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ISSN 0965-5441, Petroleum Chemistry, 2009, Vol. 49, No. 5, pp. 343353. Pleiades Publishing, Ltd., 2009.

Original Russian Text T.S. Pokidova, E.T. Denisov, A.F. Shestakov, 2009, published in Neftekhimiya, 2009, Vol. 49, No. 5, pp. 363373.

Kinetic Parameters and Geometry of the Transition State


in the Unimolecular Degradation of Alcohols
T. S. Pokidova, E. T. Denisov, and A. F. Shestakov
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432 Russia
e-mail: det@icp.ac.ru
Received April 16, 2009

AbstractExperimental data on the unimolecular degradation of structurally different alcohols, alkanols into
water and an olefin and alkenols into a carbonyl compound and an olefin, were analyzed in terms of the method
of crossing parabolas. The kinetic parameters characterizing such decomposition were calculated and factors
that affect the activation energy of the reaction (the cycle strain energy, the steric factor, and the effect of electrons neighboring the reaction center) were determined. The activation energies and the rate constants were calculated for 30 alcohol degradation reactions. The enthalpies, the activation energies, and the rate constants of
degradation of unsaturated alcohols were compared for two different degradation routes yielding a carbonyl
compound and an olefin or resulting in water and an olefin. Quantum-chemical calculations of the transition
states for three model reactions were performed. The activation energies and the rate constants were obtained
for the first time for 13 reverse reactions of the addition of carbonyl compounds to olefins.
DOI: 10.1134/S0965544109050016

High-temperature cracking of organic compounds


proceeds either in the chain mode involving free radicals or via a molecular mechanism, suggesting the degradation of one molecule into two or more molecules
[1, 2]. The theoretical treatment of these two routes of
degradation of different molecules needs a method for
the calculation of the activation energies and the rate
constants of such reactions. In our previous works, we
analyzed the degradation of alkyl and alkoxyl radicals
using the method of crossing parabolas (MCP) [3, 4].
This study is devoted to the treatment of experimental data on the degradation kinetics of alkanol and alkenol molecules in terms of the crossing parabolas
approach [58]. The parameters obtained to describe
the activation energy of these reactions as a function of
their enthalpy were used to calculate the activation
energies and the rate constants of a broader variety of
reactions of structurally different alcohols. Quantumchemical calculations relevant to the computation of
the activation energy and the transition state geometry
for the degradation of unsaturated alcohols occurring
by two different routes via the six or four-membered
transition state [9] were performed.
CALCULATION PROCEDURE
Method of Crossing Parabolas
The decomposition of the aforementioned alcohols
is characterized in terms of MCP by the following
parameters [6, 7]:

(1) Classical enthalpy He, which includes the difference between zero-vibration energies of the reacting
bonds:
He = H + 0.5hNA(i f),
(1)
where h and NA are Plancks constant and Avogadros
number, respectively, and i and f are the frequencies
of the stretching vibrations of the reacting bonds.
(2) Classical potential barrier of the reaction Ee,
which includes the zero-vibration energy of the breaking bond and the average kinetic energy of motion of
the particle and is related to the experimentally determined activation energy by the simple equation:
(2)
Ee = + 0.5hNAi 0.5RT,
where R is the gas constant and T is the temperature in K.
(3) Parameter re equal to the total elongation of the
breaking and forming bonds in the transition state.
2

(4) Parameter bi (2 b i is the force constant of the


2

breaking bond), parameter bf2 b f is the force constant


of the forming bond and coefficient = bi/bf.
(5) Experimental activation energy exp, which was
determined according to the Arrhenius equation
exp = RT(lnnA/k),
(3)
where is the preexponential factor, which is constant
for reactions of the same class; k is the empirical reaction rate constant; and n is the number of equireactive
bonds.
The degradation of alcohols is a reaction with the
concerted breaking of some bonds and the formation of

343

344

POKIDOVA et al.

other bonds. For such reactions, the preexponential factor in the Arrhenius expression of the reaction rate
constant depends on the activation energy of degradation E and the number of simultaneously broken bonds
(m). According to the oscillation model of concerted
degradation, this dependence is described by the formula [10]:
A = A0 (m/2(m 1))(mRT/E)(m 1)/2.

(4)

The reactions under consideration are an example of a


concerted two-center reaction in which two bonds
simultaneously break. The equation for the degradation
rate constant of an alcohol (concerted degradation
involving two bonds, m = 2) takes the following form:
k = A0 (2RT/E)1/2exp(E/RT).

(5)

Since the preexponential factor in this equation is temperature-dependent as well, the activation energy of
degradation E is related to the experimental activation
energy exp = RT2d ln k/dT by the following expression:
E = exp 0.5RT
(6)
(lnk = const + 1/2 lnT E/RT and exp = RT2dlnk/dT =
RT2(0.5/T + E/RT2) = 0.5RT + E, wherefrom Eq. (6) is
obtained). The parameters specified above are related to
one another by the equation [6]:
bre = (Ee He)1/2 E e .
1/2

(7)

The parameter bre, in turn, makes it possible to calculate the classical barrier for a thermoneutral reaction
analogous to the reaction in question with He = 0,
bre = const, and = const.
Ee0 = {b/(1 + )}2 r e .
2

(8)

If the parameters and bre are known for the class of


reactions of interest and the condition He min < He <
He max holds for the reactions, the activation energy for
each individual reaction of this class can be calculated
by the following equation ( = bre(1 2)1):
Ee = 2 {1 [1 He/Bbre]1/2}2.

(9)

The values of He max and He min are calculated by the


formulas [7]:
H e

= ( br e ) 2br e ( 0.5hN A f )
2

max

1/2

(10)

+ 0.5 ( 1 )hN A f ,
2

H e

= ( br e / ) + 2br e ( 0.5hN A i )
2

min

_ 0.5 ( 2 1 )hN .
A i

1/2

(11)

The sequence of operations in the calculation of the


kinetic parameters for the reactions of degradation of
alcohols with different structures was as follows.
The reaction enthalpy for the degradation of alcohols (H) was found as the difference of the standard
enthalpies of formation for the products and the reactant alcohol (data on the enthalpies are as given in [11]):

H = H f ( R R C=CR R ) + H f ( H 2 O )
1

(12)

H f ( R R CHCR R OH ),
0

H = H f ( R R CHCH=CH 2 ) + H f ( R R CO )
(13)
1 2
3 4
0
H f ( R R C=CHCH 2 CR R OH ).
0

For some compounds, the enthalpies of formation H f


were calculated with the use of thermochemical increments [12]. Unknown enthalpies of formation for
unsaturated alcohols were found with the use of an
increment that was determined by a comparison of
known enthalpies for a series of alcohols and the alkenes having the matching structure [11]. For example,
0

H f ( MeCH=CHCH 2 CH 2 OH )
0

= H f ( MeCH=CHCH 2 CH 3 ) 150.0/kJ/mol.
0

(14)

The experimental activation energy exp for the degradation of alcohols was calculated by the Arrhenius
equation (3) using a standard factor for the degradation
of alcohols in the gas phase = 1.02 1014 s1 for
alkanols (average of seven experimental values [13
18]) and = 6.61 1011 s1 for alkenols (average of five
experimental values [19, 20]) and the rate constant k
found in the experiment [1320]. The values of E were
calculated according to Eq. (6). Using these E values,
we found A0 using Eq. (5). In this manner, all of the
kinetic parameters of the reaction were calculated.
Then, the parameter bre was calculated by Eq. (7).
Quantum-Chemical Calculation
The following alcohol degradation reactions were
chosen for theoretical calculation:
CH2=CH2 + H2O
C2H5OH
Me3COH

Me2C=CH2 + H2O

CH2(OH)CH2CH=CH2
CH2(OH)CH2CH=CH2

CH2=CHCH=CH2 + H2O
CH2=CHCH3 + CH2O.

Since the decomposition yielding water involves the


four-membered transition state, it is of interest to consider the degradation of these alcohols through the sixmembered transition state as well, which is formed
with the participation of another water molecule. For
this purpose, we take the following reaction:
CH2=CH2 + 2H2O.
C2H5OH + H2O
The geometry of stationary points on the potential
energy surface of the system was found as a result of
CCD optimization with the 6-31G* basis set. The
obtained geometric parameters were used for calculation of the energy of the system by the CCSD(T)
method with the 6-311++G** basis set and allowance
for the zero-vibration energy in the harmonic approximation at the CCD/6-31G* level. As an alternative, the
hybrid density functional theory method B3LYP with
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345

Table 1. Kinetic (kexp, E, bre) and thermodynamic (T, H) parameters of the transition state for the degradation reactions of
alcohols ( = 0.769, He = 5.1 kJ mol1, Ee = 14.1 kJ mol1, Ad = 1.02 1014 s1)
H
Reaction
kJ
Me2CHOH

MeCH=CH2 + H2O

kexp (800 K)

mol1

s1

721801 1.47 103

50.7

Eexp

kJ

mol1

A0

br e

s1

Reference

262.6 259.3

28.14

1.63 1014

[13]

282.0 278.7

29.12

5.1 1014

[14]

28.89

5.0 1014

[15]

29.15

5.1 1014

[16]

29.09

5.0 1014

[17]
[18]
[18]

br e = 28.14
Me3COH
Me3COH
Me3COH
Me3COH

Me2C=CH2 + H2O
Me2C=CH2 + H2O
Me2C=CH2 + H2O

54.0

10501300 3.58 104

54.0

9351400

6.77 104

9201180

3.26 104

10201200

3.76 104
4.03 104

278.5 275.2

29.14

5.0 1014

277.4 274.1

29.05

5.0 1014

54.0

Me2C=CH2 + H2O

54.0

Me2CHCMe2OH
Me2CHCMe=CH2 + H2O

52.9

10801160

Me2CHCMe2OH
Me2C=CMe2 + H2O

46.6

10801160 7.93 105

277.7 274.4
282.6 279.3
281.6 278.3

br e = 29.04 0.11
a

(kJ mol1)1/2.

the 6-31G* basis was used for the geometry optimization followed by the calculation of the energy of the
system by the B3LYP or CCSD(T) method with the
basis set 6-311++G**. Similar approaches were used
for the study of the addition of HF to fluorinated alkenes [21, 22] and H2O to ketone [23, 24] through a fourmembered transition state.
The enthalpy and the activation energy of the reaction at 298 K were found from the partition functions in
terms of the harmonic oscillatorrigid rotator model.
The GAUSSIAN 98 program was used to run all calculations [25]. All of the reactions under consideration are

endothermic and their transition state is late in character.


RESULTS AND DISCUSSION
Degradation of Alcohols
The degradation of alkanols in the gas phase (
800 K) occurs in the unimolecular mode, as shown earlier [2], by concerted bond rearrangement via the fourmembered transition state:

R2 R3
R1

R1R2CHCR3R4OH

C C R4
H O

As a result of this decomposition, CH and COH


bonds break and HOH and CC bonds correspondingly form. In the MCP formalism, we considered such
a decomposition reaction to be a result of CH bond
breaking and HOH bond forming. As shown by quantum-chemical calculation, it is these bonds that experience the maximal elongation in the transition state (see
below). The results of the calculation of exp, , H, bre,
and A0 from the experimental data are presented in
Table 1. The following values of the terms b and
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R1R2C=CR3R4 + H2O.

()

0.5hNA calculated from spectral data were used in this


case:
Bond

b 1010, kJ1/2 mol1/2m1

0.5hNA, kJ mol1

37.43
48.68

17.4
22.5

The concerted degradation of alkanols is an endothermic process ( > 0, ranges within 46.6
54.9 kJ mol1) and has a high activation energy (rang-

346

POKIDOVA et al.

Table 2. Calculated kinetic (E, k) and thermodynamic (H) parameters of the transition state for the degradation reactions
of alcohols ( = 0.769, He = 5.1 kJ mol1, Ee = 14.1 kJ mol1, A0 = 5.0 1014 s1)
H

Reaction

kJ

k (800 K)

mol1

bre = 28.14(kJ mol1)1/2


MeCH2OH
CH2=CH2 + H2O
45.2
256.8
Me2CHOH
MeCH=CH2 + H2O
50.7
259.3
MeCH2CH2OH
MeCH=CH2 + H2O
33.1
251.3
Me2CHCH2OH
Me2C=CH2 + H2O
25.2
247.8
MeCH2CHMeOH
MeCH=CHMe + H2O
41.1
254.9
MeCH2CHMeOH
EtCH=CH2 + H2O
52.8
260.2
Me2CHCHMeOH
Me2C=CHMe + H2O
31.4
250.5
Me2CHCHMeOH
Me2CHCH=CH2 + H2O
46.5
257.4
Me3CCHMeOH
Me3CCH=CH2 + H2O
47.9
258.0
EtCH2CHMeOH
EtCH=CHMe + H2O
40.6
254.7
EtCH2CHMeOH
EtCH2CH=CH2 + H2O
50.7
259.3
bre = 29.04 (kJ mol1)1/2
Me3COH
Me2C=CH2 + H2O
54.0
277.2
Me2CHCMe2OH
Me2C=CMe2 + H2O
46.6
273.8
Me2CHCMe2OH
Me2CHCMe=CH2 + H2O
52.9
276.7

ing from 259.3 to 279.3 kJ mol1), a fact that can be due


to the formation of a strained four-membered transition
state (see above). From the data in Table 1, it is seen that
the degradation reactions of secondary and tertiary
alcohols have different values of bre (28.14 and 29.04
0.11 kJ1/2 mol1/2, respectively) and, correspondingly,
have the classical barrier to the thermoneutral reaction
of 0 = 253.0 kJ mol1 for secondary and 0 =
269.6 kJ mol1 for tertiary alcohols.
The increase in the classical thermoneutral-reaction
barrier by 16.5 kJ mol1 in the case of the degradation
of the tertiary alcohol can be associated with the
increase in the strain of the four-membered transition
state due to substutuents (steric factor (s) [7]).
The values of bre calculated from the experimental
data for the degradation of alcohols of two classes were
further used for the calculation of the activation energy
(Eq. (9)) and the rate constant k for a number of individual reactions relevant to these classes, according to
Eq. (5) (0 = 5.0 1014 s1, the average from Table 1).

|E|

s1

0.0

3.3 103
4.5 103
5.1 103
4.3 103
2.9 103
2.0 103
2.9 103
3.0 103
2.7 103
3.0 103
2.3 103

1.1
0.3
1.5

4.4 104
8.2 105
3.2 104

Along with the reactions described in the literature, the


reactions that we simulated for the degradation of other
alcohols were calculated. The results of the calculation
of and rate constants k are presented in Table 2. The
condition He min < He < He max holds in all cases.
As is seen from the data given in Tables 1 and 2, the
calculated activation energies for the degradation reaction of secondary and tertiary alcohols are close to the
experimental values (the error || ranges from 0.0 to
1.5 kJ mol1).
Degradation of Alkenols
The degradation of unsaturated alcohols that bear
the OH group to the C=C bond occurs in the unimolecular mode in the gas phase at = 650 K as a concerted degradation involving breaking and forming corresponding bonds. This degradation is characterized by
the six-membered transition state [2]:

R2
R1R2C=CHCH2CR3R4OH

R1

R1R2CHCH=CH2 + R3R4CO,

C H

(b)

O
C
R3

where R1R4 is hydrogen or an alkyl. To analyze the


reaction in this case, we considered the transition state

R4

to be a result of the rearrangement of two bonds, the


breaking OH bonds and the forming CH bond. The
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KINETIC PARAMETERS AND GEOMETRY OF THE TRANSITION STATE

347

Table 3. Kinetic (kexp, E, bre) and thermodynamic (T, H) parameters of the transition state for the degradation reactions of
alcohols ( = 1.255, He = 4.3 kJ mol1, Ee = 19.0 kJ mol1, Ad = 6.61 1011 s1)
H

Reaction

kJ

CH2=CHCH2CH2OH
MeCH=CH2 + CH2O
CH2=CMeCH2CH2OH
Me2C=CH2 + CH2O

mol1

kexp (800 K)

s1

Eexp
kJ

br e

mol1

A0
s1

Reference

61.9

650

7.37 103

173.6

170.9

27.73

2.8 1012

[19]

60.3

616676

1.89 102

168.5

165.8

27.33

2.8 1012

[20]

br e = 27.53 0.28 (kJ mol1)1/2


CH2=CHCH2CHMeOH
MeCH=CH2 + MeCHO
CH2=CHCH2CMe2OH
MeCH=CH2 + Me2CO

42.7

650

1.51 102

169.7

167.0

28.43

2.8 1012

[19]

30.3

650

2.85 102

166.3

163.6

28.78

2.8 1012

[19]

br e = 28.60 0.24 (kJ mol1)1/2


CH2=CPhCH2CH2OH
MeCPh=CH2 + CH2O
PhCH=CHCH2CH2OH
PhCH2CH=CH2 + CH2O

62.1

650

5.21 102

163.0

160.3

26.73

2.7 1012

[19]

102.2

650

1.54 103

182.1

179.4

26.11

2.9 1012

[19]

br e = 26.42 0.44 (kJ mol1)1/2


a (kJ

mol1)1/2.

results of calculation of the MCP parameters (exp, ,


H, bre, and A0) from experimental data are presented in
Table 3. The following values of b and 0.5hNA calculated from spectral data were used for this purpose:
Bond

b 1010, kJ1/2 mol1/2 m1

0.5hNA,
kJ mol1

(in alcohol)

46.98
37.43

21.7
17.4

The degradation of alkenols, like that of alkanols, is


an endothermic process, > 0 ranges within
30.362.1 kJ mol1. It is seen that the enthalpies of degradation of alkanols and alkenols are close to one
another (see Tables 1 and 3). The exception is the aromatic alcohol PhCH=CHCH2CH2OH, its enthalpy of
degradation is = 102.2 kJ mol1. The activation
energy () of degradation of alkenols is high (ranging
from 160.3 to 179.4 kJ mol1); however, its value is
~100 kJ mol1 below that of alkanols (see Tables 1
and 3). The classical potential barrier of the thermoneutral reaction for the degradation of alkenols is likewise
lower by ~100 kJ /mol (149.0 versus 253.0 kJ mol1).
As has been already noted, the degradation of alcohols
that contain the C=C bond to the OH group follows
the concerted mechanism through the six-membered
transition state. It is obvious that the major contribution
to the reduction in the activation energy is made by the
formation of the stable, unstrained six-membered transition state as compared to the four-membered state in
the case of the degradation of alkanols; the strain energy
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of the four-membered carbon cycle is 110.4 kJ mol1 [22].


Comparing the values of bre and the value of the classical potential barrier of the thermoneutral reaction 0
for the degradation of alkenols, we can distinguish
three classes of reactions of structurally alike alcohols:
bre
(kJ
CH2=CHCH2CH2OH
CH2=CHCH2CR2OH
PhCH=CHCH2CH2OH
(CH2=CPhCH2CH2OH)

mol1)1/2

27.53 0.28
28.60 0.24
26.42 0.42

0
kJ

mol1

149.0 3.0
160.9 2.7 11.9
137.3 4.6

Substituents in the -position to the OH groups


increase the classical potential barrier of the thermoneutral reaction 0 by 11.9 kJ mol1 (steric factor). The
presence of the phenyl group at the carbon atoms of the
C=C bond leads to a reduction in the classical potential
barrier of the thermoneutral reaction 0 by 11.7 kJ mol1
(see above). It is obvious that the electrons of the phenyl ring stabilize the transition state via the mesomeric
effect and thereby reduce the energy of the potential
barrier of the thermoneutral reaction.
The values of bre calculated from the experimental
data for the degradation of alcohols of three classes
were further used for calculation of the activation
energy (Eq. (9)) and the rate constant k for a variety
of individual reactions relevant to these classes, according to Eq. (5) (0 = 2.8 1012 s1, the average from
Table 3). Along with the reactions described in the lit-

348

POKIDOVA et al.

Table 4. Calculated kinetic (E, k) and thermodynamic (H) parameters of the transition state for the degradation reactions
of alcohols ( = 1.255, He = 4.3 kJ mol1, Ee = 19.0 kJ mol1, A0 = 2.8 1012 s1)
H
Reaction

|E|

kJ mol1

k (650 K)
s1

bre = 27.53 (kJ mol1)1/2


CH2=CHCH2CH2OH

MeCH=CH2 + CH2O

61.9

168.6

2.3

1.1 102

Me2C=CH2 + CH2O

60.3

167.7

1.9

1.3 102

72.2

175.0

3.8 103

80.9

180.4

1.2 103

62.1

168.8

1.1 102

42.7

168.9

1.9

1.1 102

CH2=CMeCH2CH2OH
MeCH=CHCH2CH2OH

MeCH2CH=CH2 + CH2O

Me2C=CHCH2CH2OH

Me2CHCH=CH2 + CH2O

Me2C=CMeCH2CH2OH

Me2CHCMe=CH2 + CH2O

bre = 28.60 (kJ mol1)1/2


CH2=CHCH2CHMeOH

MeCH=CH2 + MeCHO

CH2=CHCHMeCHMeOH

MeCH=CHMe + MeCHO

39.4

166.9

1.5 102

MeCH=CHCH2CHMeOH

MeCH2CH=CH2 + MeCHO

55.5

176.5

2.6 103

58.6

178.3

1.8 103

47.7

171.9

6.1 103

54.4

175.8

MeCH=CH2 + Me2CO

30.3

161.6

Me2C=CH2 + Me2CO

27.9

160.2

5.5 102

49.2

172.7

5.2 103

Me2C=CHCH2CHMeOH

Me2CHCH=CH2 + MeCHO

Me2C=CMeCH2CHMeOH

Me2CHCMe=CH2 + MeCHO

MeCH=CHCHMeCHMeOH
CH2=CHCH2CMe2OH
CH2=CMeCH2CMe2OH
MeCH=CHCH2CMe2OH

MeCH2CH=CHMe + MeCHO

MeCH2CH=CH2 + Me2CO

2.9 103
4.23 102

2.0

bre = 26.42 (kJ mol1)1/2


CH2=CPhCH2CH2OH
PhCH=CHCH2CH2OH

MeCPh=CH2 + CH2O
PhCH2CH=CH2 + CH2O

erature, the reactions that we simulated for the degradation of other alcohols were calculated. The results of
the calculation of and rate constants k are presented
in Table 4 (the condition He min < He < He max holds in
all cases).
As is seen from Tables 3 and 4, the calculated activation energies for the degradation reaction of alkenols

62.1

157.1

3.2

9.8 102

102.2

182.4

3.0

8.4 104

agree well with the experimental values (the error ||


ranges from 3.2 to 1.9 kJ mol1).
As has been shown above, unsaturated alcohols
degrade in the gas phase (experimental data) yielding a
carbonyl compound and an alkene via the six-membered transition state. There is a question of whether the
degradation of these alcohols can yield water and an
alkane through the formation of a four-membered state.

H H
CH2=CHCH2CH2OH

CH2

CH C C H
H O

Such a degradation route has not been revealed


experimentally; however, the parameters obtained in
this study and the method of crossing parabolas make it
possible to estimate the kinetic parameters of this process. To analyze the degradation of alkenols involving
the four-membered transition state, we used the values

CH2=CHCH=CH2 + H2O.

(c)

of bre obtained earlier for the degradation of secondary


and tertiary alcohols (see Table 1). The results of the
calculation are presented in Table 5.
These results show that the degradation of alkenols
through the four-membered transition state has a very
high activation energy (244.2277.8 kJ mol1), which is
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KINETIC PARAMETERS AND GEOMETRY OF THE TRANSITION STATE

~100 kJ mol1 above that for the degradation of these


alcohols via the six-membered transition state (see
Tables 4 and 5). The rate constant of degradation
through the four-membered transition state, as we see,
is four orders of magnitude below that in the case of the
six-membered state (e.g., 2.76 106 s1 versus 1.12
102 s1 for CH2CHCH2CH2OH) (see Tables 4 and 5).
Hence, it follows that the only route of degradation of
alkenols having the structure specified above is the
decomposition that passes through the six-membered
transition state and yields an alkene and a carbonyl
compound.

349

insignificantly differ from their experimental values,


and the theoretical activation energies slightly differ
from the values obtained by the MCP (see Tables 2 and
6 and figure). The only noticeable difference is that the
MCP gives a more clearly defined reduction in the activation barrier upon the elimination of water in the presence of double bonds in the reaction products. The
quantum-chemical approaches show that the energy
barrier to the degradation through the six-membered
transition state into a carbonyl compound and an alkene
is considerably lower, approximately by 100 kJ mol1,
than the energy barrier of the decomposition through
the four-membered transition state into water and
diene. The activation energies of degradation of
alkanols through the four-membered transition state are
quite close to one another and follow this rule: the
lower the enthalpy of the reaction, the lower the activation energy. On passing to the six-membered transition
state for the degradation of ethanol by virtue of the
involvement of another water molecule, the activation
energy is substantially reduced (by ~60 kJ mol1). This
circumstance definitely allows us to discriminate both
mechanisms on the basis of the experimental activation
energy. The consistence of its value with the theoretical
data leads to the conclusion that the conditions for the
autocatalysis by degradation products (water) are not
created under the experimental conditions.

Results of Quantum-Chemical Calculation


The results of the MCP analysis of the degradation
reaction of alkenols agree well with the data of quantum-chemical calculations on the degradation of alcohols. The results of the calculation of the geometry of
transition states are presented in the figure, and the
energy parameters of the reactions are given in Table 6.
As is seen from the data in Table 6, the energy profiles based on the aforementioned structures optimized
by the CCD and B3LYP quantum-chemical methods
almost coincide if the coupled-cluster method
CCSD(T)/6-311++G** is used for the calculation of
the energy of the system. This is an indication of the
minimal differences between the CCD and B3LYP
methods in the geometry optimization results, although
these methods noticeably differ from one another in
required machine time. However, the alternative calculation by the density functional theory at the B3LYP/6311++G**//B3LYP/6-31G* level gives somewhat different results and, as a rule, underestimated activation
energies. The theoretical enthalpies of the reactions

Addition of Carbonyl Compounds to Alkenes


Reverse to the decomposition of unsaturated alcohols (b) are the reactions of the addition of carbonyl
compounds to alkenes (d), with a six-membered transition state similar to that in the degradation reactions:
R2

R1R2CHCH=CH2 + R3R4CO

R1

R1R2C=CHCH2CR3R4OH.

C H
O
C
R3

Published data on the kinetic parameters of these


reactions are lacking. We used the kinetic parameters,
obtained in this work for the degradation reactions of
alcohols (b), to calculate the parameters of some reactions of the formation of alcohols via the addition of a
carbonyl compound to an alkene (d). The degradation
reactions of unsaturated alcohols are endothermic (see
above); consequently, their formation reactions will be
exothermic; thus, Hd = Hb, and Ed = Eb Hb.
The rate constants k (650 K) for the formation reactions of alcohols were calculated by Eq. (5), as in the
case of their degradation, and the preexponential factor
0d = 2.0 106 l mol1s1 was calculated from the equilibrium constant K of the reaction
PETROLEUM CHEMISTRY

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No. 5

2009

(d)

R4

CH2=CHCH2CH2OH.
CH3CH2=CH2 + CH2O
On one hand, K = exp(S/R)exp(H/RT); on the
other hand, K = kd/kb = (Ad/Ab)exp[(Ed Eb)/RT] and
Ad = Abexp(S/R) = exp (S/R). At 650 K,
S0(CH3CH2=CH2) = 334.6 J mol1 K1, S0(CH2O) =
251.2 J mol1 K1, and S0(CH2=CHCH2CH2OH) =
461.6 J mol1 K1 [26]. The entropy change in this addition reaction is S0 = 461.6334.64251.2 =
124.2 J mol1 K1; hence, it follows that Ad/Ab =
exp(S/R) = 3.3 107 l mol1 and that Ad =
Abexp (S/R) = 6.6 1011 3.3 107 = 2.2 105 l mol1.
Since the addition reaction is a two-center reaction,
then Ad = A0d(2RT/E)1/20.5 = 2.0 106 l mol1s1 in
accordance with published data [10] and Eqs. (4) and

350

POKIDOVA et al.

Table 5. Calculated kinetic (E, k) and thermodynamic (H) parameters of the four-membered transition state for the degradation reactions of alkenols ( = 0.769, He = 5.1 kJ mol1, Ee = 14.7 kJ mol1, A0 = 5.0 1014 s1)
H

Reaction

CH2=CHCH2CH2OH
CH2=CMeCH2CH2OH
CH2=CHCH2CHMeOH
CH2=CHCH2CHMeOH
CH2=CPhCH2CH2OH
PhCH=CHCH2CH2OH
CH2=CHCH2CMe2OH
CH2=CHCH2CMe2OH

E
kJ

k (650 K)

mol1

bre = 28.14(kJ mol1)1/2


CH2=CHCH=CH2 + H2O
18.8
CH2=CMeCH=CH2 + H2O
18.9
CH2=CHCH=CHMe + H2O
22.7
CH2=CHCH2CH=CH2 + H2O
52.4
CH2=CPhCH=CH2 + H2O
21.1
PhCH=CHCH=CH2 + H2O
18.5
bre = 29.04(kJ mol1)1/2
CH2=CHCH=CMe2 + H2O
27.3
CH2=CHCH2CMe=CH2 + H2O
56.6

s1
244.3
244.4
246.1
259.2
245.4
244.2

2.8 106
2.7 106
2.0 106
2.6 107
2.3 106
2.8 106

264.5
277.8

6.3 108
7.9 109

Table 6. Results of the quantum-chemical calculation of the enthalpy and the activation energy for alcohol degradation reactions
H, E kJ mol1
H
E

Crossing

45.2
256.8

H
E
H
E

54.0
277.2

H
E

18.8
244.3

H
E

61.9
168.6

CCSD(T)/6-311++
G**//CCD/6-31G*

CCSD(T)/6-311++G**
//B3LYP/6-31G*

B3LYP/6-311++G**
//B3LYP/6-31G*

C2H5OH
CH2=CH2 + H2O
44.5
44.6
283.0
283.2
C2H5OH + H2O
CH2=CH2 + 2H2O
44.5
44.6
226.0
225.8
Me3COH
Me2C=CH2 + H2O
59.0
60.9
276.9
277.6
CH2OHCH2CH=CH2
CH2=CHCH=CH2 + H2O
23.2
25.1
271.5
271.4
CH2OHCH2CH=CH2
CH2=CHCH3 + CH2O
53.3
53.8
175.1
174.0

(6). The results of calculation of the enthalpies (H),


the activation energies (E), and the reaction rate constant for the formation of alcohols (k, 650 K) are presented in Table 7.
As is seen from the data in Table 7, the addition of
carbonyl compounds to alkenes has a high activation
energy ( = 99.5132.3 kJ mol1), with the rate constants varying from 3.8 103 to 2.3 105 l mol1 s1,
respectively. Substituents in the alkene and the carbonyl compound affect the activation energy in different
manners. With the same carbonyl compound (e.g.,
formaldehyde), the introduction of a substituent into
the alkene decreases the activation energy of the addition reaction (106.7 versus 99.5 kJ mol1, see Table 7).

41.9
260.9
41.9
191.6
38.7
245.5
8.3
243.7
39.2
149.5

As the structure of the carbonyl compound becomes


more complex, the activation energy of the addition to
propylene increases in the order formaldehyde
(106.7 kJ mol1) < acetaldehyde (126.2 kJ mol1) <
ketone (132.3 kJ mol1).
CONCLUSIONS
The method of crossing parabolas (MCP) was used
for the analysis of experimental data on the molecular
degradation of structurally different alcohols, alkanols
and alkenols. The kinetic parameters characterizing
such a degradation were calculated, and factors that
affect the activation energy of the reaction (cycle strain
PETROLEUM CHEMISTRY

Vol. 49

No. 5

2009

KINETIC PARAMETERS AND GEOMETRY OF THE TRANSITION STATE


(b) 1.327

()

110.2
(109.6)

1.815
(1.878)

H
H

1.191
(1.246)

84.3
159.7 (84.3)

102.0 (161.6)
159.7
(99.0)
(161.6)
1.790
111.3 102.2
(1.897)
(110.7) (102.4)

1.493
(1.445)

1.421
(1.419)

O H

124.0
127.8
94.4 74.0
(93.6) (74.7)

(1.299)

1.114
(1.135)

1.208
(1.252)

351

H
1.450
(1.391)

1.426
(1.419)

H
= 1874i (1588i)

= 2244i (2006i)
(c)
H

111.7
(111.4)
1.249
O
(1.302)

1.924
(2.012)

H
C

1.414
(1.364)

H
C

109.6
(109.1)
1.187
(1.236)
O

129.9 H
(132.9)
90.9
(88.9)

(d)

1.425
(1.428)

1.754
(1.801)

120.5
(124.6)
96.3
(95.6)

H
76.2
(78.3)

1.435
(1.434)

1.544
(1.483)

H
C
C
H

72.4
(73.0)

H
C
H
= 2278i (1948i)

= 2091i (1951i)
(e)
1.292
(1.292)

H
C
H
1.925
(1.919)

97.9
(98.5)

1.368
(1.374)

105.8
H
(105.7)
111.4
153.1
(112.0)
(152.5)
93.7
H
(94.0)

1.278
(1.281)

H
C

1.413
(1.415)
119.4
(119.7)
H 1.395
(1.401)

= 1554i (1157i)

Structure of the transition state for the degradation reactions of alcohols yielding olefins: (a) C2H5OH, (b) C2H5OH involving a
water molecule, (c) Me3COH, (d) CH2=CHCH2CH2OH (four-membered transition state), and (e) CH2=CHCH2CH2OH (six-membered transition state) according to the CCD/6-31G* and B3LYP/6-31G* calculation data. The bond length is give in angstroms,
the angles are in degrees, and the imaginary vibration frequencies in the transition state are in cm1. The data in the parentheses
refer to the B3LYP method.

energy, steric factor, effect of electrons) were determined. The enthalpies, the activation energies, and the
rate constants for the degradation of unsaturated alcoPETROLEUM CHEMISTRY

Vol. 49

No. 5

2009

hols via two different ways: through the six-membered


transition state to form a carbonyl compound and an
olefin and the four-membered state to yield water and

352

POKIDOVA et al.

Table 7. Calculated kinetic (E, k) and thermodynamic (H) parameters of the transition state for the formation reactions of
alcohols (A0 = 2.0 106 l mol1 s1)
H

Reaction

k (650 K)

kJ mol1

l mol1 s1

MeCH=CH2 + CH2O

CH2=CHCH2CH2OH

61.9

106.7

2.9 103

Me2C=CH2 + CH2O

CH2=CMeCH2CH2OH

60.3

107.4

5.0 103

MeCH2CH=CH2 + CH2O

MeCH=CHCH2CH2OH

72.2

102.8

4.0 103

Me2CHCH=CH2 + CH2O

Me2C=CHCH2CH2OH

80.9

99.5

3.8 103

62.1

106.7

9.6 104

42.7

126.2

7.2 105

39.4

127.5

5.5 105

Me2CHCMe=CH2 + CH2O

Me2C=CMeCH2CH2OH

MeCH=CH2 + MeCHO

CH2=CHCH2CHMeOH

MeCH=CHMe + MeCHO

CH2=CHCHMeCHMeOH

MeCH2CH=CH2 + MeCHO

MeCH=CHCH2CHMeOH

55.5

121.0

1.3 104

Me2CHCH=CH2 + MeCHO

Me2C=CHCH2CHMeOH

58.6

119.7

1.6 104

47.7

124.2

3.5 105

54.4

121.4

1.2 104

Me2CHCMe=CH2 + MeCHO
MeCH2CH=CHMe + MeCHO

Me2C=CMeCH2CHMeOH
MeCH=CHCHMeCHMeOH

MeCH=CH2 + Me2CO

CH2=CHCH2CMe2OH

30.3

131.3

2.7 105

Me2C=CH2 + Me2CO

CH2=CMeCH2CMe2OH

27.9

132.3

2.3 105

49.2

123.5

7.9 104

MeCH2CH=CH2 + Me2CO

MeCH=CHCH2CMe2OH

an olefin were compared. A quantum-chemical calculation of the transition states for five model reactions of
this type was performed; its results agree well with the
experimental data. It was shown that the degradation of
alkenols involves the six-membered transition state.
The activation energies and the rate constants for the
addition reactions of carbonyl compounds with olefins,
which are reverse to the alcohol degradation reactions,
were calculated for the first time. It was revealed that
substituents in the alkene and the carbonyl compound
have an effect on the activation energy and the rate constant of the addition reaction.
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