Chemicd

Printed in Great

Engineering Science, Britain.

Vol.

41, No.

4, pp. %3-970,

1986

om9-2509/86

$3.00 +

0.00

Pergamon PressLtd.

USING

TRMPERATURE-PROGRAMNED REACTION FOR OF LIQUID-PHASE REACTIONS

KINETICS

ANALYSIS

Earth

and

Space

and Bruce A. Robinson Lee F. Brown Los Alemos National Sciences Division. New Mexico 87545, U.S.A. Los Alamos,

Laboratory

ABSTRACT Temperature-programmed reaction (TPR) is shown to be a practical method for determining raactionkinetics parameters By measuring for liquid-phase chemical reactions. rate expressions and information normally obtained from a series of reaction extent during a temperature rise, Using nonlinear least-squares isothermal kinetics experiments can be found in a single TPR Lest. regression eliminates the need for a constant temperature-rise rate, and enables reactions with significant heat effects to be tasted. Use of experimental pressures above atmospheric can extend TPR temperature ranges so that experiments can be carried out within a reasonable time for Simulations of TPR with random measurement error are used to assess the tachmost reactions. nique's accuracy and to identify the best values of operating parameters. Comparing TPR with isothermal methods shows the latter may be slightly more accurate for the same number of data but TPR is far faster and experimentally simpler, and more data points can be taken in a points, Two TPR experiments measuring alkaline ethyl-acetate hydrolysis show the given time period, technique's applicability.

KEYWORDS reaction Temperature-programmed reaction; ethyl acetate hydrolysis. regression; kinetics analysis; liquid-phase reactions; nonlinear

INTRODUCTION This paper discusses using temperature-programmed reaction (TPR) for kinetics studies of liquidThe goals of these studies are to find a chemical reaction's rate phase chemical reactions. i.e., activation energy and pre-exponential expression and the expression's kinetics parameters, Isothermal batch or steady-state experiments are usually used for kinetics evaluations, factor. and this paper compares TPR and isothermal methods for these purposes. TPR is a technique in which a chemical reaction is carried out at a controlled but varying temperature. Reaction progress is followed by chemical analysis. The temperature is often raised at a constant rate to simplify interpretation of results. While TPR has been used effectively with catalytic and gas-solid reactions (e.g., Falconer and Schwartz, 1983; Sohn and Kim, 19801, there are few experimental studies using liquid-phase systems. In these, with high reactant contemperature control difficult, and desired centrations. energy changes during reaction can make tamperature programming cannot be carried out. In many liquid systems, distances between freezing and boiling points are too small to obtain good TPR spectra within reasonable times. and TPR might be superior to steady-state methods for These drawbacks caa be overcome simply, determining a reaction's kinetics characteristics. Nonlinear regression can be used for date analysis instead of the simplified techniques suitable for TPR with a constant temperature-rise the linear temperature ramp would then be unnecessary and significant heat effects could be rate; Performing experiments under pressure can be used to extend tolerated. the range between freezing and boiling and satisfactory TPR spectra could be obtained in reasonable times for any set of These modifications should eliminate the pre-exponential factors and activation energies. problems of using TPR to study liquid-phase reactions. It remains to compare TPR with steadystate methods to see which is better for acquiring reaction characteristics. We are tracers 1984), investigating TPR because we need for measuring remote tamperatures and steady-state methods are very a technique to in geothermal time consuming. screen many reactions reservoirs (Robinson, for use Tester. as reacting and Brown.

PREVIOUS

WORK simple systems are known. Dankiewicz and ways for analyzing TGA. DTG. and DTA results, spectra. The book by Koch (1977) and various

l$any methods for interpreting TPR spectra from Wieczorek-CXurowa (1979) discuss fourteen different and ia principle all can be used to interpret TPR

cm

4*:4-x

963

964

L. F. BROWN

and B. A.

ROBINSON

H-6

reviews (e.g., Coats and Redfern, 1963; Falconer and Schwars, 1984) describe many techniques. There are All of these approaches depend upon a linear temperature ramp for their validity. hazards in these methods. When equations are linearized or regions emphasized, data are weighted incorrect implicitly, and weighting of data containing error can distort results and lead to If the system is followed continuously, as in conclusions (Kittrell, Hunter, and Watson, 1965). this may not present a mass spectrometric analyses of carrier gases from gas-solid systems, might be serious. difficulty. If limited data are taken, the problem
Nonlinear regression uses information in the TPR spectrum to the fullest extent possible; a The variance reaction-rate expression is assumed, and its parameters come from the regression. that predicted from data accuracy, and no trends should appear between should approximate predicted and measured TPR curves. If these conditions are fulfilled, the assumed reaction-rate expression is consistent with the da+a and the parameters are evaluated as well as possible. Without numerical testing, it is unknown whether Kittrell's are studying. Linear and nonlinear regressions are used here. and results are compared to see their relative worth problem is present in the systems we in the numerical simulations presented for our systems.

NUMERICAL The Fundamental

HODELLNG for TPR Experiments. nonisothermal ex-

Equation

Both TPR and periment with

For any isothermal kinetics experiments are modeled numerically. an n-th order reaction and an Arrhenius temperature depandance,

co
A constant

Jcrs = c

-A

ITremElnT
dt .

(1)
the independent variable from

To
rate and changing

temperature-rise

to

give

Tr
f(cr) 5 - t _I e-E'RT dT , in which reaction, 8 t (dT/dt). and In this equation, the function f(Cr) = Xn (Cr/Co) for a first-order (2) is used note since

equals

cc;

- c;-n )/(1-n)

for a non-first-order

reaction.

Equation

below in the two overall methods of solution to study the TPR kinetics experiment. However, technique does not require a linear temperature rise. that the nonlinear least-squares numeric81 integration for any time-temperature history is performed easily.

Nonlinear

Regression.

A first-order Both nonlinear and linear regression were used in different aspects of the study. A + products and a second-order expression were chosen for modeling a constant-density The conditions for both TPR and isothermal experiment simulations for the nonlinear reaction. Exact conversions which should have been observed for regression tests are Listed in Table 1. To simulate random measurement error in the eonthese conditions were calculated from Eqn. (2). set Gaussian distributions of errors around the -exact+' concentrations. centration data, we and the absolute errors declined Error uas assumed to be a fraction of the exact concentration. Standard deviations ranged from 0.01 to 0.05. as the concentration decreased.

TABLE Rate

Experimental

Conditions =A

Assumed -E/RTC

for A min-L

Numerical =A

Modeling - - Ae'E/RTCi 104.6 kJ/mol min-1

expressions: energies: factors: Initial Rate of

= - Ae 104.6

Activation

kJ/mol ACo 273 K

Pre-exponential TPR experiments Isothermal

A = 2 x 1010 temperature: temperature rise:

- 2 x 1010

1 K/min 573 438, K 453, AND 468 K

Final

temperature: levels: experiment error series:

Temperature experiments Number Standard of data points of in any random

9 0.01 - 0.05

deviations

in data:

H-6

Kinetics analysis of liquid-phase reactions

965

Nonlinear regression was used to disc*iminate amdng different rate exprassians to see which was and to determine activation energies and pre-exponential factors most appropriate for the data, 1n the nonlinear reqression, a search was made in which for first and second-order reactions. the activation energy and the pre-exponential factor of the rate constant wets varied in erder to minimiee the sum of the squared differences between the concentrations predicted by using these parameters and those in the synthetic data.

Linear

Regression.

Linear reqression was used to analyee effects on parameter precision of error level, sample freand ranges of kinetics parameters. quency, tamparatura-rise rata, Simplification of Ecm. (2) can be made using a series expansion of the integral (Coatas and Redfern, 1964). For large values of E/RT, the equation becomes (3) Plotting In I-f(c,)/T:] constant energy may or nearest in Eqn. versus l/Tr should yield a straight line, since .&I (AR,'pE)[l-_(2RT/E)]

is essentially the activation data point at tion can be

From this plot, over any reasonable temperature range for our systems. -E/R. By using the be obtained from the linear least-squares slope of than the intercept, the temperature and concantrac/co - 0.5, rather (31 to obtain the
best value

used

of

(Sohn

and

Kim,

1980).

CHEMICAL The first reaction of ethyl acetate: CH3Cooc2H5 we

EXPERIMENTS used to test the TPR technique experimentally was the alkaline hydrolysis

+ on-

cn3coo-

+ C2H5OH

(4)

A high pressure, high tamExperimental procedures are described in detafl in Robinson (7985). perature stirred autoclave reactor was used for the kinetics experiments. Ethyl acetate and ethanol were analyzed using gas chromatography. For the isothermal experiments, the temperature was achieved with a heating jacket which brought the reactor up to the operating point, and then was controlled to within fZ*C. In the TPR experiments, the reactor was adjusted to its maximum haatup rate, which was acceptable for our purposes. A linear temperature ramp was not achieved, but this was not necessary since nonlinear least-squares regression was used to analyze the data. The rate law
%A

is
=

first

order

in

ethyl

acetate

(EA)

and

hydroxide

concentrations

(Kirby,

1972):

-k2[OH-][EA]

we are interested in dilute aqueous reactions, so EoH-1 remains Although a second-order reaction, With a rate constant equal to k2[OU-1, a first-order exessentially constant in our systems. For the sodium bicarbonate-acetic acid buffer pression could characterize the reaction rate. [OH-] is a strong function of temperature due to the temperature dependence of the system used, water and carbonic acid dissociation constants (Robinson, 1985). Since this temperature function approximately follows an Arrhenius temperature behavior, the product retains the k2EOR-] character of a pseudo-first order rate constant and the reaction may be treated with the methods When comparinq the isothermal and TPR experiments, where the rate consuggested in this paper. stants were measured at different values of [OH-], the second-order rate constant is used.

NDWXRICAL Nonlinear Least-Squares

MODELING

RESULTS

Raqression.

Table 2 gives results of discriminating between reactionDiscrimination among rate expressions. rate exnressions bv nonlinear least-squares regression. It presents four cases using synthetic first-order reaction data -- two with error containing standard deviations of 0.01 and two with error containing standard deviations of 0.05. Wodals assuming both a first-order and a secondorder reaction were used to predict the data, and the sums of the squared differences between the predicted values and the data were evaluated. Optimal values of activation energy and preexponential factor were calculated and used for the predictions. i.e., those values which gave the minimum possible sum of squarad differences (minimum sum of squared residuals). Table 2 confirms the truism that aa data accuracy improves, it is easier to discriminate among different models. In the TPR experiments whose data have an error standard daviatlon of 0.01, a first-order reaction model fits both sets of data much better than does a second-order model. The minimum sums of squared residuals for the second-order reaction model are 26 and 47 times am great as the sums for the first-order model. This is proper, since a first-order reaction was When the data's error standard deviation is 0.05, the differences in used to generate the data. sums of squared differences are much less, differing by factors of only 2.3 and q.4.

966

L.F.

BROWN

and B. A. ROBINSON

H-6

TABLE
ErrOr

D%scriminating Assumed Reaction Order ? 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2

Between

Rate

Expressions Calculated Pre-Exponential Factor, min-l 3.245 3.658 1.151 6.685 1.813 2.663 2.379 3.949 1.811 7,234 4.661 1.674 1.547 1.926 6.149 1.162 x x x x x x x x x Y x x x x x x lOlo 1Ol6 1010 1015 lOlo lOlo 1010 1010 1011 101' lOlo 1017 1010 10" 10" 10"

Imposed on Data 0.01

Type of Experiment

Calculated Activation Energy,kJ/mol 106.5 157.3 102.5 150.8 104.2 104.1 105.3 105.6 113.0 168.9 107.7 162.9 103.7 103.1 108.8 109.6

sum of Squared Residuals

2.643 6.863 1.886 8.870 1.826 2.138 2.900 2.004 2.844 6.615 8.810 1.258 2.245 2.227 4.789 2.713 x x x x x x x x x x x x x x x x lo-* lO-3 10-4
1O-3

TPR

0.01

TPR

0.01

Isothermal

lO-4 lo-' 10-5 lo-'

1O-3

0.01

Isothermal

0.05

TPR

lO-3 10-3 lO-2 lO-3 lo-' 10-3 lo-'

0.05

TPR

0.05

Isothermal

0.05

Isothermal

For

isothermal experiments, FaCtOrS are 117 greakcr .

and 9.9 and 5.6 data. mal experiments were fit the data better. wlity of fit of the

sums of squared residuals are significantly with an error standard deviation of 0.01 in the for two cases with an error standard deviation of 0.05. Thus when isotherused. in all cases it was possible to distinguish which of the two models For the TPR experiments, it miqht not be possible to distinguish the two models in the higher-error situation.
mvZi 691 for two cases

differences

in

the

Sums of the squared residuals in Table 2 should be of the order 0.0004 when the error standard deviation is 0.01. and of the order 0.01 when the standard deviation is 0.05. were The valuea calculated from the generated data's standard deviation from the "exact" canversionsr observed sums of residuals should be less than this because optimal values of the parameters would create models closer to the generated data than to the "exact" values. Minimum sums of squared residuals reported in Table 2 are consistent with this. Similar results occurred when a order models predicted results. second-order reaction generated Here, of course, second-order data, models and first-order and secondgave the superior fit.

TABLE

3 From

Parameter TPR

Precision From Isothermal 0.01 100 104.6 104.6 0.71 0.05608 0.05610 0.00055 Experiments 0.05 100 104.6 104.7 3.77 0.05608 0.05619 0.00276

Experiments 0.05 100 104.6 106.6 6.90 0.05608 0.05690 0.00326

Std. Dav. of t?o* of cases True Mean Std. True Mean Std. B, of kJ/mol Calc. in

Error

in

Data

0.01 100 104.6 / 104.6 1.59 0.05608

E, Calc.

k.l/mol E,

Dev. k473,
of

kJ/wl

min -1

Calc.

k473,
Calc.

min-'
k473, min-l

0.05603 0.00070

mv.

in

Parameter estimation. Table 3 presents the results of parameter cstimtion studies for the TPR and isothermal-experiment approaches. In contraat to the rate-expression discrimination cparison. the two techniques qave almost equivalent results for the precision of parameter estimation. The standard deviations in the calculated values of the activation energy from the TPR experiments were at most about twice those from the isothermal experiments. and somewhat below that at the higher error levels. Standard deviatiene in the calculated rate constants from the TPR experiment.8 ranged only from 18 to 27 percent higher than those from the steady-state experiments. The rate constants from both methods are quite close to the true values7 this says that TPR can be used effectively to make accurate kinetics measurements in a single experiment. Again. the use of data generated by a second-order reaction gave snalogoue results.

H-6
Linear

Kinetics

analysis of liquid-phase

reactions

967

Least-sqtlarcs

Reqreesion.

TABLE

comparison

of Nonlinear Calculated Activation Rnergy,kJ/mcl 106.5

104.1

and

Linear

Regression

Results calculated k 4,3. n&n -1

Error Imposed on Data

0.01

Type

of

calculated

Regression

Pre-Exponential
FaCtOr, min-l

nonlinear linear nonlinear linear nonlinear

linear nonlinear 1 inear

3.245 1.767 1.151 1.302

1.811 1.383 4.661 7.443 2.000

x x

lOlo
lOlo

0.05667
0.05630

0.01

102.5 103.0 113.0

111.8 107.7 100.2 104.6

x 1010 x lOlo
x x x x x 1011 101 10 to9 1010

0.05529 0.05548
0.0 5926 0.06261 0.05960 0.06427 0.05608

0.05
0.05

True

values!

Table 4 presents four results from nonComparison of nonlinear ana linear regression resultr. In all oa*e*, results are close, ana linear least-squares reqressicns on the ~lame apta. linear For the two and the difficulty noted by Kittrell and mentioned earlier is not present here. energies were within 2.2 and casea where the error standard deviation was 0.01, the activation When the standard deviation was 0.05, energies were within 1.1 and 0.4 percent of each other. Rate constants at 473 K calculated using parametere from regressions were within 8.7 percent. when the 0.7 and 0.4 percent when the standard deviation was 0.01, ana within 5.6 and 7.8 percent The higher the error level, the more results from the two apstandard deviation wae 0.05. resulte from the two typee of regression were always close. proaches diverged. Nevertheless, Nonlinear regression carried cut on TPR data treats a responee surface with a Steep valley. If the Levenberg-Marquordt algorithm cm cause divergence, starting values are outside the valley, We used linear regression when carrying out mak+ng nonlinear rsgreesicn nmre difficult to use. since result8 from the nonlinear and evaluations which reguired Large numbers of synthetic runs. conclusions from linear reqreesion calculations would be linear reqressione are quite close. qualitatively correct, and quantitatively change only slightly if nonlinear reqreaeion were used. The next paragraphs present the effect on calculated reaction parameters of data error, sampling frequency, temperatureriae rate, pre-exponential factor, and activation energy. Uany eimulae-q., each mean and standard deviation of the activation energy came from tions were performed, Table 5 lists conditions for each case. ana Table 6 qives means and 1000 simulated TPR runsdeviations of the activation energy and the first-order rate constants at several temperatures.

TABLE

Values

Used

for Parameter-Evaluation Cmin

0.03

Teats At.,
10

case
1 2 3 4 5 6 7 8 9 10 11 12

cl

A, min -1 2 x
2 x 1010 1010

R, kJ/mcl
104.6

IMX

19, K/min
1

min

0.01
0.02 0.03 0.04 0.05 0.07 0.05 0.05 0.05 0.05 0.05 O-05

0.95

104.6 104.6 104.6 104.6 104.6 104.6 104.6 104.6 104.6 104.6 167.4

0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03

0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.9 0.9 0.9 0.9

1 1 1 1 1 1 1 0.1 1 10 1

10 10 10 10 10 5 2 100 10 1 5

2 x 1010 2 x 1010 2 x 1010 2 x 1010 2 x 1019 2 x 2 x 2 x 2 x 1019 1010 1010 1010

1.7 x 101'

Error

pected,

Caaee l-6 s ummarrze the results of varying the standard deviation of error. As exetandara deviation of activation energies increased with increasing deviation in the data error (Table 6). A systematic deviation occurred in mean activation energy, where the calculated E wae generally Icwer than the true value. the difference increasing with increaeinq c. It is ascribed to using linear instead of nonlinear reqresaion. level.

the

968

L. F. BROWN

and

B.

A.

ROBINSON

H-6

TABLE

Statistical Std. Dev. of kJ/slOl

Results E.

of

Parameter-Evaluation Rate Constants, K Std. Dev.

Tests min-l 473 Avg. K Std. Dev.

case

Average

E.

k.I/mol

423 Avg.

(104.6)
1

(2.42~10-~)
2.93

(5.61~10-~) 1.31x10-4 2.80x10-4 3.86x10-* 5.17x10-4 6.43x10-4 8.65x10-'* 4.47x10-4 2.80~10-~ 1.86x10-4 4.96x1O-4 1.31x10-4 1.44x10-4 5.63~10-~ 5.50x10-2 5.46x10-2 5.38x10-~ 5.32~10-~ 5.22~10-~ 5.39x10-2 5.46x10-2 4.99x10-2 5.46~10-~ 6.04x10-~ 5.37~10-~ (5.58~10-~) coustaut. only. Those at the top refer 2.36~10-~ 4.05XlQ_3 5.94x10-3 7.32~10-~ 8.78x10-3 l.O8xlO-* 6.72x10-2 4.62~10-~ 1.61~10-~ 7.04x10-3 6.75~10-~ 6.10x10-3

104.2 101..7 100.4 98.7 97.5 95.0 100.0 102.9 99.2 99.6 100.0 160.3 (167.4)

2.47~10-~ 2.60~10~~ 2.68~10-~ 2.78~10-~ 2.87~10-~ 3.04x10-3 2.67~10-~ 2.49x10-3 2.40~10-~ 2.75x10-3 3.22~10-~ 4.61x10-' (3.65~10-~)

2 3 4 5 6 7 8 9 10 11 12

5.56 7.66 9.83 11.7 14.8 8.36 4.90 10.1 9.04 9.62 14.0

Numbers to cases 1000

in parentheses 1-11. Those used

at in

are the each

true values of the rate bottom refer to Case 12 case.

simulations

The error level in a calculated rate constant may be significantly less than that in the activation energy or pre-exponential factor. A compensation effect exists; when a low value of E is it is offset by a low value of A, calculated, and the two low values tend to compensate for one anothet when calculating rate constants in the temperature range where the data were taken (Table This effect has bee" observed before, and methods have been proposed to treat different 6). aspects of it (e.g., Himmelbla", 1970). Sample frequency. Sample frequency has a marked effect on the accuracy of the results, as see" by comparing; Cases 5. 7, and 8. Huch more accurate values of E and the calculated rate cons-taut* are obtained when -the time between taking samples is cut from 10 to 5 and then to 2 minutes. For example, changing the sampling frequency from 1 sample/l0 min to 1 sample/l mill can increase the accuracy in E more than a decrease in the etror standard deviation from 0.05 Sample frequency is the most easily changed of the variables we evaluate here. so this to 0.02. finding is significant. Temperature ramp parameter over two orders of magnitude points fell within the range perimentally or in a 8. Cases 9-11 show that the accuracy did not chauge significantly These calculations assumed that the same number of data 8. concentration detectability Cmin to C,,. To achieve this exsampling frequency must be changed by the ssme factor as 8.

in of

simulation.

Different kinetics parameters. Results of equal accuracy can be obtained for different values of activation energy and pte-exponential factor provided the correct sampling frequency is chosen. The higher the activation energy, the more frequently samples must be taken to achieve the same accuracy, all else being equal (cases 10 and 12). In TPR, s reaction with a higher activation energy will proceed from a concentration of 1 to 0 over a smaller temperature range.

EXPERIMENTAL

RESULTS

t"o preliminary ethylTo test TPR experimentalLy for acquiring liquid-phase kinetics parameters, acetate hydrolyses were carried out. The purpose was to check the capabilities of the apparatus to see if numerical techniques we had available could analyze the dats satisfactorily. The and and the data displayed interesting properties. experiments were successful in these goals, In the temperatures where concentrations changed within limits of detectable differences from 1.0 The temperature-rise six data points were obtained in one run, and five in the second. and 0.0. and nonlinear regression was used to calculate optimal values of activarates were "ot constant, The reaction was carried out under pressure, which tion energy ahd pre-exponential factorIf the maximum operating temallowed operation above the normal bailing point of the solution. of the order of 1O-4 K/min perature had been LOO-C, solution of Eqn. (3) indicates that a 8 would have been necessary and a TPR run would have needed over a month. At our conditions, a r"" required about four hours.

Kinetics analysis of liquid-phase reactions

The

activation energies and preexponential factors obtained from the regressions are presented Also reported are kinetics parameters from isothermal experiments carried out by in Table 7. and parameter values calculated from the correlation of David and Villarmaux Robinson (19851, baaed on previous ethyl-acetate hydrolyai8 studies. (t9SO),

TABLE Source

Reeulta

of

TPR

and

Isothermal

Experiments Calc. rate constant k at 430 I dm3/~rnOl)(8~ 45.2 44.3 32.8 48.6 Calc. rate con8tantbk at 400 It, dm3/SrnOl~(S) 10.4 14.7 f3.9 17.6

Activation energy E, k.J/mol

Pr-eesponential factor A, dm3/(mo1)(s)

TPR TPR

expt. cxpt.

En-72 EA-13 expte,

70.0 52.7 40.9 49.0

1.44 1.12 3.05 4.36

x x x 8

1010 108 106 to7

Isothe-1

David-Villermaux correlation a. b. Approximate Approximate

mid-point mid-point

temperature temperature

of of

TPR experiments. isothermal experiment

for the TPR experiments is almost certainly another The observed differences in activation energy exhibition of the compensation effect oauaed by data error. Given the error level, there slere insufficient numbers of samples in these preliminary experiments to give reliable values of IXIt is encouraging that calculated fate constants in tivation energy and pre-exponential factor. the critical temperature range of the TPR experiment chow such good agreement with those caloulated from previous studies. The results of testing the effect of sample frequency on accuracy of results indicates that good values of reaction parameters can be obtained using this technique at the level of data error we now have. It appear8 almost certain that when TPR experiment8 are properly carried out and the proper amount of data are taken, they will qivc reliable values of the rate parameters.

DISCUSSION

AND

COUCLUSIONS experimental test8 show that T!PR is a practical method for deterand kinetics parameters (A and E) for liquid-phase reactions. A may be slightly more accurate for a qiven number of data points, epeed and simplicity should often make TPR the preferred method. can extend TPR spectra the temperature within reasonable range between time periods.

Both numerical simulations and mining reaction-rate expressions series of isothermal experiment8 but the virtues of experimental Operation freezing of and

the experimental system under pressure boiling and make.it possible to obtain

Nonlinear regression should be used for the analysis to obtain the mOBt accurate result, and also to eliminate the restrictive experimental reguirement of having to produce a constant rate of temperature rise. For example, the natural temperature rise of our reactor could be used for our TPR experiment8 without having to implement a sophisticated temperature control scheme to achieve 8 linear ramp temperature increase. Nonlinear regression also.makeS it possible to perform TPR for reactions with larger heat generation. Linearized equations are valuable expression. They also can be used the nonlinear regression. in preliminary attempts to find in selecting starting values of the the proper expression's reaction-rate parameters

in

variable with the most marked effect on the TPR technique ie the number of The experimental samples taken in the region where the reactant concentration is measurably below 1.0 and measurably above 0.0. This is determined by the sampling frequency. A large'increase in accuracy of the kinetic8 parameters and calculated rate constant8 may be obtained simply by analyzing more samplea.

The insensitivity of able temperature-rise nonlinear temperature The compensation observed in TPR.

results to the temperature-ramp rate between 0.1 and 10 rise we would not expect p

parameter 6 K/min appears to fall outside

is encouraginq. acceptable, and this range.

Any even

achievwith a

effect, noticed by other investigators Techniques to minimioe this remain to

when analysins isothermal be d@velaped for TPR.

data,

was

also

ACKNOWLEDGMENTS This work ments of were very we8 carried out under the auepicss of the U.S. Department of Energy, and the governzapan and the Federal Republic of Germany. Steve A. Birdsell's disousaions and graphs a8 were discussions with the University of Colorado's Professor David Clough. helpful,

970

L. F.BROWN
NOMENCLATURE

and B.

A.

ROBINSON

H-6

A C C C max

Pre-exponential Concentration, Maximum Minimum reactor raactor of

factor mol/m3

of

rate

constant.

s-1

concentration concentration reactant in in

included included reactor reactor at at

in in

interpreted interpreted t 5 t, 0,

samples. samples, mol/m3

mol/m3 mol/m3

min o

Concentration Concentration Activation First-order second-order Order of

time time

=* E kl k2 n R t Ate T T T B= Q 0

of reactant
energy in rate rate

mo1/m3

constant, conetant, constant,

J/nwl s-l m'/(mol)(e)

reaction

reaction-rate

reaction. gae

dimensionless .Y/fmol)IX)

Universal Time, s

constant,

Interval

betken K in in

taking

TPR

eamples

for

analysis,

Temperature, Temperature Temperature Rate of

reactor reactor

at at

time time rise, in

t = t,

0, X

reactor deviation

temperature of error

K/s concentrationa, dimensionless

Standard

relative

REFERENCES Coats, 924. A. W., and J. P. Redfern (1963). Thermogravimatric Analysis: A Review. Analyst, 9, 906-

Coats, A. W., Sci., Polym. Dankiericz, Syngenite David, Tank

and J. P. Redfern (1964). Part B, 2, 917-920.

Kinetic

Parameters

from

Thermogravimetric

Data.

II.

J. -

J., and K. K2Ca(S04)2.H20 J.

wieczorek-Ciurowa Under Non-Isothermal

(1979). Kinetic Conditions.

onr A

Study of J. Thermal Model for

the The-l Anal., z, a mntinuous

Dehydration 11-24.
Flow Stirred

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