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over a Zinc Oxide Catalyst

Consistency with the Adsorption Function of Isopropyl

Alcohol on Zinc Oxide

STEIN KOLBOE

From the Central Institute for Industrial Research, Oslo 3, Norway

The rate of dehydrogenation of isopropyl alcohol over a zinc oxide catalyst has been

measured at 15%195”C, at, an isopropyl alcohol pressure range of 0.03-100 torr.

The rate measurements have been tested for consistency with a previously determined

adsorption function of isopropyl alcohol on zinc oxide. The adsorption function assumes

Langmuir adsorption on a heterogeneous surface with five sets of adsorbing sites.

The corresponding kinetic equation could be well fitted to the experimental rates using

a suitable set of rate constants and activation energies, but using the previously deter-

mined adsorption function directly. In the experimental sange which covered a factor of

more than 3000 in isopropyl alcohol pressure and a factor in reaction rates of 170 the mean

deviation between observed and calculated rates was less than 6yo. The results are there-

fore an indication that a previously proposed model, assuming that a heterogeneously

catalyzed reaction may take place on more than one set of active centers on the catalyst,

is correct.

theory that there may be more than one

The two preceding papers (I, 5’) present

set of active centers on a catalyst (S), it was

a mathematical description of the adsorption

found to be of much interest to see if the

function for isopropyl alcohol on a zinc

adsorption function of isopropyl alcohol on

oxide catalyst.

zinc oxide is consistent with rate data for

It was found that on fresh (nonaged)

the dehydrogenation reaction of the alcohol

samples of zinc oxide made by heating zinc

on the cataIyst. The system isopropyl

earbonate to 350°C in air for 24 hr the ad-

alcohol/zinc oxide was chosen because

sorption function could be described by the

previous work (4) had shown that rate

following equation

measurements in this system could not be

5 fitted to the kinetic equations of Hougen

W=

WOiaipA and Watson (5).

0)

c 1 + aip.4 At this point it may be mentioned that

i=l

Schrage and Burwell (6) have recently given

with ai = eXp(AXi/R -AHi/RT) evidence that isotopic exchange between

Equation (1) corresponds to the assump- cyclopentane and deuterium on palladium-

tion that the adsorption is a Langmuir on-alumina catalysts takes place on more

adsorption on a heterogeneous surface than one set of catalytically active centers.

where there are five distinct sets of adsorp-

tion sites. The values of the 15 parameters NOMENCLATURE

of Eq. (1) have been determined (,2). They ai Adsorption equilibrium constant

are given in Table 1 of the preceding paper for isopropyl alcohol over active

(-8. center Ci

DEHYDROGENATION OF ISOPROPANOL ON ZIlO 209

Activation energy over center Ci were carried out at a total pressure in the

Adsorption enthalpy over center Ci reactor between 1.0 and 1.2 kP/cm2. The

Rate constant over Ci pressure drop from inside the reactor to the

Pre-exponential factor of rate cou- outside took place mainly in the sintered

stant over center C, glass disc which supported the catalyst.

Partial pressure of isopropyl alcohol Most of the isopropyl alcohol partial

Rate pressures were measured directly in the tail

Rate at conversion 77 gas, but at the highest partial pressures

Rate at zero conversion saturation effects in t’he det,ector of the gas

General gas constant chromatograph occurred. A relation is,

Standard deviat,ion estimate however, easily established between the

Adsorption entropy over center Ci isopropyl alcohol partial pressure in the

Absolute temperature sampling valve, and the part’ial pressure in

Adsorbed qua&t> the gas leaving the saturator, or in the

Adsorbed quantity at saturation over reactor, so the isopropyl alcohol pressures

center Ci were known within a few percent in all

Conversion of isopropyl alcohol to experiments. In order to minimize possible

acetone time effects as far as possible the measure-

Natural logarithm of the pre-expo- ments were carried out in partly random

nential factor for the rate constant order at each temperat,ure.

over Ci

RESCLTS AND DISCUSSION

EXPEHIMESTAL

Apparatus. A flow system of essen- The reaction rates which have been ob-

t’ially the same construction as previously tained are given in Table 1 together with the

described was employed (1). The following isopropyl alcohol partial pressures and

important features were not mentioned conversions. It is seen that the majority of

previously: The apparatus was equipped the rates have been obtained at very low

wit’h an additional inlet for carrier gas conversions. Separate experiments have

between the saturator and the reactor. shown that in the t,emperature and pressure

Bot’h branches were equipped with a needle range where these measurements have been

valve and flow met’er, so that t’he flow in carried out, the following relation is ap-

each branch could be varied at will, thus proximately fulfilled at, conversions up to

allowing a wide range of isopropyl alcohol a few percent

partial pressures in the reactor. The whole 1’$dl

apparatus (from the saturator on) was - = 1 + 0.005,)pA (2)

r,

heated to 70” to 80°C so that condensation of

isopropyl alcohol at. high partial pressures where q is in percent and pA in torr.

was avoided. It is obvious from Eq. (2) that when it

Materials. The catalyst was not aged applies, all the rates given in Table 1 are

ZnO (from ZnC03) previously described (1). essentially independent of conversion. The

Isopropyl alcohol and carrier gas were also assumption is therefore made in the fol-

as previously described (1). lowing that the measured rates represent

Procedure. The reaction rates were true differential rate data (probably not

found by multiplying the acetone concen- strictly correct for the rates at the two

trat,ions in the effluent gas from the reactor highest conversions).

by t,he flow rat’e through the sampling The adsorption fun&ion previously re-

device. This flow rate was not measured ported (1, 9) was measured on a nonaged

directly, but was calculated from the mea- catalyst sample, consequently the rate

sured carrier gas flows, correcting for effects measurements reported here have been

from pressure, isopropyl alcohol concemra- obtained from nonaged catalyst samples t’oo.

210 STEIN KOLBOE

TABLE 1

ISOPROPYL ALCOHOL PARTIAL PRESBURES,

CONVERSIONS, AND

DEHYDROQENATION RATES with n 2 2 can be consistent with the ‘mea-

surements. If the adsorption function [Eq.

(l)] is to be consistent with the rate mea-

surements reported here it must be possible

168°C to fit the following equation to the data:

105.9 0.004 0.1562

f6

105.9 0.003 0.1381

wdwspA

4.824 0.037 0.6300 T=

2.235 0.10 0.7424 c (1 + aipA)*

i=l

1.165 0.24 0.9143

2.259 0.13 0.6890 where

0.706 0.52 0.8660

ki = eXp[Ki - (EJRT)]

0.229 1.14 0.9780

= lci0 exp( -Ei/RT) (4)

178°C

62.94 0.072 1.249 and

31.77 0.089 1.907 ai = exp(A&/R - AHi/RT)

20.71 0.11 2.355

11.88 0.20 2.934 where K~ and Ei are unknown parameters

7.012 0.35 3.331 and Woi, AS,, and AHi are the previously

3.765 0.59 4.047 determined adsorption parameters (2) given

3.035 0.64 4.996 in Table 1 of the preceding paper (2).

2.153 0.88 5.709 Equation (4) has been fitted to the data

0.346 5.0 6.328

10.2 6.864

by the standard least-squares technique,

0.134

0.065 16.4 6.138 making the sum of squared percentage

0.036 21.1 4.822 deviations become a minimum [see ref. (S)]

15.53 0.15 2.704 for three values of n, viz. n = 2, 3, and 4. A

10.18 0.15 2.952 digital computer was used to carry out the

6.118 0.1.5 3.685 computations. Due to the fact that the

3.229 0.30 4.555 adsorption constants were given (thus fixed)

1.076 0.27 6.466 there was littlec oupling between the param-

0.771 0.40 6.892 eters and the iterative procedure necessary

0.624 0.67 7.292 to find the parameter set leading to the

0.371 1.05 6.860

0.19 5.412

smallest possible sum of squared residuals

2.153

converged rapidly. The parameter estimates

195°C and standard deviation estimates of the

2.188 0.78 22.01 rate measurements for n = 2, 3, and 4 are

3.035 0.62 18.79 given in Table 2. Calculated and observed

20.82 0.31 10.87 values are shown in Figs. 1, 2, and 3. It is

1.118 1.03 25.68 seen that Eq. (4) can be fitted to the ex-

0.682 1.78 26.26 perimental points with fair accuracy with

0.371 3.18 25.44

4.30 24.74

n having any of the values 2, 3, and 4. It is,

0.271

8.824 0.71 13.12 however, doubtful that n = 2 is really

9.882 0.67 13.00 consistent with the measurements. The

11.82 0.63 12.92 standard deviation estimate for the experi-

14.65 0.55 11.56 mental points is higher than the correspond-

117.6 0.14 4.920 ing estimate when n = 4, although the

significance is weak. It is also apparent

The rate measurements obtained are from Fig. 1 that Eq. (4) with n = 2 cannot

shown in Fig. 1. From this figure it is clear be fitted to the experimental points at the

that only rate expressions of the type two lowest isopropyl alcohol pressures,

DEHYDROGENATION OF ISOPROPANOL ON &lo 211

TABLE 2

ESTIMATED VALUES OF PIUS-EXPONENTIAL FACTORS (NATURAL LOGARITHM) AND ACTIVATION

ENERGIES OF EQ. (4) FOR n = 2, 3, AND 4, AND RATE CONSTANTS AT 178°C

n=2 n=3 n=4

Ed ES Ei

i fc* (Cal/mole) k? xi (Cal/mole) kia I< (osl/mole) ki.

2 Does not contribute 37.382 31820 6.535 36.616 30480 13.91

3 30.850 26610 3.185 29.208 24510 6.421 32.307 26760 11.48

4 33.979 28270 11.42 39.651 32260 38.68 40.977 32970 65.83

5 40.080 33780 10.90 39.006 32430 16.78 40.814 33870 21.18

Estimated standard deviation Estimated standard deviat,ion Estimated standard deviation

from this model, s = 11.0% from this model, s = 9.06% from this model, s = 8.85%

Mean deviation between cal- Mean deviation between cal- Mean deviation between cal-

culated and observed culated and obsemed culated and observed

values, 7.27% values, 6.34% values, 5.95 y0

b Not estimated from the least-squares procedure because the lack of experimental points at high pressure

makes this impossible. The value was chosen to be similar to the other activation energies.

where the calculated rates are much smaller taken into account that the rates vary by

than the observed ones (which should a factor of 170 and the isopropyl alcohol

perhaps be even higher at zero conversion). pressures vary by a factor of more than

The values of n, n = 3, or n = 4 in Eq. 3000. It is also a satisfactory result that,

(4) are seen to lead to calculated rate curves when n = 3 or n = 4 in Eq. (4), all adsorp-

which are fully consistent with the rate tion sites are found to contribute to the

points, and it must be considered very dehydrogenation rate, as is seen from the

satisfactory that n = 4 leads to a mean rate constants at 178°C which are given in

percentage deviation between observed and Table 2.

calculaOed rates of only 5.95% when it is It would have been desirable to extend

ISOPROPYL ALCOHOL PRESSURE

LOGARITHMIC SCALE

FIG. 1. Observed and calculated rates at 158”, 178”, and 195°C. The calculated rates have been obtained

from Eq. (4) with n = 2, using the parameter values given in Table 1 of ref. (a) and Table 2 of this paper.

212 STEIN KOLBOE

1 10

ISOPROPYL ALCOHOL PRESSURE

LOGARITHMIC SCALE

FIG. 2. Observed and calculated rates at 158”, 178”, and 195°C. The calculated rates have been obtained

from Eq. (4) with n = 3, using the parameter values given in Tables 1 [ref. (S)] and 2.

the pressure range by another factor of 10 to catalyst, because fresh catalyst samples

100 upwards, as this increase of isopropyl exhibit a rapid decline in activity at higher

alcohol pressure is necessary in order to get temperatures (7).

full information about the weakest adsorbing It was pointed out above that the mean

site. A pressure apparatus making this percentage deviation between observed and

possible is under construction. Also the calculated values was 5.95ojn (s = 8.85%).

temperature range could profitably have The true standard deviation of the rate mea-

been extended upwards, but this was not surements at constant catalyst activity is not

possible when working with a nonaged accurately known (it will depend upon the

0.1’

0.01 0.1 1 10 ml TORR

ISOPROPYL ALCOHOL PRESSURE

LOGARITHMIC SCALE

FIG. 3. Observed and calculated rates at 158’, 17P, and 195°C. The calculated rates have been obtained

from Eq. (4) with n = 4, using the parameter values given in Tables 1 [ref. (@I and 2.

DEHYDROGENATION OF ISOPROPANOL ON ZIlO 213

a given rate) but it is believed to be some- 1.0 X 1014 se+. When an agreement be-

-what less than 3%, except when measuring tween the adsorption function of a system

rates at 158’C at low isopropyl alcohol and the reaction rates in the same system is

pressures, when 5% standard deviation is sought for, it is implicitly assumed that the

probably a better estimate. In the present catalytic reaction is not confined to a very

case the overall standard deviation will be few active centers on the catalyst. Rather it

higher, however, because there was un- is assumed that over large areas of the cata-

doubtedly some activity decrease of the lyst an adsorbing site is also a catalytically

catalyst due to aging taking place when the active site. The agreement found here be-

measurements were carried out. It is be- tween the pre-exponential factor (frequency

lieved that this catalyst aging will increase factor) and the vibrational frequencies of

the standard deviation to about f&70/,. The hydrogen atoms is therefore highly

standard deviation estimate (s = 8.85%) satisfactory.

from the fitting of Eq. (4) is still higher than

t,he expected standard deviation of the rate CONCLUSIOn-

measurements. But all errors in the adsorp- It is apparent from the preceding dis-

t ion parameters in Table 1 of ref. (1) (which cussion that a model assuming that the

have not been varied) will increase the dehydrogenation reaction of isopropyl al-

st’andard deviation estimate from Eq. (4) of cohol on zinc oxide is taking place simul-

t.he experimental rates above the true least- taneously on several (five) sets of active

squares minimum. The two standard de- centers is in complete agreement with the

viation estimates, s = 6-7%, and s = experimental results. The reaction is de-

8.850j0, can therefore be considered to be scribed mathematically by Eq. (4) with

in full agreement. n = 3 or 4 (n = 2 cannot be rigorously

If the experimental rates are expressed as excluded but seems unlikely). According to

molecules transformed per second and gram the model the rate-determining step is a sur-

catalyst, and the values of Woi are expressed face reaction, and in the rate-determining

as sites per gram catalyst, the ~Q’Sand thus step an adsorbed isopropyl alcohol molecule

also the kio’s are seen from Eq. (4) to have reacts simultaneously with two or three

the dimension molecules site -l se+. So far neighboring free active centers (5). Detailed

t’he following units have been used: T, reaction mechanisms in agreement with such

nanomole see-’ rnm2; Woi, mg isopropyl a model can be proposed, but at the present

alcohol adsorbed per gram catalyst. The state of knowledge this is hardly warranted.

rate T is expressed as desired after mul- It is of interest to compare the results

t,iplying by N X S X 10Pg where N is obtained here with results previously ob-

Avogadro’s number and S is the surface tained for the dehydrogenation reaction of

area of the catalyst, which is 52 m2/g (1). set-butyl alcohol over a brass catalyst (3,8).

llYoi is converted to sites g-l by multiplying The brass catalyst had been oxidized in air

by 1.0 X lo-l9 (i.e., molecules isopropyl at 430°C and was then reduced in hydrogen

alcohol per mg). The conversion factor for at the same temperature. It is thus inferred

expressing ki (and k,) in units molecules that the brass was covered by zinc oxide

&e-l se& is thus N X 8 X low9 X lo-l9 = (possibly mixed with copper oxide) and

3.13 X 10P3. The values of the lci<s have copper. The presence of zinc oxide makes

been calculated in these units and they were a similarity with a pure zinc oxide catalyst

found to be of the order of magnitude 1014 likely. It is therefore to be expected that the

molecules/site sec. [The mean value (geo- reaction mechanism of dehydrogenation of

metric) of the five sites was found to be 0.5 X see-butyl alcohol over a brass catalyst will

1014molecules site-’ se+ when n = 4.1 This be similar to the reaction mechanism of

is the same order of magnitude as the vi- dehydrogenation of isopropyl alcohol over

brational frequencies of hydrogen atoms in a zinc oxide catalyst. This expectation is in

molecules, which are known from infrared fact in agreement with the results obtained

214 STEIN KOLBOE

set-butyl alcohol were consistent with The measurements were also carried out

a model assuming the same mechanisms over a much smaller pressure range rat

as proposed above (3). Also in that case no considerably higher pressures. R’o detailed

clear choice between mechanisms assuming correspondence can therefore be expected.

simultaneous reaction between an adsorbed

alcohol molecule and two or three free active

centers could be made. But a model assum-

ing reaction between an adsorbed alcohol 1. KOLB~E,S., J. Calalysis 13, 193 (this issue).

molecule and one free active center was on the 8. KOLBOE, S., J. Cakzlyti 13, 199 (preceding

whole not satisfact,ory. When the dehydro- paper).

genation of set-butyl alcohol was investigated 3. KOLBOE, S., Ind. Eng. Chem. Fundamentals 6,

a model assuming only two sets of active 169 (1967).

centers was satisfactory, whereasthe analysis 4. KOLBOE, S., unpublished.

5. HOUOEN, 0. A., AND WATSON, K. M. “Chem-

carried out here is based on the assumption ical Process Principles,” Part 3, Wiley, New

that there are five sets of active centers. York, 1952; or YANO, K. H., AND HOUOEN,

This difference does not imply that there 0. A., Chem. Eng. Progr. 46, 146 (1950).

is a discrepancy between the two investi- 6. SCHRAOE, K., AND BURWELL, JR., R. L., J. Am.

gations, however. The results concerning Chem. SOC. 88, 4549 (1966).

dehydrogenation of set-butyl alcohol were 7. KOLBOE, S., unpublished.

obtained on a different catalyst which had 8. THALLER, L. H., AND THOD~S, G., A1.Ch.E. J.

been given a different pretreatment, so the 6, 369 (1960).

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