Reactivity of the CH-bonds of 2-butanol in liquid-phase oxidation

Article abstract of DOI:10.1134/S003602441712024X

The kinetics of product accumulation is studied in the azodiisobutyronitrile-initiated oxidation of 2-butanol. The relative reactivity for all types of the CH-bonds of 2-butanol is determined for reactions with peroxyl radicals at 60°C. It is established that the hydroxyl functional group of 2-butanol activates the CHbond in position 2 (α) and deactivates CH-bonds in positions 1, 3 (β), and 4 (γ), compared to the corresponding CH-bonds of saturated hydrocarbons.

Full text of DOI:10.1134/S003602441712024X

ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2017, Vol. 91, No. 12, pp. 2337–2343. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © S.V. Puchkov, Yu.V. Nepomnyashchikh, 2017, published in Zhurnal Fizicheskoi Khimii, 2017, Vol. 91, No. 12, pp. 2050–2056.
CHEMICAL KINETICS
AND CATALYSIS
Reactivity of the CH-Bonds of 2-Butanol in Liquid-Phase Oxidation
S. V. Puchkov* and Yu. V. Nepomnyashchikh
Kuzbass State Technical University, Institute of Chemical and Oil and Gas Technologies, Kemerovo, 650000 Russia
*
e-mail: psv.toos@kuzstu.ru
Received January 25, 2017
Abstract—The kinetics of product accumulation is studied in the azodiisobutyronitrile-initiated oxidation of
2
-butanol. The relative reactivity for all types of the CH-bonds of 2-butanol is determined for reactions with
peroxyl radicals at 60°C. It is established that the hydroxyl functional group of 2-butanol activates the CH-
bond in position 2 (α) and deactivates CH-bonds in positions 1, 3 (β), and 4 (γ), compared to the correspond-
ing CH-bonds of saturated hydrocarbons.
Keywords: liquid-phase oxidation, 2-butanol, reactivity
DOI: 10.1134/S003602441712024X
INTRODUCTION
The aim of this work was to study the reactivity of
CH-bonds in 2-butanol and the paths of product for-
Oxygen-containing derivatives of saturated hydro- mation during its liquid-phase oxidation.
carbons are widely used as additives for motor fuels.
They both raise the octane number and reduce the
EXPERIMENTAL
High-purity grade 2-butanol was purified accord-
toxicity of automobile exhaust [1–3]. Among the var-
ious oxygen-containing compounds used as motor
fuel components, the ones most interesting are butyl ing to the procedure in [12] by successively treating
2-butanol with sodium bisulfite solution, boiling it
alcohols: 1-butanol, 2-butanol, and 2-methyl-1-pro-
panol (isobutyl alcohol), which are obtained (apart
from other sources) from renewable raw materials [4].
Compared to the widely used ethanol, the use of butyl
alcohols has several advantages: low hygroscopicity,
the ease of mixing it with gasoline, and an energy den-
sity similar to that of gasoline. A mixture of gasoline
and butanol is less prone to stratification than a mix-
ture of gasoline and ethanol; in addition, butyl alco-
hols have low corrosion activity [5, 6].
with 10% sodium hydroxide solution, and washing it
with water and hydrochloric acid. The washed alcohol
was dried over lime and then boiled three times with
fresh portions of lime. Finally, the alcohol was sub-
jected to fractional distillation (b. p. 98°C; according
to [13], the b. p. is 98.5°C). The purity of the resulting
preparation was no less than 99.9 ± 0.1%. According
to gas–liquid chromatography (GLC), the purified
2
-butanol contained no oxidation products. 1,2-
butanediol was synthesized by bubbling 1-butene
through a dilute solution of potassium permanganate
The increasing need for butyl alcohols as components
for motor fuels demands deep study of their oxidation
during operation and storage, and on the environmental
effects of the products of their oxidative conversions. It is
therefore seems relevant to investigate the composition
and paths of the formation of the products of 1-butanol,
[
14]. 1-Butene was obtained via the vapor-phase
dehydration of 1-butanol on Al O at 400°С [15]. Azo-
2
3
diisobutyronitrile (AIBN) was purified by recrystalli-
zation from ethanol to the desired purity.
GLC was used for quantitative determination of the
oxidation products. Determination was performed on
a Tsvet-800 chromatograph equipped with a plasma
2
-butanol, and 2-methyl-1-propanol oxidation.
The aspects studied most extensively are those of the ionization detector and a 30-m long ZB-WAX capil-
oxidative transformations of 1-butanol and isobutyl lary column, the internal diameter of which was 0.32
alcohol [5–11]. Particular scientific attention is now mm. The phase was 0.5 μm thick. High-purity argon
being given to 2-butanol because, while it has the same was used as the carrier gas. The sample was introduced
energy density as other isomeric butyl alcohols, its in the split mode at split ratio of 1 : 20. 1,4-Butanediol
octane number is the highest [7, 8]. However, works was used as an internal standard.
devoted studying the reactivity of 2-butanol in reactions
of oxidation and the directions of its oxidative transfor- determined after treatment with a 100% molar excess
mations are scarce and mostly of a theoretical nature. of a triphenylphosphine (TPP) solution in benzene.
2-Hydroperoxy-2-butanol and 2-butanone were
2337

2338
PUCHKOV, NEPOMNYASHCHIKH
1
,2-Butanediol; 2,3(R,R and/or S,S)-butanediol;
R C(OH)OOH ꢀ H O + R C=O,
(VII)
2
2
2
2
2
,3-butanediol (meso form); and 1,3-butanediol were
determined after treatment with a 100% molar excess
of a TPP solution in benzene. Isomeric butanediols
were identified by comparing their retention times
with those of pure substances, and by comparing the
order of their release to that of their release from simi-
lar columns [16, 17]. The concentrations of isomeric
butanediols in the samples of oxidized 2-butanol were
•
k
6.1
2R C(OH)OO ⎯⎯⎯
⎫
(VIII)
(IX)
(X)
2
⎪
⎪
molecular
products.
•
2
k
6.2
2
HO ⎯⎯⎯
⎬
⎪
•
•
2
k
6.3
R C(OH)OO + HO ⎯⎯⎯
⎪
⎭
2
−5
−6
low (~10 –10 mol/L), so the samples were concen-
trated under vacuum prior to GLC analysis.
According to this scheme, two type of radicals,
•
2
•
R C(OH)OO and HO , participate in chain growth
2
reactions; the oxidation of alcohols proceeds as a two-
The rate of the AIBN-initiated (0.01 M AIBN) oxi-
dation of 2-butanol by molecular oxygen was mea-
sured in the kinetic region of oxygen uptake at 60°C on
a manometric unit, the basic design of which is
described in [18, 19]. Samples of 2-butanol oxidized
under these conditions were used to study the compo-
sition of the products.
center chain process [22, 23]. Under these conditions,
rate w of radical-chain oxidation is described by the
ν
equation [22, 23]
gr
•
w
= (k2.1[R
C(OH)OO ]
ν
2
(3)
gr
2
•
2
+
k [HO ])[R CHOH],
.2
2
Equation [20] was used in calculating the rate of
initiation with AIBN:
gr
gr
in which k и k are the gross rate constants of chain
2
.1
2.2
continuation reactions (V) and (VI) with the partici-
•
w = 2ekd,AIBN[AIBN].
(1)
•
pation of radicals R C(OH)OO and HO , respec-
2
2
i
tively. The relationship between the concentrations of
Coefficient e of the withdrawal of radicals from the
•
2
•
the two types of radicals, R C(OH)OO and HO ,
can be expressed by the equation
solvent cell was taken to be 0.6 [21]. The rate constant
2
for the gross decay of the initiator (k
) was deter-
d, AIBN
mined using the equation [20]
•
2
•
[HO ] [R C(OH)OO ] = a.
(4)
2
logkd,AIBN =15.0 −126.2 (kJ/mol) 2.303RT . (2)
If the equilibrium in reaction (IV) succeeds in estab-
lishing itself, a = k k [R C = O] [22, 23]. Other-
1
−1
2
wise, a = k k [R CHOH] [24].
RESULTS AND DISCUSSION
1
2.2
2
From Eqs. (3) and (4), it follows that
The AIBN-induced radical-chain oxidation of
2
-butanol (R CHOH) can be represented by the
2
gr
gr
2.2
•
w = (k + ak )[R C(OH)OO ][R CHOH]. (5)
ν
2.1
2
2
scheme of transformations
According to the above scheme, the rate of chain ter-
mination is expressed by the equation
(
CH ) (CN)CN=NC(CN)(CH )
3 2 3 2
w
i
•
+2O
•
2
⎯
⎯ 2(CH ) (CN)C ⎯ ⎯⎯2(CH ) (CN)COO ,
3 2 3 2
•
2
w = 2k [R C(OH)OO ]
t
6.1
2
(
I)
(6)
•
2
•
•
2
+
2k [HO ] + 2k [R C(OH)OO ][HO ].
6
.2
2
6.3
2
•
(
CH ) (CN)COO + R CHOH
3 2 2
Using (4), we obtain
(
II)
•
⎯
R COH + (CH ) (CN)COOH,
2
•
2
2
3 2
w = 2(k + a k + ak6.3)[R C(OH)OO ]
t
6.1
6.2
2
(7)
•
• 2
•
= 2k6,eff [R C(OH)OO ] .
2
R COH + O ⎯ R C(OH)OO ,
(III)
(IV)
2
2
2
Under the conditions of a quasi-stationary regime
when w = w , Eq. (5) can be presented as
•
k1
•
2
ꢀ
ꢀꢁ
ꢂꢀꢀ
k−1
R C(OH)OO
R C=O HO ,
+
i
t
2
2
gr
gr
−0.5
0.5
w = (k + ak )(2k
)
[R CHOH](w )
2 i
•
ν
2.1
gr
2.2
6,eff
−0.5
R C(OH)OO + R CHOH
(8)
2
2
0.5
(
V)
= k2,eff (2k6,eff
)
[R
2
CHOH](w
i
) .
•
k2.1
⎯
⎯⎯ R C(OH)OOH + R COH,
2
2
In light of the correction for nonchain release and the
uptake of gases, rate w of radical-chain oxidation
HO + R CHOH ⎯ ⎯⎯ H O + R COH, (VI) under the conditions of the AIBN-initiated oxidation
•
ν
•
2
k
2.2
2
2
2
2
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REACTIVITY OF THE CH-BONDS OF 2-BUTANOL IN LIQUID-PHASE OXIDATION
2339
(12)
gr
−0.5
of 2-butanol is related to rate wO2 of oxygen uptake by
the equation [20]
k2 (2k6,eff
)
,eff
−0.5
α
,eff
β2
,eff
β1
−0.5
−0.5
=
k2 (2k6,eff
)
+ 3k (2k6,eff
)
2,eff
gr
−0.5
0.5
wO2 = k (2k6,eff
)
[R CHOH](w )
−0.5
γ
2,eff
2
i
(9)
+ 2k2 (2k6,eff
)
+ 3k (2k6,eff
)
,
2,eff
+
(3 2 −1 2e)wi.
while the rate of radical-chain oxidation can be pre-
sented as the sum of the partial rates:
When several types of CH-bonds are present in a mol-
ecule of an oxydated organic compound, the gross rate
constant of chain-growth reactions can be presented
as the sum of the partial rate constants for the detach-
ment of hydrogen atoms at different positions of the
substrate by peroxyl radicals, allowing for the number
of each type of the CH-bonds [25, 26].
A molecule of 2-butanol contains one α-СН bond,
five β-СН bonds (three primary β1 and two secondary
β2 bonds), and three primary γ-СН bonds:
α
ν
β1
ν
β2
ν
γ
w = w + 3w + 2w + 3w .
(13)
ν
ν
The relative reactivity of CH-bonds in reactions with
•
2
•
peroxyl radicals R C(OH)OO and HO can in this
2
case be estimated from the ratio of the partial rates of
radical-chain oxidation:
α
γ
α
2,eff
γ
3
wν w = 3k
k
,
(14)
(15)
(16)
(17)
ν
2,eff
β1
α
β2
γ
β1
γ
ν
β1
γ
CH −CH(OH)−CH
2
−CH3.
3
wν w = k
k
,
2,eff
2,eff
gr
gr
2.2
Consequently, k , k can be presented as
β2
γ
ν
β2
2,eff
γ
2
.1
3
wν 2w = 3k
2k
,
2,eff
gr
α
2.1
β1
β2
γ
2.1
k2 = k + 3k + 2k + 3k ,
(10)
(11)
.1
2.1
2.1
γ
γ
γ
γ
wν w = k
k
= 1.
2,eff
ν
2,eff
gr
.2
α
2.2
β1
β2
γ
2.2
k2 = k + 3k + 2k + 3k
,
2.2
2.2
To determine the partial rates of radical-chain oxida-
α
β1
2.1
β2
2.1
γ
2.1
α
2.2
β1
β2
2.2
γ
where k , k , k , k , k , k , k , and k are tion, we studied the kinetics of the accumulation of
2
.1
2.2
2.2
the partial rate constants for the reaction of between products by all types of CH-bonds in the AIBN
•
2
induced (0.01 mol/L AIBN) oxidation of 2-butanol at
•
R C(OH)OO (index 2.1) and HO (index 2.2) radi-
2
6
0°C. The main organic products in the oxidation of
cals and the respective CH-bonds of 2-butanol. In
light of (10) and (11), oxidation parameter
secondary alcohols by α-СН bonds are ketone and
α-hydroxyhydroperoxide [24, 27]. The oxidation of
gr
−0.5
k2 (2k
)
6,eff
(Eq. (8)) can be presented as the sum 2-butanol by the α-CH bond yields 2-butanone and
,eff
of the partial parameters of oxidizability:
2-hydroperoxy-2-butanol:
OO
O
RO2; O2
CH3 CH CH2 CH3
OH
CH3 C CH2 CH3
OH
CH3 C CH2 CH3
−ROOH
−HO2
−H O
2
2
(XI)
OOH
CH3 C CH2 CH3
OH
+RH
+RH
HO2
H O
2 2
−R
−R
2
,4-Dihydroperoxy-2-butanol can form at the same time as a result of intermolecular chain transfer [28]; under
the reducing action of triphenylphosphine (TPP), it transforms into 4-hydroxy-2-butanone:
O
OO
O
C
H
CH2
OOH
CH3 C CH2 CH2
OH
CH3 C CH2 CH3
OH
CH3
HO CH2
(
XII)
OOH
CH3 C CH2 CH2
OH OOH
O2; RH
[H]
CH3 C CH2 CH2
OH
−R
O
The latter was not found among the oxidation products erization (XII) to the total rate of conversion of the
of 2-butanol. It is likely that under the experimental α-hydroxyalkylperoxyl radical through three competing
conditions, the contribution from intramolecular isom- reactions—(IV), (V), and (XII)—is negligible.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 91 No. 12 2017

2340
PUCHKOV, NEPOMNYASHCHIKH
The composition and kinetics of the accumulation of γ-СН bonds [29, 30] suggest that the oxidation of 2-buta-
the products in the 2-butanol oxidation by β- and γ-СН nol by β- and γ-СН bonds would yield isomeric hydroxy-
bonds have barely been studied. The data on the compo- hydroperoxides, which would then be transformed into
sition of the products of cyclohexanol oxidation by β- and isomeric butanedioles under the reducing action of TPP:
[
H]
CH3 CH CH2 CH2
OH OOH
CH3 CH CH2 CH2
OH OH
+
RO2; + O2
RH
[H]
CH3 CH CH2 CH3
CH3 CH CH CH3
OH OOH
CH3 CH CH CH3
OH OH
(XIII)
+
OH
[H]
CH2 CH CH2 CH3
OOH OH
CH2 CH CH2 CH3
OH OH
It should be noted that the oxidation of 2-butanol by (ν ≈ 13), so the rates of product accumulation for the
secondary β-СН bonds (β2) adjacent to the asymmet- chain termination reactions accounted for no more
ric carbon atom could lead to the formation of a mixture than 5% of the total rate of product accumulation.
of stereoisomers: 3(R)-hydroperoxy-2(R)-butanol, This value is within the experimental error.
3
(S)-hydroperoxy-2(S)-butanol,
3(R)-hydroperoxy-
No 3-hydroxy-2-butanone and 2- and 3-hydroxy-
butanals were detected, due possibly to their extremely
low concentrations, which are beyond the scope of
GLC determination.
2
(S)-butanol, and 3(S)-hydroperoxy-2(R)-butanol.
Their reduction would in turn lead to the formation of
a mixture of 2,3(R,R and/or S,S)-butanediols and
2,3-butanediol (meso form).
After reduction, samples with TPP, 2-butanone,
Under the conditions of the AIBN-induced oxida- 1,2- and 1,3-butanediols, 2,3(R,R and/or S,S)-
tion of 2-butanol, the formation of isomeric 1,2-, 1,3-, butanediol, and 2,3-butanediol (meso) were indeed
and 2,3-butanediols and the corresponding carbonyl found among the products of 2-butanol oxidation.
compounds (2- and 3-hydroxybutanals and The kinetic curves for the accumulation of the prod-
3
-hydroxy-2-butanone) can occur according to the ucts of 2-butanone oxidation by all types of CH-bonds
reactions of the recombination of peroxyl radicals are given in Fig. 1, along with the oxygen uptake curve.
(
(VIII)–(X)) [28]. Oxidation of 2-butanol under the The results from an analysis of these curves are pre-
experimental conditions involved rather long chains sented in Table 1. It follows from Fig. 1 that there is a
linear dependence between the concentrations of the
analyzed products of 2-butanol oxidation and the
duration of oxidation. This indicates that under the
0
.10
.05
0.10
0.05
experimental conditions, these products formed via
competing parallel reactions of constant rates.
The rates of 2,3(R,R and/or S,S)-butanediol and
,3-butanediol (meso) accumulation are similar. This
2
4
2
is probably due to the reaction in which the hydrogen
atom in position 3 of 2-butanol is detached by a per-
oxyl radical. The reaction proceeds via a carbon-cen-
tered radical with a planar structure, or via a radical
with a pyramidal structure in which inversion of the
structure occurs rapidly [31].
3
1
0
5
gr
−0.5
The oxidizability of 2-butanol, k2 (2k6,eff
)
(see
,eff
6
Table 1), calculated from rate wO2 of oxygen uptake
using Eq. (9), is in good agreement with the corre-
sponding value given in [24, 28]. As is well known, the
oxidizability and the rate constants for elementary
reactions in the oxidation of alcohols depend on the
concentration of the substrate, since solvation effects
lower the reactivities of the alcohol and peroxyl radi-
cals in the reactions of chain growth and chain termi-
nation [28]. For example, in the oxidation of cyclo-
hexanol [26], oxidizability falls as the alcohol concen-
tration rises to 0.4 mol/L, after which oxidizability
5
10
τ, h
Fig. 1. Kinetic curves of (1) oxygen uptake and the accu-
mulation of products: (2) butanone, (3) 1,3-butanediol,
(
4) 2,3(R,R and/or S,S)-butanediol, (5) 2,3-butanediol
meso form), and (6) 1,2-butanediol during the AIBN-ini-
(
tiated (0.01 M AIBN) oxidation of 2-butanol with oxygen
at 60°C.
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REACTIVITY OF THE CH-BONDS OF 2-BUTANOL IN LIQUID-PHASE OXIDATION
2341
Table 1. Kinetic parameters and partial rates (mol /(L s)) of oxidation of 2-butanol by different types of CH bonds at 60°C,
[
RH] = 10.9 mol/L, and [AIBN] = 0.01 mol/L
gr
−0.5
× 104,
Type of Numberof
СН bonds СН bonds
wν × 108
wO2 × 106 wν × 106
2.54 2.42
k2,eff (2k6,eff )
Π
mol/(L s)
α
1
3
2
2-Butanol
231
5.1
β1
β2
1,2-Butanediol
2,3-Butanediol
0.65
0.88
0.74
1.62
2
,3-Butanediol (meso form)
γ
3
1,3-Butanediol
1.62
Π is the product of the corresponding position; w denotes the partial rates of product accumulation.
ν
remains almost constant. The obtained kinetic pat- its primary ε-СН bonds by a factor of 11.5; according
terns can therefore be expected to remain constant in a to [33], this ratio is 18. The reactivity of the secondary
fairly wide range of 2-butanol concentration.
CH-bond of 2,2-dimethylbutane in the reaction with
Using the obtained partial rates of the product the t-butylperoxyl radical is 25 times higher than the
accumulation in the oxidation of 2-butanol by all of its reactivity of its primary CH bonds in the reaction with
CH-bonds (Table 1), we used Eqs. (14)–(17) to calcu- the same peroxyl radical [34]. The drop in the reactiv-
late the relative reactivities of α-, β1-, β2-, and γ-СН ity of the β2-CH bond of 2-butanol can be explained
bonds in alcohol; these were 427.7, 0.4, 1.5, and 1, by the deactivating effect of the hydroxyl group. The
respectively.
reactivity of the α-CH bond of 2-butanol is 427 times
It follows from the data that the reactivity of a pri- higher than the reactivity of the γ-CH bond and 285
mary γ-СН bond is 2.5 times that of a secondary β1- times higher than the reactivity of the β2-CH bond of
СН bond, while CH-bonds of the same type in satu- alcohol. The activating effect of the hydroxyl group on
rated hydrocarbons have the same reactivity. This the α-CH bond was also observed in the oxidation of
probably indicates that a hydroxyl group has a deacti- cyclohexanol [29, 30].
vating effect on the nearest β1-СН bonds.
The dissociation energy is known to have a signifi-
The deactivating effect of the electron-acceptor
cant effect on the activation energy in radical detach-
hydroxyl group of cyclohexanol in the reaction with
ment reactions and, consequently, on the reactivity of
electrophilic peroxyl radicals is known to affect not
CH bonds [20, 28, 35]. To clarify the nature of the
effect the hydroxyl group has on the reactivity of CH
bonds in 2-butanol during reactions with peroxyl rad-
icals, dissociation energies were calculated for all types
of CH-bonds in the alcohol. The calculations were
only the nearest β-СН bonds but also γ-СН bonds
[
29, 30], so the reactivity of the γ-CH bonds of 2-buta-
nol could be expected to fall. However, this is not
obvious from the obtained results. The reactivity of the
secondary β2-CH bond of 2-butanol is only 1.5 times
higher than the reactivity of its primary γ-CH bond. In performed using isodesmic reactions (IDRs) [36]. To
contrast, the reactivity of secondary δ-CH bonds of calculate the energy of dissociation for all types of the
the acyl fragment of methylcapronate in the reactions CH bonds in 2-butanol, formal isodesmic reactions
with tert-butylperoxyl radical exceeds the reactivity of were obtained using IDRs:
•
•
CH CH CH(OH)CH + CH C(OH)CH ⎯ CH CH C(OH)CH + CH CH(OH)CH ,
(XIV)
(XV)
3
2
3
3
3
3
2
3
3
3
•
•
CH CH CH(OH)CH + CH CH(OH)CH ⎯ CH CH CH(OH)CH + CH CH(OH)CH ,
3
2
3
3
2
3
2
2
3
3
•
•
CH CH CH(OH)CH + CH CHCH (OH) ⎯ CH CHCH(OH)CH + CH CH CH (OH),
(XVI)
3
2
3
3
2
3
3
3
2
2
•
•
CH CH CH(OH)CH + CH CH CH (OH) ⎯ CH CH CH(OH)CH + CH CH CH (OH). (XVII)
3
2
3
2
2
2
2
2
3
3
2
2
The enthalpies of these reactions are equal to the dif- pound. The bond strengths in the reference com-
ference between the strengths of the corresponding pounds were determined using the G3MP2B3
CH bonds in 2-butanol and in the reference com- approach [36], while the thermal effects of IDRs were
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 91 No. 12 2017

2
342
PUCHKOV, NEPOMNYASHCHIKH
6. P. Ghiaci, J. Norbeck, and C. Larsson, PloS One 9 (7)
calculated using the CBS-QB3 approach [37]. The
calculated energies of dissociation for the α-, β1-, β2-,
and γ-СН bonds of alcohol were 386.7, 429.1, 419.6,
and 426.3 kJ/mol, respectively. The energy of dissoci-
ation of the α-СН bond in 2-butanol (386.7 kJ/mol)
was close to the energy of dissociation of the α-СН
bond in 2-propanol, which is 380.7 kJ/mol [38].
(
2014). doi 10.1371/journal.pone.0102774
7
8
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The values of the energy of bond dissociation, cal-
culated using IDRs, are in good agreement with those
of the dissociation of the CH bonds in 2-butanol, cal-
culated using the CBS-QB3 approach and presented
1
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in [37], kJ/mol: α-СН bonds, 395.8; β1-СН bonds, 11. J. Zhang, L. Wei, X. Man, et al., Energy Fuel. 26, 3368
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4
28.8; β2-СН bonds, 421.3; γ-СН bonds, 426. A com-
parison of the energies of dissociation for the α-, β1-,
β2-, and γ-CH bonds in 2-butanol, calculated using
IDRs, and the energies of dissociation for the respec-
tive CH bonds in butane [38] (primary CH bond,
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2. A. Weissberg, E. Proskauer, J. Riddick, and E. Toops,
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421.3 kJ/mol; secondary СН bond, 411.1 kJ/mol)
showed that the α-СН bond of 2-butanol is much
weaker than the secondary СН bond of butane. Its
reactivity in radical detachments reactions is thus
higher than that of the secondary CH bonds of satu-
rated carbons. The strength of the β1-, β2-, and γ-CH
1
4. E. I. Buneeva, S. V. Puchkov, and E. G. Gumbris, in
Proceedings of the 10th International Conference on
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bonds in the alcohol proved to be greater than that of 15. H. Becker, W. Berger, and G. Domschke, Organikum
the corresponding CH bonds in butane, indicating a
drop in the reactivity of these CH bonds. Based on the
results obtained in this work, we may assume the con-
siderable activation of the α-CH bond of 2-butanol
and the deactivation not only of its β1- and β2-СН
bonds, the ones closest to the hydroxyl group, but also
of the more distant γ-CH bonds.
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A similar effect of the hydroxyl group on the reac-
tivity of CH bonds in the reactions with peroxyl radi-
cals was observed in cyclohexanol. It was attributed to
the combined effect of three factors: the electron den-
sity at the hydrogen atom of the attacked CH bond;
the stabilization degree of the transition state; the sta-
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19. L. R. Yakupova, S. G. Proskuryakov, and R. N. Zari-
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