0 was recorded and compared to the
Stirring in the latter reactors was accomplished with calibration value obtained from the regression de-
a variable-speed stirrer. Thermostatic control of the scribed below. The computer was started and View-
water bath was achieved by using a NESLAB RTE-3 Dac loaded. The acetic anhydride intake tube was
 4686 S.P. ASVREVet al.
KINETICSREACTOR
RECIRCULATOR
HEATEXCHANGER
RECI~t~AT~!
~TLLEO
WATER
GEAR
PUMPS
ACE11C -
A~nD~OE
Fig. 4. A schematic of the plug-flow reactor configuration.
placed in the acetic anhydride reservoir, and the out-
put conductivity and temperature monitored. The
output conductivity was then allowed to 'line-out'.
The thermostat on the water bath was set to 55C and
the bath temperature ramped up without making any
attempt to control it (i.e. the heater remained on
during the entire ramp). As the bath temperature
'scanned' upward, the indicated bath temperature was
followed with the reactor feed water temperature by
setting the feed water controller about 4C above the
water bath temperature. A short preheater coil of
tubing inside the water bath brought the feed temper-
ature to the temperature of the bath. Once 55C had
been reached, we returned all set-points to 25C and
allowed the reactor to cool, while continuing to take
temperature and conductivity measurements. This
procedure could easily be automated for long-range
studies.
In the case of the batch reactor, an appropriate
amount of acetic anhydride (enough to make the
initial concentration roughly the same as the input
concentration in the other reactors) was injected into
the reactor filled with distilled water only, and the
temperature ramping of the water bath was started
immediately, in the manner described above.
PFR MODE
[ CONDUClIVITY
I
I
I
I
I
I
1
RESULTS
The pluo-flow reactor
By using eq. (11) to calculate the conversion in
real-time, Fig. 6 can be constructed by ViewDac and
displayed in real-time. The program calculates X from
its measurement of L, and the stored regressions for
L~ and Lo. It then plots X vs the temperature ac-
quired at the same clock time. Figure 7 illustrates the
Arrhenius plot constructed from this data by using
eq. (12). In examining these two figures, one can spot
the discrete increments in both the conversion (cal-
culated from real-time conductivity readings) and
temperature. This is due to the limited digital resolu-
tion of the data acquisition system used in the experi-
mental setup. The Keithley data acquisition board
(DAC) used here is capable of only 12-bit resolution.
High resolution equipment would remove much of
the 'scatter'.
Using data from this Arrhenius plot of the first-
order rate constant k, a linear regression was per-
formed. Using this first-order constant and the initial
concentration of the water (49.5 M) in eq. (3a) yielded
the following kinetic parameters of the second-order
rate constant k':
 Temperature scanning applications 4687

KINETICSREACTOR
CSTRMODE
)
STIRRER
>
D
RECIRCULATOR

HEATER

["1 ,.
HEAT EXCHANGER ]

RECIRCULATOR

WATER
GEaR

ACETIC ~ # 1
ANHYDRIDE

Fig. 5. A schematic of the CSTR configuration.

A r r h e n i u s Plot f r o m T S - P F R Data

-4

Conversion in the TS-PFR as a Function of Temperature

0.45 -

0.40 -

0.35 -
<!.:
v -6
0.30 -

x 0.25-
.::::.
,.s::"
0.20 - .s"
.:::.-- -7
0.15

0.10
.,li,' ....

-8 I I I r
0.05 i i i i i i
3OO 305 310 315 320 325 330 335 0.0030 0.0031 0.0032 0.0033
T (kq lrr 0/K)

Fig. 6. Conversion data calculated for the outlet of the
TS-PFR shown as a function of outlet temperature. The
dithering of the points is due to limited resolution of the data
acquisition hardware. The outliers are caused by air bubbles
passing over the conductivity metre.
Fig. 7. The real-time Arrhenius plot constructed from the
measured Lt and temperature at the outlet of the TS-PFR,
using eq. (12). The dithering and outliers from the raw data
are passed on to the Arrhenius plot when this is constructed
in real-time.
4688 S. P. ASPREY et al.

Pre-exponential factor (A): Activation energy (Ea):

2.7841 x 103 __+0.05 x 1031/gmol s 10.904 + 0.05 kcal/mol.

The noise in the CSTR data was the fault of our
Activation energy (Ea): simple setup, which allowed some air bubbles to be
aspirated, enter the reactor, and disturb the measure-
10.947 + 0.05 kcal/mol. ment of conductivity by passing or setting on the
conductivity electrodes. Aware of this, we continued
The C S T R our experiments to see if satisfactory results could be
As mentioned previously, the raw data (shown in obtained even from this imperfect setup. As Fig. 11
Fig. 2) taken from the CSTR reactor contained noise shows, the resultant scatter in the Arrhenius plot is
due to experimental and instrumental problems. minimal in comparison with that encountered in the
These data were filtered using a running average with
a 20-point 'window'. The procedure was re-applied
several times until a smooth conversion vs time curve
dX/dt in the CSTR
was attained. The smoothed data are shown in Fig. 8.
From the filtered conversion values, d X / d t was cal- 0.0014
culated numerically using a simple difference equa-
tion. Due to the smoothness of the filtered data, the
0.0012 -
resultant derivative was also quite smooth, as shown
in Fig. 9.
0.0010 -
Figure 10 shows a graph of the conversion in the
CSTR as a function of outlet temperature as temper-
ature ramping progressed, calculated using eq. (15).
By using eq. (14), the Arrhenius plot shown in Fig. 11
was constructed.
0.0008

0.0006
/
From the linear regression performed on the data
shown in Fig. 11, and using the concentration of water
(49.5 M) the following kinetic parameters were ob-
0.0004
/
tained for the second-order rate constant: 0.0002

Pre-exponential factor (A): 0.0000

i i i i i i i i
100 200 300 400 500 600 700 800 900
1.8725 x 103 + 0.05 x 1031/gmols
Time(s)

Fig. 9. A derivative of the filtered data shown in Fig. 8.

Filtered Conversion Data for the TS-CSTR

0.40
Conversion in the TS-CSTR as a Function of Temperature

0.35 - 0.40

0.35 -
0.30 -

0.25 -
0.30 - .y/"
x
0.25 -
f"
fl
0.20 - ,,J

j.,..," f
0.20 -

0.15 -
0.15 - :f

0.10 -
0.10 -

0.05 I 1 I i i i i i 0.05 i i r i i i I
0 100 200 300 400 500 600 700 800 900 295 300 305 310 315 320 325 330 335
T i m e (s) T(IO
Fig. 8. The filtered conversion data obtained after process- Fig. 10. The conversion in the TS-CSTR shown as a func-
ing of the data in Fig. 3. The data were smoothed by ap- tion of reaction temperature. Equation (15) was applied to
plying several running averages on the raw data shown in the filtered data shown in Figs 8 and 9 to obtain Fig. 10.
Fig. 3. Both the noise and the dithering is removed. Again,the resolution of the data acquisition can he seen here.
 Temperature scanning applications 4689

Arrhenius Plot from TS-CSTR Conversion as a Function of Temperature in the TS-BR

1.0
-4

0.8
i1f'"
-5
0.6 <1/
x 0.4

v -6
_c
0.2

0.0

I I I I
280 290 300 310 320 330
T (K)
I I I I

0.0030 0.0031 0.0032 0,0033 0.0034

l r r (l/K)
Fig. 11. The Arrhenius plot constructed from the TS-CSTR
data, by using eqs (14) and (15). The linear regression used for
determining the kinetic parameters is also shown.
Fig. 13. Conversion data for the TS-BR shown as a function
of reaction temperature. Resolution problems can be seen
here in the temperature readings; however, noise levels are
still better than those in the CSTR configuration.

Arrheniu$ Plot for the TS-BR

Conversion in the TS-BR
-5
1.0

0.8
-6-

0.6

_~-7
0.4-
>

O
0.2
-8

0.0

-9
I I I I I I I
0.0030 0.0031 0.0032 0.0033 0.0034 0.0035 0.0036
50 100 150 200 250 300 350 400
1or (l/K)
Time (s)

Fig. 14. The Arrhenius plot constructed from the TS-BR

Fig. 12. Conversion data for the TS-BR as a function of
clock-time. The batch run shown here was performed using
a slightly modified setup. A large beaker heated by an inter-
nal circulator was used, in which rapid temperature ramping
was possible. As a result, the results obtained are less noisy.
At the temperature ramping rate of 10C/min used, only one
reading by the conductivity metre was collected at each
temperature.
Arrhenius plots derived from standard isothermal
reactors by various authors.
The batch reactor
Figures 12 and 13 depicts the conversion within the
batch reactor as a function of, respectively, the clock
data, obtained by using eq. (12) in a manner similar to that
for the TS-PFR.
time and the reaction temperature. By using eq. (12)
in the form used in the case of the plug-flow reactor,
but using clock time (t) instead of space time (z), the
first-order reaction rate constants were calculated.
The resultant Arrhenius plot is shown in Fig. 14. The
following second-order kinetic parameters were deter-
mined by using a linear regression on the data points
shown in Fig. 14 and 55.0 M as the initial concentra-
tion of water we introduced in this case:
469O S. P. ASPREYet al.
Pre-exponential factor (A):
1.8177 x 103 -t- 0.05 x 1031/gmols
Activation energy (Ea):
10.805 + 0.05 kcal/mol.
DISCUSSION
Comparison with previous results
Table 1 provides a means of comparison of the
kinetic parameters determined here to those found in
the literature.
Note that kinetic parameters are reported for acetic
anhydride hydrolysis investigated in dilute solution
only. In their publication, Shatynski and Hanesian
(1993) report literature kinetic parameters using sec-
ond-order units, probably incorrectly. The values re-
ported here have the correct units. We have recal-
culated some reported first-order rate constants to
yield second-order constants (in 1/g mol s) by dividing
the first-order constants by the reported concentra-
tion of water, where available.
By reporting second-order rate constants, we are
able to say something about the frequency factors
observed as they relate to the number of collisions
calculated from collision theory. The frequency of
collisions for two nonlinear molecules is roughly
1061/gmols (Wojciechowski, 1985). By comparing
our frequency factors with this number, we can calcu-
late the stearic factor as the ratio between the ob-
served frequency factor and the number of collisions.
In our work the steric factor is in the order of 10 2,
quite reasonable for reactions between two nonlinear
molecules such as acetic anhydride and water.
Preparatory experiments and data handling
Although the TSR techniques can be implemented
in real time for this system, in order to analyze the
results, L~ must first be known as a function of
temperature. This entails preliminary runs which in-
volve taking L~ values at, say, 10 points along the
temperature ramp. One procedure which was used to
do this in both the TS-CSTR and the TS-BR was the
Table 1. Experimental activation energies and In(A) values for hydrolysis of acetic
anhydride
Activation energy
(kcal/g mol)
This work
PFR
CSTR
Batch
Average
Shatynski and Hanesian (1993)
Bisio and Kabel (1985)
Glasser and Williams (1971)
Cleland and Wilhelms (1956)
Eldridge and Piret (1950)
King and Glasser (1965)
following: set the temperature of the reactor at the
lowest temperature used and wait until the conductiv-
ity has 'lined-out' in the CSTR mode. Stop the flow
and allow the mixture within the reactor to react for
several hours. Then, while collecting conductivity and
temperature measurements, ramp the temperature of
the reactor, now operating in a batch mode: i.e. no
inlet flow. The data collected in this manner will give
the behavior of L ~ as a function of temperature. We
can repeat the same operation with only distilled
water in the reactor to obtain L0 as a function of
temperature. This procedure will yield data such as
that shown in Fig. 7. The procedure cannot be conveni-
ently used for the plug-flow reactor configuration,
although it is possible in principle to set a flow rate so
low that complete conversion is obtained in the PFR.
Failing that, one cannot avoid taking ten separate
readings at selected temperatures in the manner pre-
viously described or make sure that the conductivity
probe at the PFR outlet gives the same readings as the
probe used in the Batch or CSTR.
In the case of the TS-CSTR, a derivative of conver-
sion (X) with respect to clock time is required. Due to
the noise caused by the air bubbles and the data
acquisition equipment, post-run data smoothing of
conductivity measurements was found to be neces-
sary. Any noise in the raw data is greatly amplified
when numerical derivatives are taken. In order to
perform the required filtering, SigmaPlot was used to
apply a low-pass filter was to the conductivity read-
ings. The quantity dX/dt was then determined from
the filtered data and used to produce Fig. 9.
The efficacy of temperature scanning
The TSR technique described here saves much ex-
perimental effort and time. In less than one hour,
using simple un-automated equipment, all the reac-
tion data we show for each reactor were scanned over
the pre-selected 30 K temperature range. The amount
of useable data collected using the temperature-
scanning technique is arbitrarily large; by contrast,
only three to five data points are normally collected in
a conventional isothermal experiment. This allowed
an Arrhenius line to be constructed, instead of the
In(A)
10.95 + 0.05 7.93 + 0.51/gmols
10.90 ___0.05 7.54 + 0.51/gmol s
10.80 + 0.05 7.51 + 0.51/gmols
10.9 ___0.15 7.66 + 0.41/gmol s
11.2 12.74 s- 1
11.1 12.80s-
10.8 7.95 l/g mol s
10.6 7.80l/g mol s
10.3 7.53 l/g mol s
9.5 9.93 s- 1
 Temperature scanning applications 4691

conventional method which requires a linear regres- Literature Arrhenius Plots

sion on three or five data points. One need only
compare the estimate of the standard error in fitting
-i ~ Thi sWork
Cleland and Wilhelm
Eldridge and Piret
the Arrhenius line in both situations to see the benefits Glasser and Williams
in precision. Cleland and W~lhelm (raw data)
We do not need to limit ourselves to the hydrolysis Eldddge and Piret (raw data)
of acetic anhydride when considering the applications -7
of the methods described in this work. There are many
other liquid-phase reactions, with very similar chem- -8
ical mechanisms [i.e. the hydrolysis reactions of alkyl
halides and esters (including both acid- and base- ~\\" ,,

catalyzed)] which could be easily studied using the -9

\ \ -.
techniques described here.
As we will show in future publications, the TSR
v -10
technique is also applicable to much more complic- -=
ated reactions, where it also greatly accelerates the "'x

collection of valid kinetic data. Experimentalists will -11

not have to settle for three or four data points when
determining the activation energy of a reaction. They
will know exactly how the reacting system behaves
over a wide range of conditions in a matter of a few
working days or less. Mechanistic studies of ionic
strength effects, catalysis by acid or base, the effect of
the dielectric constant of the medium, and many other
such influences on reaction kinetics can easily be
determined using the setup described in this work.
There is a stark contrast in the ease of experimenta-
tion, and in the time required to collect adequate data,
between the method presented here and those re-
ported in previous literature. From an operator's
point of view, the TSR is very easily implemented, and
can readily be automated.
It should be noted that in these more complicated
situations the rate of the reaction is not given by
dX/dz unless due attention is paid to how X and z are
collected and assembled. The theory of the temper-
ature scanning methods makes it clear that only ap-
propriate procedures are acceptable. However, as
long as appropriate procedures have been followed
the values of dX/dr thus determined do indeed report
the overall rate of reaction. This rate includes any
effects of diffusion or temperature disequilibrium
present during the scanning procedure. Rather than
seeing this as a negative we find that this offers us
a means of determing the 'effectiveness factors' for the
reaction as the influence of these ancillary effects is
varied in a succession of appropriately designed TS
experiments.
Global averaain9 of rate parameters
By averaging the kinetic parameters obtained in all
three reactors studied here, the following average
parameters were obtained,
Pre-exponential factor (A):
2.16 x 103 -t- 0.54 x 1031/gmols
Activation energy (Ea):
10.9 + 0.15 kcal/mol.
-12
-13 I I I I I I I
2.9 3.0 3.1 3,2 3.3 3.4 3.5 3.6 3.7
1/T (1/10 x 103
Fig. 15. Comparison of Arrhenius plot of the computed
results with those found in the literature. The literature
Arrhenius plots show that previous k values are larger than
those obtained in this work.
Figure 15 shows a comparison of the Arrhenius plots
cited in the literature with the Arrhenius plot deter-
mined here. We can see that previous results lie signif-
icantly higher on the Arrhenius plot. This means that
previous values of the reaction rate constant, k, are
greater than those obtained by us. At this time we
have no explanation for this.
CONCLUSIONS
Using temperature-scanning methods, the amount
of kinetic data collected in a given amount of time is
increased by many orders of magnitude. As shown
here in the case of the simple reaction of acetic an-
hydride hydrolysis, the TS techniques allow us to
collect enough kinetic data to actually draw an Ar-
rhenius plot in real time using a PFR, and to obtain
results which are in good agreement with previous
literature. Our own results are in excellent agreement
for data from a PFR, CSTR and a BR run using the
same reagents.
Such an increase in the rate of production of kinetic
data will allow thorough kinetic investigations to be
done within a reasonable amount of time. For
example, our setup would allow a rapid evaluation of
ionic strength effects, catalysis by acid or base, the
effect of dielectric constant of the medium, and many
other such influences in this reaction. Using the tech-
niques described, this work could be done at the rate
of four or five such systems in one day. At the end of
4692 S. P. ASPREYet al.
the week, acetic anhydride hydrolysis could then be
the most thoroughly investigated reaction in the liter-
ature.
The same TS methods can be extended to deal with
much more complicated reactions, such as reactions
on heterogeneous catalysts, where more elaborate
curve fitting would be required to determine the nu-
merous kinetic parameters present in the applicable
rate equations. There the rate constants are not nor-
mally available in real time and have to be evaluated
post-run. In the present study, real-time calculation of
the rate constants is made possible by the fact that the
form of the rate equation is known a priori to be
a simple first-order expression.
Investment in more up-to-date laboratory equip-
ment would allow for more precise conversion and
temperature measurement, improving thereby on the
raw results reported here. Experimental noise prob-
lems present in the extensive data sets available from
TSRs can be overcome by using a low-pass filter on
the raw data obtained. Such a procedure allows for
the elimination of noise in the numerical derivatives in
the case of the TS-CSTR and will probably prove to
be a much more satisfactory method of dealing with
experimental noise in large data sets than the currently
used replicate runs.
NOTATION
Ac (e.g. acetic group
Ac20)
A pseudo-first-order pre-exponential factor
A' true second-order pre-exponential factor
CA concentration of principle component A
CAo initial concentration of principle com-
ponent A
Ea (or E) activation energy
k pseudo-first-order rate constant
k' true second-order rate constant
geq equilibrium constant
L0 initial conductivity at time t = 0
Lt conductivity at time t during the course
of the reaction
L~ conductivity at infinite time (i.e. reaction
is at equilibrium)
R gas constant
t clock time
T temperature
I) o volumetric flow rate of feed through the
reactor
V volume of the reacting fluid
x~ conversion of principle component A
Greek letters
z space time
q~ unknown constant relating conductivity
to concentration
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