H2S-PromotedThermal Isomerization

of Cis-2-Penteneto 1-Pentene and

Trans-2-Pentenearound 800 K

D. PERRIN, C. RICHARD, and R. MARTIN

LTniversitkde Nancy I , Laborutoire de Chimie Radicalaire, U . A . n'328 du C.N.R.S.,
BP 239, 54506 Vandoeuvre les Nancy, Cedex, France

Abstract
H,S accelerates the thermal isomerization of cis-2-pentene (P2c)to 1-pentene (P1)and
trans-2-pentene (P2t) to around 800 K. This effect is interpreted on the basis of a free
radical mechanism in which 2-pentenyl and thiyl radicals are the main chain carriers.
P1 formation is essentially explained by the competing processes:
i 10) CH;CHCHC,H, + H,S -+ PI + HS
(2) C H ~ C HCHC,H, CH,. + I,~-C*H,
P2t formation is due to addition-elimination processes:
(113(-11)(123 HS. + P2c F=? C5HIoSH. - P2t
the importance of which has been evaluated against process ( - 4 ~ ) :
+ HS.

14p)i -4p) CHXH

CHC,H, + H,S ep2C + HS.
The following ratios of rate constants have been measured and are discussed:
klO/& 10-2 19- 2.1 exp(31,200 ? 800/RT) mol cm3
k , , / k - a , = 10 R9+49 exp(2100 * 1700/RT)
IRT in cal mol-'1.

Introduction
It has been shown that the thermal decomposition of cis-2-pentene is
essentially a free radical chain reaction yielding nearly equal amounts
of methane and 1,3-butadiene a t low extent [ll. By contrast, the 2-1 and
cis-trans thermal isomerization appears to be partly molecular, partly
free radical, due to the low reactivity of 2-pentenyl free radicals 121.
H2S has been shown to increase the productions of methane and
1,3-butadiene and to inhibit those of other products (e.g., 3-methyl-
1-butene) while its own consumption rate is negligible [31. In the latter
work, the influence of H,S on the 2-1 and cis-trans thermal isomer-
izations of the olefin has not been examined.
International Journal of Chemical Kinetics, Vol. 20, 621-632 (1988)
k 1988 John Wiley & Sons, Inc. CCC 0538-8066/88/080621-12$04.00
622 PERRIN, RICHARD, AND MARTIN

The object of the present work is t o complete the study of the

H2S-promoted thermal reaction of cis-2-pentene and to get a better
knowledge of the reactivities of HS. and 2-pentenyl free radicals.

Experimental
The reaction was studied in a conventional static system previously
described [ll. The reaction vessel was a 250 ml Pyrex sphere enclosed
in a n electrically heated steel cylinder. The furnace temperature was
controlled to within +0.5”Cwith a thermoregulator. The course of the
reaction was followed by product analyses at various time intervals.
Products were analyzed by gas chromatography and identified by mass
spectrometry. A 10 m squalane column and a 4 m pp ‘-oxydipropionitrile
column associated with a 3 m adiponitrile column gave a good sepa-
ration of the reaction products. Mixtures of gas were prepared in a
spherical vessel with an axial cold finger which gave efficient mixing
by convection. Nevertheless, several hours were allowed for thorough
mixing.
Cis-2-pentene was a “Chemical Sample” product, of molar purity
higher than 99%.The main impurities were trans-2-pentene and traces
of l-pentene and 2-methyl-2-butene. Hydrogen sulphide was a product
from La Socibt6 Nationale des Pbtroles d’Aquitaine and did not show
any impurity by GC analysis.

Results
The reaction was studied in the temperature range 743-772 K, at
initial cis-2-pentene pressures of 10-100 torr and up to 5 torr of hydro-
gen sulphide. The yields of products were followed in conditioned Pyrex
vessels a t conversions as low as 0.1%. Results were reproducible. Addi-
tion of nitrogen did not show any influence on the reaction rate and
wall effects were not studied further.
As shown in Figures 1 , 2 , and 3, H,S strongly enhances the produc-
tions of P1 and P2t. It has been shown that the reaction is self-
accelerated at a low extent and that the conventional initial rates are
not easily accessible in the temperature and pressure ranges [I,31. The
rate values given in Tables I and 11 and in Figure 3 are therefore
maximum rate values which are reached a t a very low extent of reac-
tion. Data on methane and 3-methyl-l-butene(M3B11, though already
discussed [31, are recalled in Tables I and I1 because they will be used
in the interpretation.
Let us recall that H,S consumption is quite negligible as compared
to that of cis-2-pentene and that no sulfur compound has been detected
in the reaction products [31.
 THERMAL ISOMERIZATION 623

/
P
I
Figure 1. Trans-2-pentene versus time. T 743 K. Initial concentration of cis-
2-pentene: 1.08 mol ~ m -Without
~ . H,S ( - - - ) and with 10% H,S (-),

Interpretation
The thermal decomposition of cis-2-pentene (P2c) in presence of
hydrogen sulphide has been described by a free radical chain mecha-
nism [31, propagated by HS., CH,. and two resonance-stabilized C,H,.

(2)
(3)
CH',CHCHC,H,
CH3. + P2c
-
free radicals in the following steps:

- CH,
CH,. + 1,3-C&
+ CH',CHCHC2H,
(3') C H ~+
. ~2~ -+ CH, + CH~CH~HCHCH,
(4)(-4) CH,CH'CH C H C H ~eCH',CH CHC,H,
(4p) + HZS --+ CH, + HS.
CH3.
( 4 p~
~ 4 ~ ) CHC,H, + H,S e~2~ + HS .
CH',CH
624 PERRIN, RICHARD, AND MARTIN

(-4p')
(4~') CH3CHCHCHCH3+ H,S e P2c + HS.

(i) P ~ c-
Initiation follows classical breaking of the weakest C -C bond:
CH3. + CdH,.
and, since the bond strength in H,S is 91 kcal mol-l, H,S cannot give
rise to initiation steps which would be important in the experimental
conditions. But HS. free radicals are involved in termination steps with
CH3. and C5H9.free radicals [see [311.
I n t h i s scheme CH3CH: C H C H 2 C H 2 . , CH3d : CH C z H 5 a n d
CH3CH:C CzH5 free radicals have been ignored. Their formation is
difficult and they would easily isomerize into allylic C5H9.free radicals.
 THERMAL ISOMERIZATION 625

r /r
X,H25 X

.02 .04 .06 (H,S)o/ CP2clo

Figure 3. Rate ratios for X formation in presence and in absence of H,S. X =

T = 743 K. (PBc), = 1.08
1-pentene [@I; X = trans-2-pentene (0); mol cm '.

TABLEI. Rates of product formation x (mol ~ r n s-');

- ~ (P2c). = 1.08 x
mol ~ r n - ~ .

1 OSx(H2S)o.rnol c m ~ 3 0 1.08 2.16 4.32 6.48 8.64 10.8

CH4 732 875 928 1074 1135 119 150

-13 K 398 148 250 4 96 787 107 156
P2l 59 1 409 638 1060 1490 1960 2380
M381 4 38 354 2 79 2 09 160 142 145

_ _ . _____~___ ______~~_____
CH4 174 221 241 277 300 318 313

-57 K 814 258 448 9 18 136 203 23 6

P21 113 825 1270 2200 3200 4400 5000
M381 10 1 853 7 41 5 41 4 42 3 77 2 87

_ _ _ _ _ _ _ _ __ _ _ _ _ _ _ _ _ _ _ _~~ _______ ~ _ __ _ _ _ ______----__

~

CH4 417 526 613 723 779 042 857

772 K 1.49 4.42 7.7 15.9 24.7 36 46.9

P2t 270 1620 3000 4800 7000 9000 10000
M381 24.9 22.1 18.1 15.9 13.0 11.2 10.1
626 PERRIN, RICHARD, AND MARTIN

TABLE11. Rates of product formation x lou (mol cm-3 s-'); T = 743 K.

1 0 7 x j ~ ~ s i ~ I O ~ X ( P ~ C ) rnol
~ . cm-3

rnoi c m - 3 216 432 648 864 1 51 2 16

0 143 31 2 433 570 100 1 138

C"4
1 08 43 6 75 1 998 124 181 231

0 ,0314 ,094 .145 ,255 .723 135

P1
I .oa 4.91 8.25 10.95 13.3 19.9 25.6

0 9.33 20.0 31.2 42.7 76.5 126

P2f
1.oa 970 1565 1820 2280 2950 3595

0 .90 1.86 2.33 3.53 5.91 8.49

M301
I.08 .119 .351 ,627 1.01 2.37 3.81

Let us first examine the case of 1-pentene formation. In absence of

H2S, 1-pentene (Pl) arises from three distinct sources [2]:
metathetical steps:
( 8)
(8')
+ ,~2~ --+
CH~CHCHC~H
CH',CH CHC2H5+ P2c - P1
PI + CH',CHCHC,H,
+ CH3CHCHCHCH3
free radical disproportionations:
(9)
(9')
2 CH',CH CHC,H,
CH',bH CHC2H5+ CH,CHCH CHCH3
- - P1 + 1,3-C5H8
P1 + 1,3-C&
molecular isomerization:
(m) P2c - P1
The presence of H,S strongly increases the formation rate of 1-pentene.
Since thermochemistry indicates that the global initiation rate is the
same in presence and in absence of H2S (process i), the accelerating
effect of H,S may only arise from process (10):
(10) CHiCHCHC2H5+ H2S - P1
which is a fourth source of P1. The maximum rate of P1 formation in
+ HS .
presence of H,S may be expressed as the sum of four terms:
2
(A) rP1,H2S= C1(P2C)orCH4.H2S+ C2(rCH4,H,S)
+ CdP2C)O + C4(H2S)orCH,,H2S
 THERMAL ISOMERIZATION 627

with

is the rate of formation of product X in presence

Here and after, rx,H2S
of H,S. In this expression, rCH4,H,S/k2 represents the quasi-stationary
concentration ofthe chain carrier CH2CHCHC2H5[see e.g. [311. The con-
stants C1,Ca,and C, have already been evaluated in absence of H2S[21:
Cl = exp(24600/RT) mol-l cm3
C2 -- 10-1600 exp(78600/RT) mol-' cm3 s-'
c, = 101378 exp(-71900/RT) s-'
Here and after RT is in cal mol-'. Using these values, relation (A)
has been adjusted to the experimental data of Tables I and I1 and a
value of C, has been obtained by linear regression:
klo/kz = 10-319i23 exp[(31200 i 8 0 0 ) / R T ]mo1-l cm3
Quoted uncertainties are standard deviations.
Since the formation of P1 is much more strongly accelerated by H2S
than that of methane, the fourth term of relation (A) is by far the most
important and the accuracy on C4 is much better than those on C1, C2,
and C, determined in absence of H2S. The present value of C4 will be
discussed in the next paragraph.
Let us turn now to the case of truns-2-pentene (P2t). It has been
shown that cis-trans isomerization of P2c in absence of HzS is mainly
molecular:
(m') P2c - P2t
the free radical part of the reaction being practically negligible [a]. In
presence of H2S, P2t may arise from two extra sources:
metathetical steps similar to (10):
(10')
( 10")
CHiCH CHC2H5 + H,S
CH,CHCH CHCH, +H~S
-- P2t + HS .
~ 2 +t HS .
addition-elimination steps:
(11)(-11)
(12)
HS. +P
CSHIOSH. -
~I
c CSHioSH.
P2t + HS .
Let us notice that C5HloSH.is hardly able to give rise to thiols because
the C-S bond is much weaker than C-H bond and QSS concen-
tration of C5Hl0SH.is very low.
628 PERRIN, RICHARD, AND MARTIN

Since processes (lo), (10’) and ( 1 0 ) have about the same relative
importances, the first source of trans-2-pentene must be comparable to
the total amount of 1-pentene and it is unquestionably negligible com-
pared with the second one. The global rate of P2t formation in presence
of H2S may be written:
(B) rPZt,H?S rPZt + kllk,,(p2c),(Hs.)/(k-ll + kl2)

where rPZtis the rate of P2t production in absence of H,S [process (m’)].
With the usual QSS assumptions for every free radical and supposing
chains are long, relation (B) for maximum rates may be written:
(C) Y = B1 + BZX
with y = [rPZt.HzS - rPZtI/[(HZs)o rCH,,HaSl
X = 11 - RM~BI/RcH.,I/(H~S),
R M S B=~ rM3B1,HzS/rM3B1
R C H=~ ~ c H . , H, ~ S / ~ C H ,
Bz = kllklZ/(k-ll + kl2) (k-4, + k-4,,)

Bi = Bdk4, + kio + kio (k4,* + kio,)k--4/hl/kz

Relation (C) was adjusted to the data of Table I and I1 and values of
Bl and B2 were obtained by linear regression (see Table 111).
Assuming the equalities kl1= k12 and as a first approximation
E-,, = E-,,, -- Ell, by analogy to the case of methyl free radical, then
Bz should not be temperature dependent. If we take, in the tempera-
ture range, the mean value B2 -- 7.2, we get with a better approxi-
mation for B1:
Bl = 10-2.27?0.92 exp[(35100 ? 3200)/RT] mol cm-3
If we further write reasonable equalities [see [411:
k-4, = k-4,,, k1,/k4, = CY, k1o,/k4,, = klo/k4, p

TABLE
111. B, and B, values computed from experimental data
on P2t.

T(K) 743 757 772

l o - ? B1 91 i 10 90?09 594 0 5
moi 1 0 3
~- ~ - - - - ~ _- ~~~

B2 9 O i O 8 6 3 t 0 6 6 3 + 03

Uncertainties are standard deviations.

 THERMAL ISOMERIZATION 629

where LY and p are the equilibrium ratios (Pl)/(P2c) and (P2t)/(P2c)

respectively, we get:
kgl,/k4+= k4/k-, and B1 = B2(a + 2p + 2)k,,/k2
Taking LY and p values from thermochemical tables [51:
ff = 1024 exp(-2300/RT) and p = 10- l2 exp(460/RT)
we obtain:
k 4l, /k, = 10-377C92 exp[(35100 t 3200)/RT] mol-l cm3
k,,,/k, = ak4JkZ = 10-3 53%92 exp((32800 ? 3200)/RT] mo1-l cm3
Let us recall that from data on P2c t o P1 isomerization in presence
of HPS, we got:
klo/kz = exp(31200/RT) mol-I cm3
Both values of kI0/k2,obtained by two independent methods, agree
quite well within the experimental error limits.
In the modelling of cis-trans isomerization, the poor precision of the
determinations of B1 and Bz led us to assume that BP was not tem-
perature dependent. As, on the other hand, the ratio klo/k2 (and
k4,/k2 = klO/akp)has been determined with good accuracy from re-
lation (A),we are entitled to use the latter values in order to get a more
precise expression of B, from relation (C). We thus obtain:
B1 = B2 x exp(33500/RT).
Relation (C) can now be written:
B, = Y/[X + exp(33500/RT)]
Writing the Arrhenius form of B,, we obtain by linear regression of all
the experimental points:
Bz = loz3' 49 exp(2400 t 1700/RT)
Assuming the reasonable equalities k-41, ;= k-4p and k-ll -- klz, we
compute:
kll/K-4p = 10'' exp(2100/RT)
with:
klo/k2 = exp(31200/RT) mo1-l cm3
k4,/k, = exp(33500/RT) mol-' cm3.

Discussion
Absolute values of rate constants may be estimated from the above
ratios. In a preceding article 131 we got for the rate constants of pro-
cesses ( - 4 ~ 1 ,(-4p'), and (4p):
630 PERRIN, RICHARD, AND MARTIN

k-,, -- k-,, = exp(-2300/RT) mol-' cm3 s-'

h4, = exp(-4700/RT) mol-' cm3 s-'.
From these values, we obtain:
k" = exp(-200/RT) mol-' cm3 s 1

k, -- 101310 exp(-38200/RT) s-'

kl, I- logg1exp(-7000/RT) mol-' cm3 s-'
The expression of k, which is proposed here is interesting because it
has never beer?measured before. From thermochemical data [3,6] con-
cerning CH,CH CH C,H5 free radicals, we compute for equilibrium
(2) (-2) around 800 K:
(2) (-2) CH',CHCHC2H5 CH3. + 1,3-C4H6
K2 = k 2 / k 2 = loz3exp(-30700/RT) mol cm-3
Two values of k-, may be found in the literature. The first one,
k-2 = 10" l3 exp(-4500/RT) mol-' cm3 s-'
obtained from data given by Cvetanovic and Irwin 17,81, has been re-
vised on the basis of 1121:
h = exp(-8000/RT) mol-' cm3 s-'
for the competitive process:

It would give:
CH,. + i-C4H10 - CH, + C,H,.

ha = exp(-35200/RT) SKI

This expression is much higher (by a factor 14 a t 800 K) than our

estimated k2 value. The second value of h-, has been measured by
Mandlecorn and Steacie [91; it has been discussed by Benson (see [61
page 168):
k 2= l o l l 3 exp(-5400/RT) mol-' cm3 SK'
It is consistent with:
k, = exp(-36100/RT) s-'
This evaluation is still higher than ours. In fact, there are two distinct
processes:
(-2)
(-2') CH,.
CHB. +
+ 1,3-C4H6
1,3-C4H,j
-- CH',C'H CHC,H,
CH2CH(CH&H:CH2
and the k-* rate constant discussed in the literature is a global rate
constant which corresponds to processes (-2) and (-2').
 THERMAL ISOMERIZATION 63 1

If we consider our own value of k,, we get from thermochemistry:

k-, = Wo8exp(-7500/RT) mol-' cm3 s-'
This value may be compared to that of process ( 5 )which was previously
proposed [21:
(5) CH,. + P ~ C--, (CH~)~CHCHC,H,
k, = lo1'' exp(-82OO/RT) mol-' cm3 5-l.
It is practically the same. This is not unreasonable for two similar
exothermic addition processes, even though a resonance-stabilized ad-
duct radical has been formed in one case (process (-211, and not in the
other one. However, literature data indicate that process (-2) + (-2')
would be about 15 times faster than (5) at 750 K 181.
The expression for k,, is also interesting. From thermochemical data
we compute, for the equilibrium:
(io)(-io) CH',CHCHC~H,+ H ~ S
I PI + HS.
klo/k-lo = 10 l3 exp(- 4 7 0 0 / ~ ~ )
Assuming the equalities kl0 k - 4 p I- I- exp(-2300/RT) mol-'
cm3 s-l, we get:
hlo = logg1exp(-7000/RT) mol-' cm3 5-l
It is exactly the same as our klo value computed from P2c to P1 iso-
merization. We did not find in the literature any kinetic data on
process (10). In the case of butene-2 cis, Richard et al. [lo] studied
similar processes:
( a )(-a) C,H,.+ H,S e1-C4H8+ HS.
(b) C4H7. + ~is-2-CqHR 1-C4H8 + C4H7.
and measured the ratio:
k,/kb = lo4 exp(6500/RT)
The authors had no reliable value for k b , but estimated an activation
energy Eb = 15800 cal mo1-l. Due to their underestimate of the en-
thalpy of formation of 2-butenyl radical, this value has to be corrected
to E b = 13600 cal mol-'. As process (b) is very similar to processes (8)
and (8'1, we may write k b == (k8 + k 8 ) ,and, from the expression of C1,
hb = log4' exp(-13600/RT) mol-' cm3 s-' [see [211. Finally we get:
h, 109%' exp(-7100/RT) mol-' cm3 s-l.
Thus, the results of Richard et al. on process (a) are quite consistent
with the present values of klo which have been obtained either from
cis-1 isomerization or from our value of k-4wusing the thermochemistry
of processes (101(- 10).
632 PERRIN, RICHARD, AND MARTIN

As for process (111, no determination of its rate constant has ever

been made. From the present estimation, it appears that the addition
(11)of an HS. free radical to the double bond of P2c has a very low
activation energy. This may be compared with the addition of polar OH
radical to ethene [lll:
k = 1012.6
exp(-BOO/RT) mo1-l cm3 s-'
the A factor of the latter reaction is higher than All.
In conclusion, H,S strongly enhances the thermal 2-1 and cis-trans
isomerization of cis-2-pentene. This effect is interpreted on the basis of
a free radical mechanism which is entirely consistent with the mecha-
nism proposed in absence of H2S.Interesting rate constants ratios are
measured and several absolute values of rate constants are obtained on
the basis of previous results or of thermochemical data. There is a very
strong consistency between rate constant values which are obtained
from kinetic data on different products of the reaction or from con-
ventional thermochemical data. This gives support to the idea that
conventional kinetic studies of global systems can contribute to rate
constant measurements.

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Organic Compounds, Wiley, New York, 1969.
[61 S. W. Benson, Thermochernical Kinetics, 2d ed., Wiley, 1976.
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Received November 16, 1987

Accepted February 22, 1988