INVESTIGATION OF AT n-PENTANE LOW PARTIAL

OF THE ON T H E

KINETICS HYDROGEN

OF THE FORM

ISOMERIZATION OF MORDENITE

PRESSURES

OF HYDROGEN

V.V.Kharlamov, V.I. and Kh.M. Minachev

Garanin,

UDC 541.127:542.952.1: 547.215:661.183.6

It was shown e a r l i e r [1] that the i s o m e r i z a t i o n of n - p e n t a n e on the H - f o r m of m o r d e n i t e without m e t a l s of group VIII is inhibited by H 2 in the r a n g e of p r e s s u r e s 7-30 a t m . However, it is known [2] that without H 2 the r e a c t i o n on this c a t a l y s t p r a c t i c a l l y does not o c c u r . T h e r e f o r e , to d e t e r m i n e the m e c h a n i s m of the i s o m e r i z a t i o n on the H - f o r m of m o r d e n i t e , it is of i n t e r e s t to i n v e s t i g a t e the k i n e t i c s of the r e a c t i o n at low p a r t i a l p r e s s u r e s of hydrogen (from 0 to 7-10 atm). T h i s was the p u r p o s e of the p r e s e n t work. To c o n s i d e r the influence of d e a c t i v a t i o n of the c a t a l y s t under t h e s e conditions on the r a t e of the p r o c e s s we developed a s p e c i a l p r o c e d u r e for conducting the e x p e r i m e n t s and t r e a t i n g the e x p e r i m e n t a l data. METHOD The i s o m e r i z a t i o n of n - p e n t a n e was studied in a flow-through r e a c t o r , into which 10 c m 3 of m o r denite in the H - f o r m with a d e g r e e of exchange of Na + ions for H + of 95 e q . % , was loaded. The c a t a l y s t was p r e p a r e d by the method of ion exchange of Na + c a t i o n s in the i n i t i a l N a - f o r m for NH4+, by five t r e a t ments of m o r d e n i t e with a 10% solution of NH4NO3. B e f o r e the e x p e r i m e n t s the c a t a l y s t was t r e a t e d with a i r at 520 ~ for 5 h. R e g e n e r a t i o n of the c a t a l y s t a f t e r each e x p e r i m e n t was conducted under the s a m e c o n d i t i o n s . Since the c a t a l y s t works unstably at low p a r t i a l p r e s s u r e s of hydrogen {Fig. 1) and l o w e r s its a c t i v i t y to s o m e constant level, which depends on the e x p e r i m e n t a l conditions, we used the following p r o c e d u r e . I s o m e r i z a t i o n under the c o n t r o l conditions at Ptot = 30 arm; pH2/PC 5 = 3.2, vc5 = 1-3 h -1 (depending on the t e m p e r a t u r e ) was conducted on a f r e s h , r e g e n e r a t e d c a t a l y s t . A f t e r this, the p r e s s u r e was l o w e r e d to the set value (Ptot = 4-8 arm), and we o p e r a t e d in t h i s s y s t e m for 60-90 rain. In this c a s e the a c t i v i t y of the c a t a l y s t , as has a l r e a d y been noted, was lowered (see Fig. 1). Then the c o n t r o l e x p e r i m e n t was r e p e a t e d a g a i n . The d e g r e e of d e a c t i v a t i o n of the c a t a l y s t (7) during w o r k at low t e m p e r a t u r e was c a l c u l a t e d a c c o r d i n g to the f o r m u l a = ~nit/rfin (I)

w h e r e rinit is the r a t e of i s o m e r i z a t i o n under the c o n t r o l conditions b e f o r e the b a s i c e x p e r i m e n t was c o n ducted; r f l n is the r a t e of the i s o m e r i z a t i o n r e a c t i o n under the c o n t r o l conditions a f t e r the b a s i c e x p e r i ment was conducted at low p r e s s u r e . C o n s i d e r i n g the a c t i v a t i o n of the c a t a l y s t , we c a l c u l a t e d the c o r r e c t e d r e a c t i o n r a t e ( r c o r r ) in the b a s i c e x p e r i m e n t , which would be o b s e r v e d in the a b s e n c e of poisoning of the c a t a l y s t , a c c o r d i n g to the f o r m u l a

~21
f

,
JO
l

/7

~O

90

F i g . 1. Dependence of the y i e l d of i s o p e n t a n e on the t i m e of work of the c a t a l y s t at 200 ~ and a p a r t i a l p r e s s u r e of h y d r o g e n (PH2) 6 arm (1) and 230 ~ and pH 2 2 a t m (2).

min N. D. Z e l i n s k i i Institute of Organic C h e m i s t r y , A c a d e m y of S c i e n c e s of the USSR. T r a n s l a t e d f r o m I z v e s t i y a A k a d e m i i Nauk SSSR, S e r i y a K h i m i c h e s k a y a , No. 5, pp. 1006'1012, May, 1973. O r i g i n a l a r t i c l e s u b m i t t e d May 17, 1972.
9 1973 Consultants Bureau, a division o[ Plenum Publishing Corporation, 227 West 17th Street, New York, N. Y. 10011. All rights reserved. This article cannot be reproduced [or any purpose whatsoever without permission of the publisher. A copy o[ t/~is article is available [rom the publisher [or $15.00.

970

rcorr = Yrobs

(II)

w h e r e r o b s i s t h e o b s e r v a b l e r e a c t i o n r a t e , c o r r e s p o n d i n g to t h e l o w e r s t a b l e l e v e l of a c t i v i t y of the c a t a l y s t ( s e e F i g . 1). F r o m t h e d a t a o b t a i n e d ( T a b l e 1) it i s e v i d e n t that t h e d e g r e e of d e a c t i v a t i o n of t h e c a t a l y s t v a r i e s f r o m 3 . 5 to 10, d e p e n d i n g on t h e c o n d i t i o n s of i s o m e r i z a t i o n . RESULTS

0

q .~o jo $/s9iotu

AND

DISCUSSION

,( '~s/[Ie~eo ~o uo!a -eA~lOeop~O O~I~(I q, ~e~ Jo 8/ uou.o~zs oIq~^a~sqoi o/~'zrreau~d-u I~!l~.u! u! SD-! Jo ~u~auoD

r~ (D

In o r d e r t o h a v e a g e n e r a l i d e a of t h e d e p e n d e n c e of t h e r a t e of i s o m e r i z a t i o n on t h e p a r t i a l p r e s s u r e of H2, t h e d a t a o b t a i n e d in t h i s w o r k w e r e c o m p a r e d ( F i g s . 2-4i w i t h the r e s u l t s of our p r e v i o u s i n v e s t i g a t i o n in t h e r e g i o n of p r e s s u r e s 7-30 a t m [1]. A s c a n b e s e e n f r o m F i g s . 2-4, t h e o b s e r v a b l e r e a c t i o n r a t e p a s s e s t h r o u g h a m a x i m u m , w h i c h l i e s in t h e r e g i o n of p a r t i a l p r e s s u r e s of h y d r o g e n 7-10 a t m . T h e n a t u r e of t h e r i g h t - h a n d b r a n c h e s of t h e c u r v e s on t h e s e f i g u r e s w a s e x p l a i n e d in o u r p r e v i o u s c o m m u n i c a t i o n [1] on t h e b a s i s of the p r o p o s e d r e a c t i o n m e c h a n i s m Ill]Ill% n-CsHl~ ~- HM ~ n-CsHll - - M -q- H2 1111111% ~qKq~qg~ n-CsH11 - - M ~ i-C5Hll - - M i -C5Hll - - M ~- H 2 ~- i-C5H12 4- HM (1) (2) (3)

u.ta~ ' e l l d

%' s~Id

w h e r e HM i s the h y d r o g e n f o r m of m o r d e n i t e ; n - C s H l l - M and i - C s H t l - M a r e c a r b o n i u m c a t i o n s , bound to the a c t i v e c e n t e r s of m o r d e n i t e . F r o m t h e s c h e m e p r e s e n t e d it i s e v i d e n t that H 2 s h i f t s t h e e q u i l i b r i u m of t h e f i r s t s t e p of t h e r e a c t i o n , in w h i c h the c a r b o n i u m c a t i o n and H 2 m o l e c u l e a r e f o r m e d in the i n t e r a c t i o n of a m o l e c u l e of n - p e n t a n e with a p r o t o n of t h e a c i d h y d r o x y l g r o u p of m u r d e n i t e . T h e d r o p in the o b s e r v a b l e r e a c t i o n r a t e with d e c r e a s i n g p a r t i a l p r e s s u r e of h y d r o g e n in the i n t e r v a l f r o m 0 to 7-10 a t m i s a s s o c i a t e d w i t h d e a c t i v a t i o n of t h e c a t a l y s t . T h e c o r r e c t e d r a t e of t h e i s o m e r i z a t i o n r e a c t i o n in t h i s r a n g e of p r e s s u r e s d o e s not d e p e n d on t h e p a r t i a l p r e s s u r e of h y d r o g e n ( s e e F i g s . 2 - 4 ) . In o u r p r e v i o u s c o m m u n i c a t i o n [1] we d e r i v e d a k i n e t i c e q u a t i o n , w h i c h f o r t h e r e a c t i o n in t h e f o r w a r d d i r e c t i o n t a k e s the following form

.~

'SOT d -~uesTr

~2

r----- kap~-ci/PH2 I + aP,,-cjpm

(III)

~op~
,-~ <D

w h e r e a i s t h e e q u i l i b r i u m c o n s t a n t of the f i r s t s t e p ; k i s the r a t e c o n s t a n t of i s o m e r i z a t i o n of t h e n o r m a l c a r b o n i u m cati'on t o a c a t i o n of i s o - s t r u c t u r e . A c c o r d i n g to t h i s e q u a t i o n , the r a t e of t h e r e a c t i o n (r) at c o n s t a n t t e m p e r a t u r e d e p e n d s only on t h e r a t i o of t h e p a r t i a l p r e s s u r e s of n - p e n t a n e and H 2 (Pn_C5 /PH2). M o r e o v e r , at low r a t i o s P n _ C J P H 2 , when 1:~ a p n _ c 5

/PH2"
r = kap~-cs/pH~ w h i l e at high P n _ C J P H 2 , when 1<< a P n _ C 5 / P H 2 r = k . (V) (IV)

971

"8 8

"e

,o

zo

PNz,arm Fig. 2

;o

pxz~ arm

Jo

Fig. 3 T he dotted

Fig. 2. Dependence of the reaction rate (r) on pH 2 at 200 ~ line belongs to the observable reaction rate.

Fig. 3. Dependence of the reaction rate (r) on pH 2 at 210 ~ T he dotted line belongs to the observable reaction rate. Figure 5 p r e s e n t s the dependence of the r e a c t i o n rate on the ratio of the partial p r e s s u r e s of n-pentane and H 2 at various t e m p e r a t u r e s . As can be seen f r o m Fig. 5, Eqs. (IV) and (V) are actually fulfilled under the c o r r e s p o n d i n g conditions. T h e dependence of the rate constant of i s o m e r i z a t i o n of the carbonium ion [Eq. (V)] on the t e m p e r a t u r e c o r r e s p o n d s to an activation energy of this step equal to 20 k c a l / m o l e . Since the activation energy of the reaction was e a r l i e r [1] found equal to 31 k c a l / m o l e for the region in which the reaction is d e s c r i b e d by Eq. (IV), the t h e r m a l effect of the first step, calculated according to the difference of these values, is - 1t k c a l / m o l e , i . e . , the formation of a carbonium ion is an endothermic p r o c e s s . If the first step is c o n s i d e r e d as adsorption of a n-pentane molecule on the surface of the catalyst, with the formation of a c a r b o n i u m ion, then its endothermicity is unexpected, since usually adsorption is an exothermic process. Since Eqs. (IV) and (V) permit a calculation of the equilibrium constant a, then, knowing the heat of the p r o c e s s Q, it is possible to find the entropy change AS, corresponding to the formation of a carbonium cation. The calculation gives AS = - 2 0 c a l / m o l e , deg. T o c o n f i r m the postulated m e c h a n i s m it is of interest to determine the values of Q and AS by some independent method and to c o m p a r e the values obtained with the experimental values. The first step of the p r o c e s s can be r e p r e s e n t e d as follows n-C.sHz~ -k H--O--M ~ n-CsHlx--O--M+H2 where M is the aluminosilicas f r a m e w o r k of mordenite. In this r e a c t i o n the C - H bonds in the molecules of the initial hydrocarbon and the O - H bonds in the acid hydroxyl groups of mordenite are broken, while H - H and C - O bonds are formed. The heat of this p r o c e s s can be approximately estimated aecording to the differences of the energies of the bonds f o r m e d and broken, with the aid of the equation 3 25
r

f5
t o o -

2
1

A
,.2

lo

210 pNz,atm Fig. 4

30

12

~6

1,0

P.-cs/P,z
Fig. 5 The dotted

Fig. 4. Dependence of the reaction rate ( r ) o n pH 2 at 230 ~ line pertains to the observable reaction r a t e .

Fig. 5. Dependence of the reaction rate (r) on the ratio of the partial p r e s s u r e s of n-pentane and hydrogen (Pn_CJPH2).

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T A B L E 2. Data on Bond Energies, k c a l / m o l e

Bond

C - H (secO--H C - O (in ondary in alcohols) LiO--I:I NaOH H~O paraffins) 90 94 ]127 1tt5 Average I 1 1 5 t 0 9

H--H

Literature referenee [31

103

S, entropy u n i t s
so

1~'~

Q = DH-H + Qc-o -- DC-H -- DO-H

(VI)

20 ~
0

/
i

.
_

Sol

Liq

Gas

Fig. 6. Dependence of the entropy on the aggregated state of the substance (sol - solid phase; l i q liquid; gas . - g a s e o u s substance): 1) water; 2) methanol; 3) cyclohexane; 4) n - a m y l cation.

where D r e p r e s e n t s the energies of cleavage of the bonds. The energies of cleavage of the C - H and H - H bonds a r e known [3]. As for the e n e r g y of cleavage of the O - H bond in the hydroxyl group of mordenite, it can be approximately c o n s i d e r e d that it is c l o s e to the e n e r g y of this bond in metal hydroxides or in water. The energy of the C - O bond can be a s s u m e d equal to the e n e r g y of this bond in alcoholates, whieh in turn evidently does not differ g r e a t l y f r o m the cleavage e n e r g y of C - O bond in alcohols (Table 2). The value of Q, caMulated aeeording to Eq. (VI) on the b a s i s of the data of Table 2, is equal t o - 1 6 k c a l / m o l e . The coincidence of this value with the experimentally found value is satisfactory, if we consider the low a c c u r a c y of the experimental data and the approximate nature of the calculation.

A calculation of the entropy of the reaction according to the entropies of the bonds participating in the reaction leads to poor coincidence with the experimentally found value. The cause of this may be the unconsidered contribution to the entropy of the r e a c t i o n of the change in the entropies of the bond in the h y d r o c a r b o n molecule that do not participate in the reaction (as a result of the disappearance of translational and rotational d e g r e e s o f ' f r e e d o m during formation of a c a r b o n i u m ion on the surface of the catalyst f r o m a molecule of n-pentane in the gas phase). T h e r e f o r e , a m o r e c o r r e c t result should be obtained in calculation according to the formula AS = S m + Sn-C,H,,+ -- S~-C,H,, -- So-~ (VII)

where SH2 and Sn_CsHI 2 are the entropies of H 2 and n-pentane in the gaseous state; Sn_CfHII+ is the entropy of the n - a m y l cation on the s u r f a c e of the catalyst; SO _ H is the entropy of the O - H bond inthe acid hydroxyl groups of the c a t a l y s t . Let us construct the dependence of the entropy of H20 on the aggregated state (Fig. 6). The distances between the. solid, liquid, and gaseous states were selected along the X - a x i s in such a way that the point would fit or~ a straight line. The entropies of HzO in the liquid and gaseous states are known [4], while for the solid state we took an a v e r a g e value, obtained by calculation on the basis of the known entropies of c a l cium and copper sulfate (Ssalts) and the c r y s t a l hydrates (Scrh) according to the formula (Sm~ $crh -- Ssalts n

where n is :he number of I-I20 molecules per salt molecule in the c r y s t a l hydrate. The entropy of the O - H bond in the acid hydroxyl group can be estimated approximately according to the formula SO_ H = 1 / 2 (SHoO)so1. Plotting the data for other substances on the graph (see Fig. 6)shows that the straight lines conE s t r u c t e d through the points c o r r e s p o n d i n g to the liquid and gaseous states are approximately parallel, and t h e r e f o r e , ':he entropy for the solid state can be found by extrapolation of the straight line to intersection with the Y - a x i s . The slopes of the straight lines c o r r e s p o n d i n g to substances of different c l a s s e s differ somewhat f r o m one another, which is evidently a s s o c i a t e d with the different distances between the a g g r e gated states of substances of different c l a s s e s (for example, alcohols and hydrocarbons). On the b a s i s of this, the g r a p h of the entropy of the adsorbed amyl cation can be estimated by constructing a straight line through a point c o r r e s p o n d i n g to the entropy of the gaseous amyl cation, to intersection with the Y-axis. T o obtain the entropy of the amyl cation in the gas phase, it is n e c e s s a r y to deduct the entropy of the C - H

973

bond, which is equal to 1 / 4 SCH4,from the entropy of n-pentane. Substitution of the values thus obtained into Eq. (VII) gives AS = - 1 2 . 2 c a l / d e g . m o l e , which, if we consider the a p p r o x i m a t e nature of the c a l c u l a tion, s a t i s f a c t o r i l y c o r r e s p o n d s to the e x p e r i m e n t a l l y found value. Thus, an investigation of the kinetics of the i s o m e r i z a t i o n of n-pentane on the H - f o r m of m o r d e n i t e at low p a r t i a l p r e s s u r e s of hydrogen gave additional evidence in support of the m e c h a n i s m of the p r o c e s s proposed earlier. CONCLUSIONS 1. T h e kinetics of the i s o m e r i z a t i o n of n-pentane on the H - f o r m of m o r d e n i t e w a s investigated at p a r t i a l p r e s s u r e s of hydrogen of 2-6 a t m . 2. T h e d e g r e e of deactivation of the c a t a l y s t and the c o r r e c t e d r e a c t i o n r a t e under these conditions were determined. 3. The heat and entropy of the f o r m a t i o n of the n - a m y l cation w e r e determined, and an independent a p p r o x i m a t e calculation of t h e s e p a r a m e t e r s was p e r f o r m e d . LITERATURE 1. 2. 3. CITED

4.

Kh. M. Minachev, V. I. Garanin, and V. V. Kharlamov, Izv. Akad. Nauk SSSR, Ser. K h i m . , 835 (1970). Kh. M. Minachev, V. I. Garanin, V. V. K h a r l a m o v , T . A. Isakova, and E . l~. Senderov, Izv. Akad. Nauk SSSR, S e r . K h i m . , 1737 (1969). V . I . Vedeneev, L. V. Gurvich, V. N. K o n d r a t ' e v , V. A. Medvedev, and E. L. Frankevich, C l e a vage E n e r g i e s of Chemical Bonds. Ionization P o t e n t i a l s and Electron Affinity, Handbook [in Russian], Izd-vo AN SSSR (1962). Ya. I. G e r a s i m o v , V. P . Dreving, E. N. Eremin, A. V. Kiselev, V. P . Lebedev, G. M. P a n c h e n kov, and A. I. Shlygin, Course in P h y s i c a l C h e m i s t r y [in Russian], Vol. 1, Khimiya (1969).

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