836 GUNTERCASPARIAND ALRRECHTGRANZOW

The Flash Photolysis of Mercaptans in Aqueous Solution

by Giinter Gaspari and Albrecht Granzow

Department of Chemistry, Boston University, Boston, Massachusetts 02216 (Received J u n e 17, 1969)

The flash photolysis of 2-mercaptoethanol, benzenethiol, and cysteine hydrochloride in deoxygenated aqueous
solutions of various pH values was studied. Transient spectra (A, -420 nm) were observed which were iden-
tified as arising from the RSSR radical anion. The transient decay was first order with approximately equal
rate constants for cysteine and 2-mercaptoethanol; the benzenethiol decayed about ten times faster, It is
proposed that the formation of RSSR from flash photolysis is via the fast reaction of the primary RS radical
with an RS- anion. The validity of the mechanism is supported by the effect of added allyl alcohol on the decay
rates of the transient.

Introduction age oscilloscope. A Vycor filter restricted the flash to

The primary reaction in the photolysis of mercaptans
in the and liquid4 phase is the formation of RS.
radicals to which has been attributed the strong absorp-
tion (A, -420 nm) observed when alkylmercaptans are
photolyzed at 2537 .& in a rigid EPA matrix.6 Similar
absorptions have resulted from the y radiolysis of
mercaptans in rigid matrices at 77’K.‘j However,
pulse radiolytic studies of cysteine7,*and 2-mercapto-
ethanole have indicated that the absorbing species is
-
not the RS radical but rather the RSSR radical anion.
There is support for this proposal from the analysis of
the esr spectra of such trapped radicals.Io
I n the radiolysis cases, the primary process is the
generation of transients fyom the attack of solvated elec-
trons or 013 radicals on the mercaptan. The question
must be raised concerning the nature of the transient
produced in the photolysis and toward this end the
flash photolysis study was directed.
Experimental Section
2-MercaptoethanoI (K & E( Laboratories), benzene-
thiol (Matheson Coleman and Bell), and allyl alcohol
(Fisher) were purified by distillation. Cysteine hydro-
chloride (Fisher, research grade) was used without
further purification.
Solutions of the mercaptans were prepared with
deionized water that had been deoxygenated by a stream
of purified nitrogen for at least 1 hr. The mercaptan
was then added with a syringe. The pH value was
adjusted using perchloric acid and sodium hydroxide
and measured with a Leeds and Northrup pH meter.
A fresh solution was used for each flash delivered.
The flash apparatus (Xenon Corp., Medford, Mass.)
delivered a flash with an energy of up to 250 J from
xenon-filled flash lamps. The flash exhibited a rise
time of 5 psec, a half-peak duration of 20 psec, and a
total duration of 50 psec. The decay of the transients
was monitored using a Hilger-Engis 0.6-m combination
spectrograph-monochromator, an RCA 1P28 photo-
multiplier and dynode chain, and a Tektronix 564 stor-
h >230 nm and a Pyrex filter in front of the analyzing
lamp was used to prevent unwanted photolysis. The
quartz irradiation vessel was 22 cm long with a 2-cm
diameter and had optically ff at quartz windows at both
ends.
The absorption spectra of the mercaptan solutions
were determined using a Cary 14 recording spectropho-
tometer.
Results and Discussion
In the spectral region X >230 nm, mercaptans show
absorption bands which are attributed to n 4 CT* or
n --t. n* transitions of the free electrons at the sulfur
atom. The ultraviolet absorption spectra of the mer-
captan solutions show that, whereas these bands are
quite strong in basic solution, no absorption occurs in
neutral or acid medium except for benzenethiol. The
spectrum of 2-mercaptoethanol in aqueous solution at
various pH values is shown in Figure 1. The spectrum of
cysteine is reported to show a similar pH dependence-l‘
In both cases the extinction coegcient at the band max-
imum is directly proportional to Ihe anion concentra-
tion as is seen by a comparison with the titration curves
of these compounds. l 1 For benzenethiol this anion
(1) 31.JIeissner and H. W. Thompson, Trans. Faraday Soc., 34, 1238
(1938).
(2) N. P. Skerret arid M. W. Thompson, ibid., 37, 81 (1941).
(3) T. Inaba and B. deB. Darwent, J . Phus. Chem., 64, 1431 (1960).
(4) W. E. FIaines, G. L. Cook, and J. S. Ball, J. Amer. Chem. Soc., 78,
5213 (1956).
(5) K. J. Rosengren, Acta Chem. Scand., 16, 1418 (1962).
(6) J. Wendenburg, W. Moeckel, A. Granzow, and A. Henglein, 2.
Naturforsch., B, 21,633 (1966).
(7) G. E, Adams, G. 8 . McNaughton, and B. D. Michael, “The
Chemistry of Ionization and Excitation,” Taylor and Francis Ltd.,
London, 1967, p 281.
(8) G. E. Adams, “Symposium on Radiation Research,” North-
Holland Publishing Co., Amsterdam, 1967, p 195.
(9) G. Meissner, A. Granzow, and A. Henglein, unpublished results.
(10) F. K. Truby, J. Chem. Phys., 40,2768 (1964).
(11) It. E. Benesch and R. Benesch, J. Amer. Chsm. Soc., 77, 5877
(1955).

T h e Journal of Physical Chemistry

FLASH
PHOTOLYSIS IN AQUEOUSSOLUTION
OF MERCAPTANS 837

d
0

Cnml
Figure 1. The uv absorption spectra of aqueous solutions of
2-mercaptoethanol: [mercaptan] = 2.0 X 10-4 M ; cell path
length = 1 cm; pH of solutions: 1, 13.0; 2, 10.5;
3, 9.7; 4, 9.0; 5, 6.0.
x Cnml
Figure 2. The uv absorption spectra of aqueous solutions of
benzenethiol: [mercaptan] = 1.25 X 10-4 M ; cell path length
= 1 cm; pH of solutions: 1, 5.9; 2, 6.6; 3, 8.9; 4, 12.5.

Table I: Rate Constants for the Decay of R$SR Radical

Anion Transient Spectra
band is shifted to about 260 nm, but at low pH values
another absorption at 235 nm is observed which is due Compound Concn, M PH k , sec-1 Amax, nm
to the undissociated form (Figure 23.
2-Mercapto-
In all three systems strongly absorbing transients are ethanol 1.0 x 10-3 12.2 4 . 9 x 103 420
observed after the flash. The absorption maxima are Cysteine 1 . 0 x lo-* 8.1 2 . 7 x lo8 420
a t 420 nm for 2-mercaptoethanol and cysteine and a t Benzenethiol 5.0 x lo-' 10.6 3 . 8 X lo4 470
470 nm for benzenethiol. The spectra of the transients
in Figure 3 are measured a t those pH values where the
highest intensity of the transient absorption is obtained. of methanol or acetone has no effect on the intensity
If the solutions are flash photolyzed without the Vycor or decay constant of the transient absorption. On the
filter so that X <230 nm radiation is also absorbed, other hand, the transient spectra are not observed in the
no noticeable change in the shape or the intensity of presence of oxygen.
the transient bands is observed. This fact suggests that When allyl alcohol is added, the intensity of the
only the long wavelength absorption band of the mer- transient absorption decreases and the decay constants
captans is responsible for the formation of the transients. increase proportionally with the concentration of the
In the case of cysteine and 2-mercaptoethanol the alcohols. From the slope of these straight lines the
wavelengths of the transient absorption maxima are second-order rate constants for the reaction of the
identical with those observed in pulse radiolytic stud- transients with allyl alcohol can be calculated (Table
ies'+' and are accordingly attributed to the correspond- 11). In the case of benzenethiol the decay constant is
ing R$SR radical anions. Nothing has yet been re already so large that any additional enhancement in the
ported on the transient arising from benzenethiol, but presence of allyl alcohol cannot be determined.
it is doubtless due to the formation of the analogous
CeH&SCeHs radical anion. The higher intensity and
the bathochromic shift of the transient absorption for Table 11: Rate Constants for the Reaction of Transient RSSR
this compound are readily explained by the influence of Radical Anions with Allyl Alcohol. Concentration of the
the benzene rings. Mercaptans, 1.0 X 10-3 M
The decay of the transients is first order; the rates are Compound Concn range, M pH k, M-1 mc-1
about the same for cysteine and 2-mercaptoethanol,
whereas the benzenethiol transient decays more rapidly. 2-Mercaptoethanol 1-20 x 10-3 12.2 1 . 0x 106

The rate constants are listed in Table I. The addition

Cysteine 2-15 x 10-3 8.1 1.4 x 106

Volume 74,Number 4 February 19, 1970

838 GUNTERCASPARIAND ALBRECHT
GRANZOW

I I I I I I I 1
0.3 t
a

I I

b
d
0
1

O0.I ' * V

I I I I I I I 1 1 I I I I I
360 400 440 480 520 560 4 6 6 IO 12 14
Wavelength [nm] PH
Figure 3. Absorption spectra of transients: (a) cysteine, 1.0 x Figure 4. pH dependence of the transient absorption: (a)
10-3 M ; pH 8.7; (b) 2-mercaptoethanol, 5.0 X 10-3 M, cysteine, 1.0 X M , X 420 nm; (b) 2-mercaptoethanol,
pII 10.5; (c) benzenethiol, 5.0 X IO-' M ; pH 11.8. 5.0 X 10-8 M, X 420 nm; (c) benzenethiol,
5.0 X 10-4 M ; X 470 nm.

Since the intensity and wavelength of the uv absorp-

tion of the mercaptan solutions show a strong depen-
dence on the pH, the effect of pH on the transient
absorption was examined (Figure 4). For cysteine and
2-mercaptoethanol, no transient absorption is observed
in acid and neutral solution because in this pH range,
these two compounds do not show substantial uv ab-
sorption at X >230 nm. On the other hand, the un-
dissociated benzenethiol has an absorption maximum
a t 235 nm. Therefore, in this case, the absorbing tran-
sient is also formed in acidic solution and the intensity
of the transient absorption increases with increasing
pH, reaching a constant value at pH -8.5. In all cases
the decay constants of the transients do not show a
noticeable dependence on the mercaptan concentration
or the pH of the solution.
For mercaptoethanol, the intensity of the transient
absorption decreases again at pH >12. It appears
that the formation of the absorbing RSSR radical anion
is inhibited by high OH- concentrations. As in the case
of the pulse radiolysis experiments,O a weak transient
absorption with a maximum at A <300 nm is observed
in solutions of pH >12. This short wavelength tran-
sient absorption may be tentatively attributed to the
RS. radical, since mercaptan radicals in the gas phase
are known to absorb in this region.12 The fact that
this transient is only observed in solutions at high pH
can be explained in terms of the inhibition of the radical
anion formation in a strongly basic medium. This
should result in an enhanced lifetime for the primary
-
RS radicals.
In the case of cysteine, the intensity of the transient
absorption has a distinct maximum at pH -8.5. This
behavior can be explained in terms of the different
steps in the dissociation of cysteine. In the pH range
8-10, cysteine exists mostly as a mixture of HSCH2-
CH(NH2)COO- and S-CH2CH(NHs+)COO-, whereas
at higher pH the doubly negativeS-CH2CH(NH2)COO-
anion if f0rmed.l' Therefore, in this latter pH region
the formation of the absorbing RSgR radical anion
would have to take place via the reaction of two par-
ticles, each of which carries two negative charges.
Since a reaction of that kind is energetically unfavorable,
this may account for the observed decrease of the
transient formation at high pH.
(12) R.G. W. Norrish and A. P. Zeelenberg, Proc. Roy. Soc. (London),
A240,293 (1967).

T h e Journal of Physical Chemistry

 PHOTOLYSIS
FLASH OF MERCAPTANS SOLUTION
IN AQUEOUS
The reaction mechanism which leads to the forma-
tion of the absorbing RSSR transients may be assumed
to be similar to the one established for the formation
of the same species by pulse r a d i o l y ~ i s . ~ - ~The
~ ' ~first
-
step is the formation of a RS radical by photodetach-
ment of an electron from a RS- anion. In the case of
benzenethiol, a photodissociation of the neutral mer-
captan must also be considered if the transient is pro-
duced in neutral or acidic solution
RS-+ hv (230-270 nm) +RS. + e- (1)
RSH + hv (230-270 nm) +RS. + Ha (2)
The uv absorption bands of the mercaptan solutions in
the region of 230-270 nm correspond to the energy of
105-125 kcal mol-'. The dissociation energies of al-
kylmercaptans in the gas phase have been determined
to about 88 kcal mol-' l 4 making reactions 1 and 2 ener-
getically feasible and leaving enough excess energy
available to account for differences in solvation ener-
gies.
The second step is the fast reaction of a primary
RS . radical with a RS- anion forming the RSSR radical
anion that is responsible for the observed transient
absorption. The decay of the transient complex prob-
ably takes place by reaction 3 with the stable end prod-
uct being mainly the corresponding disulfide
RgSR F! RS + RS- +products (3)
839
The equilibrium position in reaction 3 has to be far to
the left to account for the first-order decay kinetics.
The structure of the RSSR species is expected to be
similar to that of the dihalide radical anion, such as
ci2-.7
The validity of this two-step mechanism is supported
by the effect of added allyl alcohol on the decay con-
stants of the radical anions. It is well established that
RS . radicals are efficiently scavenged by compounds
with olefinic double bonds, the addition leading to the
formation of an anti-Markovnikov product. 15*l6 There-
fore, the addition of allyl alcohol shifts the equilibrium
of reaction 3 to the right, in agreement with the observed
enhancement of the decay constants. The much faster
decay of the b'enzenethiol transient as compared to the
aliphatic mercaptans can also be understood by a shift
of the equilibrium.to the right due to the higher st%
bility of the aromatic thieyl radical.
Acknowledgment. The authors wish to thank Pro-
fessor M. Z. Hoffman for his interest in this work.
The flash photolysis apparatus was purchased with
funds from NSF Grant GP 7048.
(13) W.Karmann, G.Meissner, and A. Henglein, 2. Nuturforsch. B ,
22,273 (1967).
(14) J. L. Franklin and H. E. Lumpkin, J.Amer. Chem. Soc., 7 4 , 1023
(1952).
(15) M. S. Kharash, A. T. Read, and F. R. Mayo, Chem. Ind.
(London), 51,752 (1938).
(16) R.H.Pallen and C. Sivertz, Can. J . Chem., 35, 723 (1957).
Volume 74, Number 4 February 19, 1970