Académique Documents
Professionnel Documents
Culture Documents
Original Russian Text T.S. Pokidova, E.T. Denisov, A.F. Shestakov, 2009, published in Neftekhimiya, 2009, Vol. 49, No. 5, pp. 363373.
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
(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
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)
(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)
(9)
= ( 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)
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
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.
Vol. 49
No. 5
2009
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
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
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
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
R2 R3
R1
R1R2CHCR3R4OH
C C R4
H O
Vol. 49
No. 5
2009
R1R2C=CR3R4 + H2O.
()
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
|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
R2
R1R2C=CHCH2CR3R4OH
R1
R1R2CHCH=CH2 + R3R4CO,
C H
(b)
O
C
R3
R4
Vol. 49
No. 5
2009
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]
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]
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]
mol1)1/2.
0.5hNA,
kJ mol1
(in alcohol)
46.98
37.43
21.7
17.4
Vol. 49
No. 5
2009
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
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
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
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
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
H H
CH2=CHCH2CH2OH
CH2
CH C C H
H O
CH2=CHCH=CH2 + H2O.
(c)
Vol. 49
No. 5
2009
349
R1R2CHCH=CH2 + R3R4CO
R1
R1R2C=CHCH2CR3R4OH.
C H
O
C
R3
Vol. 49
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
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
41.9
260.9
41.9
191.6
38.7
245.5
8.3
243.7
39.2
149.5
Vol. 49
No. 5
2009
()
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
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.
REFERENCES
1. N. N. Semenov, Selected Works, vol. 4: Some Problems
in Chemical Kinetics and Reactivity (Nauka, Moscow,
2004) [in Russian].
2. Comprehensive Chemical Kinetics: Decomposition and
Isomerisation of Organic Compounds, Ed. by C. H. Bamford and C. F. H. Tipper (Elsevier, Amsterdam, 1972),
Vol. 5, p. 443.
3. T. S. Pokidova and E. T. Denisov, Neftekhimiya 46(2),
100 (2006) [Pet. Chem. 46, 84 (2006)].
4. T. S. Pokidova and E. T. Denisov, Khim. Fiz. 25 (6), 33
(2006).
5. E. T. Denisov, Usp. Khim. 66(10), 953 (1997).
6. E. T. Denisov, Usp. Khim. 69(2), 166 (2000).
7. E. T. Denisov, in General Aspects of the Chemistry of
Radicals, Ed. by Z. B. Alfassi (Wiley, London, 1999),
p. 79.
Vol. 49
No. 5
2009
PETROLEUM CHEMISTRY
Vol. 49
No. 5
2009
353