62 V . A . Fo~rr~ et a/.

of Organosulphur Compounds Contained in Oils and Oil Products). 8, Vyshchaya

shkola, Moscow, 1968
9. U.S.A. Pat. 3206465; 1965. RZhKhim., 22N68P, 1966
10. R. D. OBOLENTSEV, S. S. KRIVOLAPOV, T. L ALLILUYEVA, G. V. GALEYEVA,
V. S. NIKITINA, R. P. KANAYEVA and N. N. LYUSHINA, Sb. I~ihimiya seroorga-
nicheskikh soyedinenii, soderzhashchikhsya v neftyakh i nefteproduktakh, 8, Vys-
shaya shkola, Moscow, 1968
11. R. V. HOPKINS and H. M. SM.ITH, Analyt. Chem. 26, 206, 1954
12. R.D. OBOLENTSEV, Ye. A. MAKOVA, A. I. VOROB'YEVA and F. Sh. IBRAGIMOVA,
Neftekhimiya 1O, 584, 1970
13. R. D. OBOLENTSEV, N. K. LYAPINA, V. S. NIKITINA and M. A. PARFENOVA,
Neftekhimiya 11, 125, 1970
14. V. S. NIKITINA, N. K. LYAPINA and A. D. ULENDEYEVA, Ncftekhimiya 1O, 594,
1970
15. D. E. HIRSCH, R. L. HOPKINS, H. S. COLEMAN, F. O. COTTON and C. J. THOMP-
SON, Analyt. Chem. 5, 915, 1972
16. N. P. VOLYNSKII and I. K. CHUDAKOVA, Zavodsk. lab., :No. 21, 1435, 1955
17. I. A. RUBINSHTEIN, V. A. KLEIMENOVA and Ye. P. SOBOLEV, Sb. Metody
analiza organicheskikh soyedinenii nefti, ihk smesei i proizvodnykh (Methods of
Analysis of Organic Compounds of Petroleum, their Mixtures and Derivatives).
1, Izd. AN SSSR, Moscow, 1960
18. F. D. GAL'PERN, G. P. GIRINA and V. G. LUK'YANITSA, Ibid. 58
19. A. A. POLYAKOVA, Molckulyarnyi mass-spektrometricheskii analiz neftei (Molecular
Mass-Spectrometric Analysis of Petroleums) l~edra, Moscow, 1973

Petrol. Chem.U.S.S.R. Vol. 18. pp. 62-68. 0031-6458/78/0301-0062507.5010

~) PergamonPress Ltd. 1979.Printed in Poland

REACTIVITY OF SODIUM MERCAPTIDES DURING OXIDATION

IN THE PRESENCE OF COBALT DISULPHOPHTHALOCYANIN*
V. A. FoM~, A. M. MAZGAROVand N. N. LEBEDEV
All-Union Scientific Research Institute of Hydrocarbon Raw Material
(Received 18 February 1977)

MERCAPTANS f o r m t h e m a i n p a r t o f o r g a n o s u l p h u r c o m p o u n d s in light h y d r o -
c a r b o n fractions. L i g h t f r a c t i o n s o f O r e n b u r g g a s - c o n d e n s a t e s c o n t a i n a b o u t
1 % wt. m e r c a p t a n sulphur, which is r e p r e s e n t e d b y lower a l i p h a t i c m e r c a p t a n s
o f b o t h n o r m a l a n d i s o m e r s t r u c t u r e [1]. T h e presence of m e r c a p t a n s in oil
p r o d u c t s explains to a large e x t e n t t h e i r corrosive a c t i v i t y , u n p l e a s a n t o d o u r
a n d low s t a b i h t y . T h e m o s t effective m e t h o d o f freeing light h y d r o c a r b o n
f r a c t i o n s f r o m m e r c a p t a n s is b y e x t r a c t i o n of m e r c a p t a n s w i t h a n alkaline
s o l u t i o n a n d s u b s e q u e n t r e c o v e r y f r o m alkali b y o x i d a t i o n o f m e r c a p t i d e s

* Neftekhimiya 18, No. 2, 298-303, 1978.

 l~oactivi~y of sodium mercaptides during oxidation 63

with atmospheric oxygen in the presence of catalysts--metal phthaloeyanin

of variable valency [2]. The study of the reactivity of aliphatic mercaptans by
catalytic oxidation with oxygen in alkaline medium is therefore of consider-
able interest.
A study was made [3] of the reactivity of mercaptans during radiation
oxidation and it was concluded that with an increase in molecular weight
the rate of oxidation decreases. The limiting stage of this process is the forma-
tion of a thiyl radical by the reaction
hv
RSH ~I~S'+tt'.
The same order of reactivity of mercaptans was observed by authors of
another study [4] during oxidation of mercaptans with oxygen in the presence
of sulphur dyes. The limiting stage in this process is, apparently, the solution-
of mercaptans in the alkaline phase to form mercaptides.
Authors examined non-catalytic oxidation of mercaptans in an alkaline
medium according to oxygen absorption and showed that the reactivity of
mercaptans decreases in the order

n-CsHTSH >n-C4HpSH>n-CsHllSH,
which is, apparently, due to oxygen consumption of secondary reactions.
that take place during oxidation of low molecular weight mercaptans. Results
of the reactivity of mercaptides in catalytic oxidation with molecular oxygen,
are absent from the literature.
This study is concerned with the reactivity of aliphatic sodium mereap-
tides during oxidation with molecular oxygen in the presence of cobalt disul-
phophthalocyanin.

EXPERIMENTAL METHODS

Sodium mercaptides were oxidized in a dilute solution of sodium hydroxide

with commercial oxygen at atmospheric pressure in a device used for batch
processes. The reactor was a cylindrical glass vessel, provided with a tubular
stirrer, diffuser, sampler, reflux condenser, deflecting plates and contact
thermometer connected with an electron relay. The reactor was heated with
a nichrome spiral and temperature controlled with an accuracy of ~0.5 °.
All experiments were carried out under the following conditions: stirrer speed
2000 rev/min, oxygen feed rate 300 ml/min, temperature 30 °, concentration,
mole/l: RSNa--0.36, catalyst 1.110 × 10 -6.
Oxidation takes place in the kinetic range under these conditions. Chemi-
cMly pure sodium hydroxide, technical sodium salt of cobalt disulphophthalo-
cyanin were used for the experiments. Methyl mercaptan, isobutyl-, secondary
butyl- and tertiary butyl mercaptans were synthesized by methods previously
described [6]. Other mercaptans were used as ready pure reagents. All m e r -
~4 V.A. FOMIN et al.

captans were purific4 by two-fold distillation over a column at atmospheric

pressure. Physical and chemical constants of mercaptans used in experiments
show satisfactory agreement with results in the literature [7]. It was estab-
lished using a "Tsvet-4" gas-liquid chromatograph that all mercaptans are
individual substances.
Mercaptide solutions were prepared by mixing corresponding mercaptans
with 10% dilute solution of sodium hydroxide in a flask provided with a
mechanical stirrer. Preliminary experiments verified the conversion of mer-
captans to mercaptides, n-Amyl mercaptan (92.7%) and n-butylmercaptan
(98.7%) have the lowest degree of conversion. Consequently, all mercaptans
used under experimental conditions were in the form of sodium mercaptides.
~The catalyst (cobalt disulphophthalocyanin) was previously dissolved in
distilled water for the experiments. Blending of mercaptide and catalyst
solutions and heating of the reaction mass to a given temperature were carried
out in argon. The reaction was studied by the concentration variation of
,sodium mercaptides, determined by potentiometric titration in a pH-340
.device by methods previously used [8].
RESULTS

Table 1 shows the concentration variation of sodium n-propylmercaptide

~over a period of time and effective reaction rate constants, calculated from
t h e formula of a first order reaction rate constant by the method of short
,intervals [9].
The stability of reaction rate constants over a period of time proves a first
,order reaction for sodium mercaptide.
Table 2 shows effective rate constants of oxidation of aliphatic sodium
mercaptides and the constants of substituents. The effective rate constant
was calculated as the arithmetic mean of three parallel experiments; the
relative error of determining effective constants varied between 1 and 8%.
Table 2 shows that the reactivity of aliphatic normal mercaptides increases
with an increase of molecular weight in the following sequence:
CHsSNa<CzHsSNa<n-CsHvSNa<n-C4HpSNa<CsHnSNa,
which agrees with a number of ~liphatic induction constants (Tuft) a* of
corresponding substitimnts (Table 2). However, attempts to correlate the
rate constant of all mercaptides studied with constants a* appeared unsuccess-
ful. It was only for a group of mercaptides consisting of normal mercaptides
from ethyl to n-amylmercaptide and for isobutyl mercaptide that the rate
constant showed satisfactory correlation with induction constants. A typical
feature of mercaptides of this group is the fact that sulphur in them is com-
bined with a carbon atom containing two a-hydrogen atoms. Another group
is formed by ~sopropyl- and sec-butylmercaptides containing an a-hydrogen
.atom and as shown by Table 2, having reduced rate constants in spite of the
 R e a c t i v i t y of sodium m e r c a p t i d e s during oxidation 65

high Tuft constants (a*). Tert-butylmercaptide free from a-hydrogen atoms

altogether has an even lower rate constant. It should be noted that methyhner-
captide containing three a-hydrogen atoms has an increased rate constant.

TABLE 1. EFFECTIV~ l~A~m COlVSTAI~rS OF OXlDATtOlV OF SODIII~ n - P R O I ~ Y L ~ E R C ~ m

vs, C,, ks× 104, vf, Us, ks× 104, zs, Us, ks× 104,
see molefl, scc -1 see molcfl, see -1 see molofl, see -1

0 0.3946 -- 1620 0.2697 2.21 3240 0-1862 2.23

600 0.3424 2.37 2160 0.2392 2.23 3780 0.1629 2.47
1095 0-3027 2.48 2700 0.2100 2.40

The reactivity of mercaptides therefore depends on the number of a-hydrogen

atoms, which is evidence of the h3Ter-conjugation effect of a-hydrogen atoms
of alkyl groups. Using an equation of the type
k
log~0=p*a*+h(n--3)

bearing in mind the Tuft induction constants and constants (n--3) expressing
the effect of hyper-conjugation, gives a satisfactory correlation (Figure, a).
In this case p*=--17.84, h =1.91 and the equation takes the form
k
logic =--17.84 a*+1.91 (n--3),

where n is the number of a-hydrogen atoms in a given substituent, no= 3, the

number of a-hydrogen atoms in a standard (methyl) substituent. Correlation
coefficient (R) is 0.961, standard deviation (so) being 0.133. Parameters of
the ~quation were calculated from formulae of multiple regression [10].
Table 2 shows that in a series of mercaptides containing two a-hydrogen
atoms, isobutyl mercaptide somewhat disrupts the correlation between the
T A B L E 2. E F F E O T I V ~ R A T E C O N S T A N T S OF O X I D A T I O l g OF S O D I U M M E R C A P T I D E S (RSNa)
A N D C O N S T A N T S OF S U B S T I T U E I ~ T S

Hypor-con-
Tuft
Substituents
kerr X 1 0 -'t,
SOC- I
log induction
constants
jugation
constants
Steric
constants
(sD
(n--3)

- - CHs 0-9064-0.0091 0 0.000 0 0"00

1.0204-0.016 0.0516 0.100 --I --0.38
n-C3H, 2-3004-0.19 0-4046 --0.115 --1 --0"67
n-C4H, 4.5004-0.36 0.6960 --0.130 --I --0"70
n-CsHll 11-7004-0-50 1.1109 --0.162 --1 --0.71
--iso-C4H, 2-2004-0.13 0.3852 --0-125 --I -- 1.24
-- iso-C3H, 0.7004-0.015 --0.1121 --0-190 --2 --1.08
--sec,-O~H, 0.7404-0-037 --0.0879 --0.210 -- 1"74
--tert.-O4H~ 0.4504-0.022 --0-3039 --0.330 --3 --2"46
66 V.A. Fo~aw ~ a/.

reactivity of mercaptides and the Tuft induction constants of substituents.

The reduced rate constant for isobutyl mercaptide is explained b y the con-
siderable steric effect of the substituent, compared with other mercaptides
of this group. Consequently, to achieve a better correlation between the reac-
tion rate constant and effects of substituents, it is essential to calculate not

I-~'- a mc~, j

o~ - "-oc*"

04/- C_H_ ~,~ ~ Lso-CqHgLso-CqHg R= 0"96f

0 ~o-CjH 7 ~ C H a $o=0"133
o ",:,~ °~-C+Hs
....~o t~.~C019 , I I Z t l
-0"q -0"2 O 0"2 0"Z~ 0"6 0"8 I'0
-17"8#0"*+1"9f(n-3,)
[orj k/ko
1.2 b /~.-~H,,

,¢~rte~t.r C4HJ I I I I I I
-~-ez o ~z ~# o.6 o~ t.o
-t ~ az ~ * + t. za(n-a )+ OOaE]
Ralation between log k/ko and Tuft induction constants and hyper-conjugation con-
stants (a) and Tuft induction constants, hyper.conjugation constants and steric con-
stants (b).

only the induct.ion and hyper-conjugation interaction of the reaction centre

with the substituent, but also their steric interaction. Attempts to use an equa-
ion of the type

which incorporates steric constants of Tuft substituents Es, were unsuccessful.

Constant Es reflects the steric and hyper-conjugation effects of substituents
at the same time, but the hyper-conjugation effect is only reflected partially.
The use of the equation in the general form
]~ $ $ c
l o g ~ = p a -kh(n--3).-k6B~, (1)

in which induction, hyper-conjugation and sterie effects were considered

appropriately, increases the correlation coefficient to 0.982. (Fig. b), where:
 Reactivity of sodium mercaptides during oxidation 67
E~ is the steric constant of the substituent, free from the hyper-conjugation
effect of ~-hydrogen atoms (Table 2).
The general correlation equation therefore takes the form

l o g ~ = - - 1 9 . 3 2 a*~1.78 (n--3)-~-0.33 Esc ;

R-----0.982, s0-=0.092. (2)

The negative sign of the reaction constant p* indicates that oxidation is
accelerated with an increase in the electron-donor properties of the substituent.
Since electron-donor substituents increas8 electron density in the reaction
centre, negative sign p* denotes aucleopl~ilic (in relation to reagent RSSTa)
reaction in the limiting stage. The high absolute value of the reaction constant
indicates a high degree of polarity of the transitional state of the stage, which
is most difficult energywise and determines process rate, in which ions take
part directly. The positive sign of the hyper-conjugation reaction constant h
denotes an acceleration of oxidation on increasing hyper-conjugation of
a-hydrogen atoms. Since a-hydrogen atoms increase electron density in the
reaction centre (apparently, as a result of the formation of an overall orbitaI
with overlapping the ls atomic orbit of hydrogen and the free 3d orbital of
the sulphur atom), positive sign h denotes the nucleophilic reaction in the
limiting stage. The positive sign of the steric reaction constant 5 denotes t h a t
oxidation slows down with an increase in steric hindrances of the substituent
to the approach of the substratum to the reaction centre of the reagent.
Results agree with the well-known anion-radical mechanism of catalytic
oxidation of thiols in an alkaline solution [11] and suggest that the nucleo-
philic attack of the mercaptide anion on the phthalocyanin metal cation is
the limiting stage in catalytic oxidation of aliphatie mereaptides.
The reactivity of aliphatic mercaptides is therefore determined mainly
by the induction and hyper-eonjugation effects of substituents. I f we consider
the steric structure of the mereaptide molecule, it becomes clear that reac-
tivity also depends on steric effects of substituents. A general correlation
equation [12] enables us to calculate fairly accurately the reactivity of mer-
captides with corresponding constants of substituents.
As indicated, natural hydrocarbons contain mercaptans of both normal
and isomer structure. Oxidation of a mercaptide mixture is therefore of
practical interest. We studied the joint oxidation of n-butyl- and sec-butyl-
mereaptides of sodium with oxygen at a temperature of 30°, catalyst con-
centration of 1-110 × 10 -s mole/1., [RSNa]-~ 0.18 mole/1, of each mercaptide.
During the experiment samples were taken, in which the overall concentration
of mercaptides was determined. Effective rate constants of the reaction were
calculated for given time intervals and are given below:
~, sec 310 600 900 1250 1510 1800 2105
k × 1 0 t , sec -1 2-63 2-24 2.90 2.71 2.46 2.31 2.41
68 V.A. Fo~ et al.

I t follows f r o m t h e v a l u e s g i v e n t h a t ~ffective r a t e c o n s t a n t s are close t o

t h e c o n s t a n t c a l c u l a t e d as t h e a r i t h m e t i c m e a n o f effective const~,uts o f
i n d i v i d u a l m e r c a p t i d e s . C o n s e q u e n t l y , in a m i x t u r e m e r c a p t i d e s u n d e r g o
o x i d a t i o n in parallel a n d i n d e p e n d e n t l y .
SUMMARY

1. A s t u d y w a s m a d e o f t h e r e a c t i v i t y of a l i p h a t i o s o d i u m m e r c a p t i d e s
in o x i d a t i o n in t h e p r e s e n c e of c o b a l t d i s u l p h o p h t h a l o c y a n i n . A m o n g m e r -
e a p t i d e s o f n o r m a l s t r u c t u r e r e a c t i v i t y increases w i t h a n increase in m o l e c -
ular weight
Ctt3SNa<C2HsSNa<n-CattTSNa<n-C~HgSNa<n-CsttllSNa .

F o r m e r c a p t i d e s w i t h t h e s a m e m o l e c u l a r w e i g h t r e a c t i v i t y decreases w i t h
an increase of structural branching
n - C 4 H g S N a > i s o -C4ItgSNa > s e c - C 4 t I g S N a > t e r t - C~HgSNa.

2. T h e r e a c t i v i t y of a l i p h a t i c m e r c a p t i d e s is d e t e r m i n e d m a i n l y b y t h e
i n d u c t i o n a n d h y p e r - c o n j u g a t i o n effects o f s u b s t i t u e n t s ; t h e steric effect o f
• s u b s t i t u e n t s is negligible.
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