Electrochemical Reactivity of Strong Sulfuric Acid:

Some Unusual Behavior at Pt Electrodes

B. E. Conway* and D. M. Novak *,1
Chemistry Depart~zent, University oS Ottawa, Ottawa, Ontario, Canada K I N 6N5

ABSTRACT
In v e r y strong, 98%, sulfuric acid c y c l i c - v o l t a m m e t r y e x p e r i m e n t s at P t
r e v e a l u n u s u a l r e d u c t i o n a n d o x i d a t i o n processes as distinct f r o m those as-
sociated w i t h electrodeposition a n d ionization of atomic H, and surface oxide
f o r m a t i o n a n d reduction, w h i c h are f a m i l i a r in d i l u t e aqueous solutions of
I.I2SO~ at Pt. No r e d u c t i o n processes are o b s e r v e d on a less e l e c t r o c a t a l y t i c
metal, Au, u n d e r the s a m e conditions. H o l d i n g the p o t e n t i a l of a P t elec-
trode n e a r the HH+/H2 p o t e n t i a l ( E H ) in 98% H2SO4 gives rise to r e d u c t i o n of
the acid, p r o d u c i n g a species t h a t is i m m e d i a t e l y c h e m i s o r b e d a n d becomes
oxidized in the a d s o r b e d state in a following anodic p o t e n t i a l sweep over the
"surface oxide f o r m a t i o n " Potential region. In the succeeding cathodic sweep,
a l a r g e cathodic c u r r e n t p e a k follows surface oxide reduction. By m e a n s of
chemical s i m u l a t i o n e x p e r i m e n t s , it is shown t h a t the r e d u c t i o n b e h a v i o r is
accounted for first b y f o r m a t i o n of SO2 or H S O s - at potentials n e a r EH, fol-
l o w e d b y oxidation to a species, possibly a d s o r b e d d i t h i o n a t e ($2062-), or
some o t h e r chemisorbed s u l f u r - o x y g e n species, in a following anodic sweep.
This o x i d a t i o n process cannot be from SO2 or I-ISO3- b a c k to H2SO4 or H S O 4 -
since, in the n e x t cathodic sweep, a r e - r e d u c t i o n occurs in a w e l l - d e f l n e d peak,
a l i t t l e positive to EH. E x p e r i m e n t s at a r o t a t e d P t d i s k electrode e n a b l e dis-
tinctions to be m a d e b e t w e e n processes associated w i t h s t r o n g l y b o u n d c h e m i -
sorbed species a n d o t h e r species t h a t can be spun off into solution, giving
d i m i n i s h e d c u r r e n t s in successive cyclic v o l t a m m o g r a m s . A d d i t i o n s of s m a l l
quantities of w a t e r diminish the r e d u c t i o n r e a c t i o n o b s e r v e d in 98% HHaSO4.

In the course of e x p e r i m e n t s (1) on the surface o x i -
d a t i o n of P t in nonaqueous m e d i a containing traces
of w a t e r , we i n v e s t i g a t e d the b e h a v i o r of P t electrodes
in v e r y strong 98% sulfuric acid. Some u n u s u a l and
interesting b u l k and surface electrochemical processes
a r e f o u n d w h i c h a r e not o b s e r v e d in o r d i n a r y aqueous
solutions of I.I2SO4. A t the 98% level of concentration
of H2SO4, the m e d i u m is essentially a nonaqueous so-
l u t i o n w i t h H30 + a n d H S O ~ - ions as the e l e c t r o l y t e
at about 1.1M concentration. Some higher, condensed
sulfuric acid species, e.g., I'i28207, a r e also p r e s e n t in
traces (2).
Studies in v e r y strong acid m e d i a are of i n t e r e s t in
f u e l - c e l l technology w h e r e acids such as H3PO4 a n d
CF~SO3H a r e used a t ca. 85% concentrations, often at
elevated temperatures.
As far as we a r e aware, no previous studies of the
electrochemical surface r e a c t i v i t y of p u r e H2SO~ to
give chemisorbed decomposition products at electrode
interfaces have been r e p o r t e d except in the w o r k of
A r v i a et al. (3) who i n v e s t i g a t e d electrochemical s u r -
face processes at I r in 96% H2SO4. In this work, h o w -
ever, only the usual surface reactions of I r a r e r e -
v e a l e d w i t h H a d s o r p t i o n a n d surface oxide f o r m a t i o n
regions being observed in the n o r m a l way, b u t w i t h
d i s p l a c e m e n t of these two processes to m o r e n e g a t i v e
and m o r e positive potentials, respectively, due to
H S O 4 - ion adsorption, as is k n o w n in m o r e dilute so-
lutions at P t w i t h SO42- (4) and I.ISO4- ion (5), d e -
p e n d i n g on concentration and pH.
A n i n t e r e s t i n g s t u d y was also m a d e b y A r v i a et aL
(6) on the e l e c t r o c h e m i s t r y of f u m i n g sulfuric acid
containing various concentrations of SOs a n d s m a l l
quantities of SO~, a n d c o m p a r a t i v e l y on 97.4% H2SO4
in the same paper. Most of this w o r k was concerned
with the steady-state current-potential behavior arls-
ing from r e d u c t i o n of SOs at s t a t i o n a r y and r o t a t e d
P t electrodes, which gives rise to SO2 and some S.
* Electrochemical Society Active Member.
Present address: Research Laboratories, Eldorado Nuclear Lim-
ited, T u n n e y ' s Pasture, Ottawa, Canada.
Also, the cathodic evolution of H2 and the anodic de-
composition to 02 and p e r s u l f u r i c acid was i n v e s t i -
gated. The question of adw species t h a t m i g h t be
involved in the reactions was not t r e a t e d in this work,
I n w o r k b y L a l et al. (7-10) a n d b y Lou~ka (11-13),
however, a d s o r b e d species f r o m SO2 solutions a n d S
l a y e r s f o r m e d f r o m I.I2S and SO2 w e r e recognized and
investigated. As we discuss later, some of these results
a r e r e l e v a n t to the i n t e r p r e t a t i o n of the e x p e r i m e n t s
in the p r e s e n t work.
A r v i a et aI., in a series of p a p e r s (14), have also
r e p o r t e d u n d e r p o t e n t i a l deposition of H a n d surface
o x i d a t i o n of P t a n d I r in KHSO4 a n d NaI-ISO4/KHSO4
melts.
I n the p r e s e n t paper, w e r e p o r t some u n u s u a l r e -
duction and o x i d a t i o n processes at P t in 98% HH2SO4
at o r d i n a r y t e m p e r a t u r e s , s t u d i e d b y m e a n s of the
l i n e a r p o t e n t i o d y n a m i c sweep m e t h o d a n d r e l a t e d p r o -
cedures. A t t e m p t s to i d e n t i f y the p r i n c i p a l i n t e r m e d i -
ates i n v o l v e d w e r e m a d e b y means of chemical s i m u -
l a t i o n e x p e r i m e n t s using l i k e l y species such as SO2,
dithionite, and dithionate.
Experimental
Method.--A conventional s y s t e m for a p p l y i n g single
and r e p e t i t i v e l i n e a r p o t e n t i a l sweeps to an electrode
was used, e m p l o y i n g the e q u i p m e n t and p r o c e d u r e
r e f e r r e d to in previous p u b l i c a t i o n s (5, 15, 16). I n
the c y c l i c - v o l t a m m e t r y mode, the system enables a
series of sweeps in an anodic or cathodic direction to
be m a d e to successively m o r e positive or m o r e n e g a -
tive potentials, respectively, using the t r i g g e r i n g ca-
p a b i l i t y for sweep r e v e r s a l at a constant sweep r a t e
which is p r o v i d e d b y a S e r v o m e x L F 141 function
g e n e r a t o r o p e r a t i n g on a W e n k i n g potentiostat. This
system also allows the p o t e n t i a l to be h e l d conveni-
e n t l y at a controlled fixed value ( p o t e n t i a l "holding"
e x p e r i m e n t ) for r e c o r d e d times before a following
anodic or cathodic sweep is initiated. This t y p e of a p -
p a r a t u s enabled c u r r e n t - d e n s i t y (i) vs. p o t e n t i a l (V)
profiles to be recorded, as described p r e v i o u s l y b y us

2262
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 VoI. 128, No. 11 H~SO4 REACTIVITY 2263

(1, 5, 16) and by other authors, e.g., Ref. (15). Most reversal and in constant potential holding experiments
experiments were conducted at 298 K at a Pt disk (see below).
electrode (Pine Instrument Company) that could be ( i ) Cyclic-voltammetry at 70 m V sec- Z.--Cyclic-
rotated when desired. Some comparative experiments voltammetry experiments were first made by means of
were made at a high p u r i t y grade Au wire. a repetitive symmetrical triangular sweep, referred to
H2SO~ electrolyte:--B.D.H. Aristar pure ( 9 8 % ) as program (i) (Fig. 1). Several potential limits to
H~SO4 was used as the electrolyte, initially without the cathodic and anodic sweeps were employed and
dilution. This is the acid which gives, at ordinary con- are defined on the experimental i vs. V profiles shown
centrations (0.5 ,-, 1M), the best clean aqueous solu- in Fig. 2a and b and Fig. 3a and b. Experiments in this
tion of H2SO4 for cyclic-voltammetry experiments at mode established the normal i vs. V profiles for the
Pt, as we have described in earlier papers (5, 16). In surface processes at Pt in 98% H~SO4, as shown in Fig.
some experiments, where controlled small additions of 2 and 3.
water are made, pyrodistilled water (16) was used. (ii) Cyclic-voltammetry experiments over progres-
Cell.--A small 3-compartment cell capable of being sively decreasing ranges of potentiaL--These were
fitted to a rotating disk electrode system was used, as made by reversing the sweep at successively increas-
described previously (1). It was provided with a com-
partment in which either a reversible HMH+ electrode
or an (~ + ~)PdH electrode was situated.
Reference electrodes.--A platinized-Pt hydrogen
electrode was employed as the reference electrode di-
rectly in the strong H2SO4. In the 98% HeSO4, the
potentials are not true reversible potentials but rather
steady mixed potentials due to the slow electrocata-
lytic reduction reaction involving HeSO4 which is the
subject of this paper. Very satisfactorily steady poten-
tials (-+- < 1 mV) could, however, be maintained
over an hour or so. In some experiments the (a +
~)PdH reference electrode was used. Potentials on
all graphs to be shown below are on the scale of the
He/H + electrode in the same solution as that in which
the working Pt or Au (see below) electrodes were
studied. This scale is designated for convenience by
EH.
Potential programs.--The potential-time programs
shown in Fig. 1 were applied to the working Pt elec-
trode in 98% H2SO4 in order to investigate the nature
of the observed electrochemical reactivity of H2SO4
and to distinguish the currents from those arising in
the normal w a y [cf. (5, 15, 16)] from underpotential Fig. 2. (a) Cyclic-voltammetry i vs. V profiles for Pt in 98%
deposition of H, or OH and O species; the potentials H2SO4 at 70 mV sec -1 at 298 K, [program (i)]. Deslgnations of
employed were adjusted on the function generator principal anodic and cathodic processes are shown. (b) As in Fig. 2
and the potentiostat and read with an accuracy of (a) but with holding the potential constant at the positive end of
1 mV on a high impedance digital millivoltmeter. At the anodic sweep giving rise to growth of the surface oxide at Pt
all times, the latter instrument was used to monitor (70 mV sec -z, 298 K). Curves 1 to 9 for ~t~,a = 0, 5, 10, 15, 20,
numerically the various potentials involved at sweep 60, 120, 240, and 360 sec.

+ 1,22 v

program (i)
V
~ -0.23 V

o,v
Vorious limits
.p
"\ A "
of V (0) (b)

V Fig. 3. (a) Cyclic-voltammetry i vs. V profiles for Pt in 98%

H2SO4 at 70 mV sec -1 at 298 K showing the effects of reversing
- - "-0.22 V ~- . . . . J - 0,22 V
(a) r " , c (b) the direction of potential sweep at successively more positive
potentials in the anodic sweep direction [program (lib)]. (b) As in
t t Fig. 3 (a), but showing the effects of reversing the direction of
potential sweep at successively less positive potentlals in the
Fig. i. Potential programs cathodic sweep direction [program (iia)].
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 2264 J. E l e e t r o e h e m . Soc.: E L E C T R O C H E M I C A L
ing potentials in the anodic or successively decreasing
potentials in the cathodic sweep directions. These p r o -
cedures are i l l u s t r a t e d in Fig. 1 and a r e r e f e r r e d to as
p r o g r a m s (iib) a n d (iia), respectively. These p r o -
cedures give i n f o r m a t i o n on w h a t processes o b s e r v e d
in, e.g., a cathodic sweep ( w h e r e a c u r r e n t p e a k arises)
are conjugate to processes in the p r i o r anodic sweep,
o r vice-versa, as shown in Fig. 3a a n d b. The changing
p o t e n t i a l limits in the p r o g r a m s (iia) a n d (lib) a r e
e v i d e n t f r o m the p o t e n t i a l s of r e v e r s a l of the series
of curves shown in Fig. 3a, b.
(iii) Potential holding e x p e r i m e n t s . w H o l d i n g the p o -
t e n t i a l at e i t h e r the end of an anodic sweep for a time
~h,a [ p r o g r a m (ilia) ] or at the end of a cathodic sweep
for a time, ~h,c [ p r o g r a m ( i i i b ) ] followed b y initiation
of a f u r t h e r cathodic or anodic sweep, respectively,
e n a b l e d the f o r m a t i o n a n d r e a c t i v i t y of products of
slow processes to be followed. It was in these e x p e r i -
ments, w i t h .cathodic h o l d i n g of t h e p o t e n t i a l n e a r
(--0.2V EH) the s t e a d y - s t a t e h y d r o g e n electrode p o -
tential (see a b o v e ) , t h a t the u n u s u a l r e a c t i v i t y of
H2SO4 was observed. The potentials at which cathodic
or anodic holding for times ~n was m a i n t a i n e d a r e
shown l a t e r in the respective figures.
A f t e r each change of conditions, e.g., p o t e n t i a l h o l d -
ing, the electrode was allowed to r e t u r n to the r e p r o -
ducible state g e n e r a t e d i n i t i a l l y as in section (i)
above b y r e p e t i t i v e a n o d i c / c a t h o d i c cycling [ p r o g r a m
( i ) ] u n t i l the initial i vs. V curve, corresponding to
the c y c l i c - v o l t a m m e t r y profile shown in Fig. 2, was
recovered. This i vs. V profile, u n d e r continuous c y -
cling, was e x a c t l y r e p r o d u c i b l e f r o m one e x p e r i m e n t to
a n o t h e r and b e t w e e n different P t electrodes w i t h n o r -
malization to the same r e a l area. It was also v i r t u a l l y
identical w i t h the initial anodic a n d cathodic i vs. V
profile o b s e r v e d w h e n an electrode, p r e c y c l e d in 1M
aq H~SO4, w a s t r a n s f e r r e d to the 98% H~SO4.
Real electrode area.--The real a r e a of the disk P t
electrode used in most of the e x p e r i m e n t s was d e t e r -
mined, in the usual way, f r o m the charge for d e s o r p -
tion of the u n d e r p o t e n t i a l deposited H l a y e r m e a s u r e d
s e p a r a t e l y in 0.05m aq H2SO4, using the figure 2.10 C
m - 2 for the H m o n o l a y e r at P t [cf. (17)]. A f t e r sev-
e r a l days' e x p e r i m e n t s in the 98% H2SO4, the r e a l a r e a
of the electrode d e t e r m i n e d b y the H a c c o m m o d a t i o n
r e m a i n e d u n c h a n g e d w i t h i n 0.5%.
E x p e r i m e n t s at A u . - - I n o r d e r to establish h o w spe-
cific the o b s e r v e d H2SO4 r e d u c t i o n was to Pt, c o m p a r a -
tive e x p e r i m e n t s w e r e c a r r i e d out on a noble m e t a l
less e l e c t r o c a t a l y t i c t h a n Pt, viz., Au.
Reflectance e x p e r i m e n t s . ~ I n o r d e r to see if c h e m i -
sorbed i n t e r m e d i a t e species which arise, as shown later,
in the r e d u c t i o n of H2SO4 can be distinguished from
other, e.g., surface oxide, species on the electrode,
r e l a t i v e reflectivities ( h R / R ) w e r e m e a s u r e d in t h e
tl
c y c l i c - v o l t a m m e t r y e x p e r i m e n t s using the a p p a r a t u s
and p r o c e d u r e s p r e v i o u s l y described (18).
Results and Discussion
Phenomenology of the ef]ects.--CycZic-voltamme~ry
and potential-holding experiments: programs (i) and
(iii) . - - T h e u n u s u a l electrochemical r e a c t i v i t y of H~SO4
at P t arises in the cathodic holding e x p e r i m e n t s , (iiib).
However, it is first n e c e s s a r y to show the n o r m a l b e -
havior of a P t electrode in 98% H2SO4 u n d e r condi-
tions w h e r e the u n u s u a l reactions either do not t a k e
place significantly in the time scale of an a n o d i c / c a t h -
odic sweep at 25 mV sec -1 or at all, if the p o t e n t i a l
r a n g e in the sweep is a d j u s t e d a p p r o p r i a t e l y .
F i g u r e 2a shows the i vs. V profiles for a P t elec-
trode in 98% H2SO4 over the p o t e n t i a l r a n g e --0.244 to
~- 1.210V EH and w i t h cycling over successively d i -
m i n i s h e d ranges of p o t e n t i a l in the anodic (Fig. 3a)
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SCIENCE AND TECHNOLOGY November i98I
or cathodic (Fig. 3b) sweeps. These figures define
the general b e h a v i o r of P t in the 98% H2SO4 w i t h o u t
a n y f u r t h e r a d d e d water. Characteristic regions of
the i vs. V profile are designated b y Ia, IIa, Ic, IIc, etc.,
where "a" and "c" denote anodic a n d cathodic p r o -
cesses, respectively.
U n d e r the above conditions, the o b s e r v e d currents
a r e p r e d o m i n a n t l y for surface processes since the r e -
duced c u r r e n t densities, i/s, ( viz., the a p p a r e n t p s e u d o -
capacitance p e r unit a r e a ) are almost constant w i t h
changing sweep rate, s, a f t e r a given holding period,
Th,c.
The i vs. V profiles for P t in 98% H~SO4 u n d e r the
conditions of Fig. 2 and 3 differ s u b s t a n t i a l l y from
those w e l l k n o w n (5, 15, 16) for P t in dilute (~0.05M)
aqueous H2SO4. Principally, no region of u n d e r p o t e n -
tial deposition of H is seen, i.e., before H2 is evolved at
the most negative end of a cathodic p o t e n t i a l sweep.
This is p r e s u m a b l y due to strong adsorption of H~SO4
molecules and H S O 4 - ions and to the changed n a t u r e
of the solvent. The regions Is, IIa (Fig. 2a) of the
anodic sweep, which are p r e s u m a b l y a t t r i b u t a b l e in
the usnal w a y to surface o x i d a t i o n (since, e.g., the
charge in the r e d u c t i o n p e a k increases l o g a r i t h m i -
cally w i t h time of holding at the positive end of the
anodie sweep and the hysteresis b e t w e e n f o r m a t i o n
and r e d u c t i o n regions increases w i t h time of anodic
h o l d i n g ) , are b r o a d a n d almost structureless, showing
less w e l l - r e s o l v e d states t h a n are o b s e r v e d in a d i l u t e
aqueous solution (15, 16) of H2SO4.
A n oxide reduction region, which a p p e a r s to be con-
j u g a t e w i t h the b r o a d surface oxidation region, Ia, IIa,
shows a p e a k (IIc) a n d a shoulder (Ic). A s i m i l a r b e -
h a v i o r is only resolved in m o r e dilute H2SO4 solutions
u n d e r special low t e m p e r a t u r e conditions (I9) or w i t h
w e a k l y a d s o r b e d anions, e.g., C104-. T h a t the c u r r e n t s
in the r e g i o n Ia, c a n d IIa,c c o r r e s p o n d to surface p r o -
cesses is indicated b y a p p r o x i m a t e constancy (to 5%)
of the charges Under the curves in e x p e r i m e n t s con-
ducted at various sweep rates.
A p p l i c a t i o n of the p o t e n t i a l h o l d i n g p r o g r a m (ilia)
at the positive end of an anodic sweep gives the results
shown in Fig. 2b. O n l y g r o w t h of the surface oxide oc-
curs, as i n d i c a t e d b y the increasing r e d u c t i o n charges
w i t h time, ~:h,a, in t h e cathodic sweep w h i c h increase
l o g a r i t h m i c a l l y in Th~a. This is the n o r m a l k i n d of b e -
havior, e.g., as observed (20, 21) in dilute solutions at
Pt.
It is u n d e r the cathodic holding p r o g r a m (iiib) t h a t
the u n u s u a l b e h a v i o r of tt2SO4 is observed. When the
p o t e n t i a l is held at the n e g a t i v e end of a cathodic
sweep at --0.244V, EH for various times, ~h.c, an i n -
creasing anodic c u r r e n t a p p e a r s i n i t i a l l y over the s u r -
face oxide region in a following anodic sweep (Fig. 4).
W i t h increasing ~h.~, the currents in following anodic
sweeps after the holding period: (a) i n i t i a l l y increase
b u t e v e n t u a l l y r e a c h a s a t u r a t i o n limit; (b) are i n -
d e p e n d e n t of solution m a s s - t r a n s f e r r a t e at a r o t a t e d
electrode [see the following section]; also, (c) a c o m -
p o n e n t of anodic c u r r e n t in these anodic sweeps a p -
pears at a l o w e r t h a n usual (Fig. 2) anodic potential,
giving a shoulder. IIIa, (Fig. 4), on the anodic i vs. V
profiles after holding for m o r e t h a n 20 sec.
As this s h o u l d e r c u r r e n t a p p e a r s a n d increases w i t h
increasing ~h.c, the oxide r e d u c t i o n c u r r e n t profile (Ic,
IIc) diminishes a n d a n e w cathodic c u r r e n t p e a k (IIIc)
a p p e a r s and p r o g r e s s i v e l y increases w i t h increasing
9h.c, e v e n t u a l l y reaching saturation. This b e h a v i o r is
i l l u s t r a t e d in the succession of i vs. V profiles shown
in Fig. 4 for various times of holding.
The dependence of the e x t r a anodic currents w h i c h
a p p e a r o v e r the oxi6e f o r m a t i o n region and of the n e w
cathodic currents which a p p e a r in the cathodic sweep,
and also of the oxide r e d u c t i o n charges, on time of
cathodic holding, Vh,c, is shown as i n t e g r a t e d charges in
 Vol 128, No. 11 H~SO4 REACTIVITY 2265

for m o n o l a y e r processes, suggesting the role of c h e m i -

Fig. 4. A series of anodic followed by cathodic cyclic-voltammetry
curves for Pt in 98% H2SO4 at 298 K after various times ~ . e of
holding the potential constant at --0.244E. Sweep rate 70 mV
see-l; times Th,c: curve 1, 0; curve 2, 5; curve 3, 10; curve 4, 15;
curve 5, 20; curve 6, 40; and curve 7, 80 sec.
Fig. 5. T h e r e a p p e a r s to be some induction p e r i o d in
the f o r m a t i o n of w h a t e v e r species (see l a t e r ) that gives
rise to the e x t r a cathodic p e a k in the cathodic sweep
w h i c h follows the first anodic sweep a f t e r holding.
A l l the charges d e r i v e d f r o m i n t e g r a t i o n of the c u r -
r e n t s over various regions of the i vs. V profiles cor-
respond, in o r d e r of m a g n i t u d e ( s e e Fig. 5), to values
~ ~ o - ~
400
sorption in the reactions involved.
If, a f t e r the e x p e r i m e n t at a series of successively
increasing cathodic holding times, the electrode is
allowed to be f r e e l y cycled [ c y c l i c - v o l t a m m e t r y mode
( i ) ] , the n e w cathodic p e a k IIIc g r a d u a l l y diminishes,
the c u r r e n t s over the surface o x i d a t i o n region diminish,
and the surface oxide r e d u c t i o n region e v e n t u a l l y r e -
covers to its initial charge a n d p e a k currents. As this
r e c o v e r y takes place (slowly, as shown in Fig. 6), an
isopotential point (22) is o b s e r v e d b e t w e e n the series of
decreasing c u r r e n t p e a k s at 0.05V for process IIIc and
the series of increasing surface oxide r e d u c t i o n c u r -
rents Ic a n d IIc. This suggests t h a t t h e r e is a coupling
b e t w e e n the processes, Ic, IIc, a n d the r e d u c t i o n p r o -
cess, IIIc, p r o b a b l y t h r o u g h a d s o r p t i o n a n d occupancy
of surface sites on the P t e l e c t r o d e b y two species.
Behavior at the rotated P t electrode.--If the e x p e r i -
m e n t s c o r r e s p o n d i n g to the results shown in Fig. 4
and 6 a r e p e r f o r m e d a t a r o t a t i n g P t d i s k electrode
(1000 ~ 3000 r p m ) , t h e i n i t i a l (Th.e --" 0) i VS. Y p r o -
file shown in Fig. 2a r e m a i n s unchanged. If, h o w e v e r ,
the cathodic holding e x p e r i m e n t is c a r r i e d out u n d e r
r o t a t i o n conditions, the d e v e l o p m e n t of the enhanced
anodic and n e w cathodic c u r r e n t s in following sweeps
(as shown in Fig. 4) is r e t a r d e d , b u t eventually, as
Th.e --> 90 sec (Fig. 7) the same ( s a t u r a t i o n ) anodic
c u r r e n t profiles are a t t a i n e d as in the static solution
w i t h Th.c --~ 45 see (curve for IIa + I I I a in Fig. 5).
This r e s u l t suggests t h a t (a) the i m m e d i a t e p r o d u c t of
r e d u c t i o n becomes spun-off into solution, b u t (see'
below) m a y become r e - a d s o r b e d a f t e r its f o r m a t i o n ;
and (b) the p r i m a r y reduction process involves H2SO4
r a t h e r t h a n a n o t h e r species such as H2S~O7 (2) at
low concentration, since electrode rotation r e t a r d s
r a t h e r than enhances the r e d u c t i o n process; thus, if the
r e d u c t i o n effects o b s e r v e d in 98% H2SO4 were, in
fact, due to a small concentration of electroactive
H2S207, r o t a t i o n w o u l d t e n d to enhance r a t h e r t h a n
diminish the o b s e r v e d reduction effects, due to the
e x p e c t e d facilitation of mass t r a n s f e r of H2S207 m o -
lecular to the electrode surface u n d e r r o t a t i o n condi-
tions.
A n e x p e r i m e n t in which t h e cathodic holding is
conducted at a s t a t i o n a r y P t disk electrode, b u t the
.... -O---lilac 110

30c

~ ~0,--Peak m" c
'E
o
(J ///
~L I o"
o" ! //
/
20C I /
/
li /
I /"
/ /
/ //

t /

/~ /" ~X~ ...... X. . . . . . . . x----Oxide

Ic,Ilc
r ~g'J (decrease)
// ~01
G._~~..-0~ n I I 1c~0
~O ~ 60 80
"rh,c (sec)
Fig. 6. "Recovery" of initial cyclic-voffammetry i vs. V profile
Fig. 5. Charges in #C cm - ~ for the three principal time-de- [Fig. 3(a)] after a series of 25 repetitive potential sweeps at 70
pendent processes in the curves of Fig. 4 as a function of cathodic mV sec -1, following a period Th~c of holding the potential at
holding time Th,e sec. (~) Charges for process IIIc; @ charges for --0.244V EH. Time scale of the succession of the 25 curves is de-
processes in the region Ilia -]- Ila; and • charges in the surface termined by the sweep rate of 70 mV sec -1 and the potential
oxide reduction region Ic, IIc. range of 1.54V.
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 2266 J, E l e c t r o c h e m . Soc.: E L E C T R O C H E M I C A L
Fig. 7. Cyclic-voltammetry i vs. V profiles for a Pt disk electrode
in 98% H2S04 at 70 mV sec -1 after 0 and 90 sec cathodic hold-
ing, with ("rot") and without ("stat') electrode rotation at 3000
rpm. Current-density profiles in regions Ilia, Ila are independent
of electrode rotation.
following anodic sweep is t a k e n w i t h o r w i t h o u t r o -
tation at 3000 rpm, shows (Fig. 7) t h a t the profiles
of the e x t r a anodic c u r r e n t s t h a t pass at the r o t a t e d
electrode on the anodic sweep i m m e d i a t e l y following
the r e d u c t i o n d u r i n g the t i m e Th,c, are identical w i t h
those o b s e r v e d at the s t a t i o n a r y electrode u n d e r o t h e r -
wise the same conditions. This suggests that, a l t h o u g h
the i m m e d i a t e p r o d u c t (say "X") of r e d u c t i o n in the
cathodic holding e x p e r i m e n t m a y be a species w e a k l y
a d s o r b e d and hence able to be spun a w a y into solu-
tion (as i n d i c a t e d b y the r e s u l t r e f e r r e d to in the
previous p a r a g r a p h ) , e v e n t u a l l y a s t r o n g l y b o u n d
species (say "Y") becomes, and remains, c h e m i s o r b e d
up to a s a t u r a t i o n l i m i t (Fig. 4 and 5) at the P t elec-
trode d u r i n g the s u b s e q u e n t anodic sweep.
If, however, a f t e r cathodic holding for 80 sec w i t h -
out rotation, free p o t e n t i a l cycling is allowed to occur
as in Fig. 6, b u t now w i t h electrode rotation, the
cathodic p e a k c u r r e n t s m a r k e d IIIc and the e x t r a
anodic currents ( m a r k e d I l i a and IIa) which o v e r l a p
with the o r i g i n a l surface oxide f o r m a t i o n region
Ia ~ IIa, r a p i d l y d e c a y (as shown in Fig. 7) almost
to the level of c u r r e n t s in the initial i vs. V profile (cf.
Fig. l a ) w i t h o u t holding. This shows t h a t while the
species (Y, say) w h i c h originates from the species X
p r o d u c e d in the cathodic holding t r e a t m e n t is a chemi-
sorbed species, it can, however, following oxidation
on the surface in processes Ia W IIa -t- I I I a (Fig. 4),
be spun a w a y into the b u l k solution a f t e r r e d u c t i o n
and slow desorption in the n e x t cathodic sweep, so
that currents in s u b s e q u e n t cathodic and anodic sweeps
p r o g r e s s i v e l y diminish; Y itself and its products of
o x i d a t i o n in I I I a and IIa are bound species unaffected
by m a s s - t r a n s f e r conditions (Fig. 7).
The reduction process in IIIc a p p e a r s to be associ-
ated w i t h a species t h a t arises from IIc a n d is loosely
b o u n d on the surface since electrode rotation e l i m i -
nates most of the r e d u c t i o n c u r r e n t in this region a l -
most from its c o m m e n c e m e n t in the IIIc region (Fig.
7), y e t the r e m a i n d e r of the anodic and cathodic
i vs. V profile is i n d e p e n d e n t of rotation, e.g., a f t e r
9h,c = 90 sec. However, u n d e r successive cycling con-
ditions (Fig. 6) a f t e r Th,c = 90 sec w i t h no rotation, it
then t a k e s ca. 20 cycles (ca. 400 sec) for the p e a k
c u r r e n t at IIIc to decay to the level in Fig. 7 a f t e r 1
cycle w i t h rotation, so t h a t the species being r e d u c e d
at the surface in IIIc r e m a i n s in some loose a t t a c h m e n t
to the P t sufficient for r e o x i d a t i o n i m m e d i a t e l y in the
following anodic sweep w i t h little loss of the level
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SCIENCE AND TECHNOLOGY N o v e m b e r 1981
of currents over the regions IIIa, and Ia (Fig. 4).
(Possibly a p o l y m e r i c f o r m of S or a polysulfide is
involved.) The l a t t e r r e s u l t indicates c l e a r l y t h a t
the species g e n e r a t e d a t t h e end of the cathodic sweep
t h r o u g h the IIIc region (e.g., the top curve, Fig. 6) i.q
the same as t h a t f o r m e d in the initial holding period
for ~h,r s e c .
Possible m e c h a n i s m of the e~ects: eZucidation b y
chemical simulation e x p e r i m e n t s . - - T h e results of Fig.
4, 5, and 6 suggest t h a t a product, X, d e r i v e d from
the sulfuric acid is first f o r m e d b y r e d u c t i o n near the
Hs/H+ s t e a d y potential. Some of X, p r o b a b l y in a
f u r t h e r r e d u c e d chemisorbed state Y (see b e l o w ) ,
t h e n becomes oxidized to a species Yo in the following
anodic sweep. The r e d u c t i o n of H~SO4 to f o r m detect-
able X and Y, as i n d i c a t e d b y its subsequent o x i d a t i o n
to Yo and the following r e d u c t i o n of Yo in the next
cathodic sweep, is quite slow, r e q u i r i n g ca. 20 sec for
f o r m a t i o n of a detectable a d s o r b e d i n t e r m e d i a t e at
298 K.
In the n e x t cathodic sweep, following f o r m a t i o n of
u b y oxidation of Y d e r i v e d f r o m X, Yo is r e d u c e d to
a species "Z", giving (Fig. 4) the s u b s t a n t i a l p e a k
IIIc on the cathodic i vs. V profile n e a r the H s / H +
potential. The r e d u c t i o n c u r r e n t giving Z d e p e n d s on
how m u c h X, and hence Y ( a n d thus Yo f r o m Y), w e r e
p r o d u c e d in the cathodic holding.
The observation of the r e d u c t i o n p e a k IIIc p r o -
ducing Z, after o x i d a t i o n of X and Y to Yo species in
the previous anodic sweep, means t h a t the process of
oxidation of X or Y is not r e - f o r m a t i o n of H2804 or
HsSG4- ion (i.e., Yo is not one of these species) since
HeSO4 (or H S O 4 - ) itself is not r a p i d l y r e d u c e d in a
single cathodic sweep, as follows f r o m the b e h a v i o r
in Fig. 2, a n d f r o m the fact t h a t the p r i m a r y r e d u c -
tion process w h i c h takes place d u r i n g cathodic h o l d -
ing is quite slow.
Consideration of the c h e m i s t r y of 98% H2SO4 sug-
gests that the first reduction p r o d u c t X is l i k e l y to
be SOs or H S O 3 - p r o d u c e d e i t h e r f r o m H2SO4 m o l e -
cules or a n y dissolved SOs p r e s e n t [cf. Ref. (6)].
However, the l a t t e r possibility is quite u n l i k e l y since
the concentration of SC)s in 98% HsSO4 (ca. 1~r in
H20) is k n o w n to be v a n i s h i n g l y small (2). The effects
are u n l i k e l y to be due to o t h e r adventitious i m p u r i t i e s
since we have found p r e v i o u s l y (16) with this B.D.H.
acid, and in the p r e s e n t work, t h a t its solutions in
p y r o d i s t i t l e d w a t e r give e x c e l l e n t cyclic v o l t a m r n o -
grams for P t w i t h o u t a n y i m p u r i t y problems. This is
also i n d i c a t e d b y the b e h a v i o r of A u (see l a t e r ) in
this acid.
Since only m o n o l a y e r m a g n i t u d e s of i n t e r m e d i a t e s
in the H2SO4 reduction are p r o d u c e d in the e x p e r i -
ments (e.g., see Fig. 5), d i r e c t chemical analyses and
characterizations w e r e not feasible, especially in e x -
cess of 98% H2SO4. However, chemical simulations of
the behavior of s e v e r a l l i k e l y intermediates, b y a d d i -
tion of k n o w n sulfur compounds in trace amounts,
w e r e found to be profitable for the purpose of i n d i c a t -
ing some of the initial processes t h a t t a k e place.
First. in o r d e r to test the possibility t h a t X is SO2
(or H S O s - ) , a s m a l l a m o u n t of SOs was a d d e d (as
SO~ 2- in a c r y s t a l of NasSO3) to the 98% H2SO4 in
which the p o t e n t i a l of the P t electrode was being
cycled as in Fig. 2a (full p o t e n t i a l r a n g e ) . I m m e d i -
a t e l y the characteristics of Fig. 4 were developed, i n -
cluding q u a n t i t a t i v e l y the finer details. Therefore,
the initial r e d u c t i o n of HsSOa is e v i d e n t l y to SOs or
HSO3-. However, it is k n o w n [e.g., Ref. (7)] t h a t
SO2 itself can be r e d u c e d at P t to sulfur species in
l o w e r oxidation states, e.g., HeS or S. This could e x -
plain the initial effects of electrode r o t a t i o n in the
cathodic holding e x p e r i m e n t ; thus, SOs (X) is first
p r o d u c e d a n d some can be spun away, b u t some m o r e
s t r o n g l y b o u n d r e d u c e d species Y, such as one-site
 Vol. 128, No. 11 H2S04 R E A C T I V I T Y 2267

a n d t w o - s i t e c h e m i s o r b e d S a n d c o r r e s p o n d i n g SO (23): 2SO32- --> S206 s - ~u 2e. This suggests an a l t e r -

species (7, 8) are e v e n t u a l l y built up on the surface native p a t h w a y for the reduction and r e o x i d a t i o n
f r o m the SO2 a n d give rise the anodic s a t u r a t i o n processes o b s e r v e d in 98% H~SO4 at Pt, as follows:

H2SO4 or S(~3
Cathodic (slow) \ Anodic sweep (not the p r i n c i p a l anodic r e o x i d a t i o n process
holding since no p e a k can be given on a following cathodic s w e e p for
(,h,~) such a process)
!

X SO2 o r HSO3 ~ Anodic s w e e p ( c u r r e n t s i n d e p e n d e n t of r o t a t i o n )

$2062- Yo
Cathodic sweep ( p e a k I I I c )
Rotation ................. 9 Some spin off into b u l k solution on r e p e t i t i v e recycling

c u r r e n t s for p a r t i a l r e o x i d a t i o n of these species in Here it is supposed t h a t the species Yo (which can-

regions IIa + I I I a (Fig. 4, 5, and 7) w h e n Th,c is suf- not be H2SO4 or SO3) is $2062-, f o r m e d in the anodic
ficiently long (90 sec). The subsequent o x i d a t i o n of sweep over regions Ia and IIa from X (SO2 or H S O s - ) ,
these s t r o n g l y b o u n d species, or of the SO2 i n i t i a l l y and that $2082- can be r e d u c e d w i t h facility b a c k to
produced, in the anodic s w e e p following the t i m e zh.c SOe or H S Q - in the cathodic s w e e p ( p e a k I I I c ) , fol-
cannot be b a c k to H2SO4 or SOa, otherwise no f u r t h e r lowing its f o r m a t i o n from SO2 or H S O 3 - .
facile r e d u c t i o n of Yo to Z in the n e x t cathodic sweep A f u r t h e r s i m u l a t i o n e x p e r i m e n t was p e r f o r m e d in
w o u l d be observed, as we m e n t i o n e d earlier. which $2062- (as the Na + salt) was a d d e d at the b e -
T h e r e is some induction time in the d e v e l o p m e n t of ginning of the surface oxidation region (Ia) in an
the species (Y) t h a t is oxidized in the anodic sweeps anodic sweep. No e n h a n c e m e n t of anodic c u r r e n t s is
a f t e r cathodic holding and after this induction time o b s e r v e d u n d e r these conditions, b u t on the following
an e x t r a anodic c u r r e n t s h o u l d e r ( I I I a ) a p p e a r s on cathodic sweep, the cathodic c u r r e n t p e a k IIIc n e a r
the anodic sweep. It is w h e n this s h o u l d e r is d e v e l o p e d the H2 reference p o t e n t i a l is observed, as in the e x -
t h a t the r e - r e d u c t i o n peak, IIIc, on the s u b s e q u e n t p e r i m e n t s w i t h slow r e d u c t i o n of t h e H2SO4 (Fig. 4)
cathodic sweep is d e v e l o p e d (Fig. 4). The efficiency in the absence of an a d d e d compound. A s u b s e q u e n t
of the p r o d u c t i o n of Y a n d Yo from X d e p e n d s on the a n o d i c / c a t h o d i c cycle gave a s u b s t a n t i a l increase in
m a s s - t r a n s p o r t conditions and these d e t e r m i n e the this cathodic ueak; the b e h a v i o r of a d d e d $2062- is
induction time. i l l u s t r a t e d in Fig. 8.
The c h e m i s t r y of t h e o x y - and t h i o - o x y - a c i d s of sul- These observations are consistent w i t h Yo b e i n g an
f u r is v e r y complex (23) a n d a n u m b e r of possibilities a d s o r b e d form of $2062- (or H S 2 0 6 - or dithionic
exists for the i d e n t i t y of the species Y a n d Yo. G e n - acid) since if Yo is $2062- a n d it is a d d e d at the b e -
e r a l l y speaking, t h e r e are two types of species t h a t ginning of the surface o x i d a t i o n region, no e x t r a
m a y be involved: (a) t h i o - o x y - a c i d or anion species anodic c u r r e n t s should be observed; this is as found.
that m a y be p r o d u c e d in an a d s o r b e d state on the Moreover, if Yo is $2062- f o r m e d from the SO2 or
electrode, b u t correspond stoichiometrically to k n o w n H S O 3 - p r o d u c e d in the r e d u c t i o n e x p e r i m e n t s in
molecules or ions; or (b) chemisorbed species, not H2SO4, then it could be r e d u c e d b a c k to SO2 o r H S O s -
necessarily k n o w n molecules, d e r i v e d from reduction (or some o t h e r species such as HsS) in the cathodic
of SO2 ( p r o d u c e d i n i t i a l l y f r o m the I--I2SO4) and f r o m p e a k sweep ( p e a k I I I c ) ; this is o b s e r v e d in the s i m u -
the r e o x i d a t i o n of these species on the electrode s u r - lation e x p e r i m e n t (Fig. 8).
face, e.g., Ref. (7, 8). First, we shall d e a l w i t h possi-
bilities of t y p e (a).
The e x p e r i m e n t w i t h a d d e d SO~ as SOs 2 - gives the
u n a m b i g u o u s conclusion t h a t the initial p r o d u c t (X)
of electrochemical r e d u c t i o n of H2SO4 at P t is SOs or
HSO3-. P r o d u c t s of f u r t h e r r e d u c t i o n could be di-
thionite (X', see b e l o w ) , and of subsequent r e o x i d a -
tion in the following anodic sweep, t h e y could be SOs
(or H S O s - ) or d i t h i o n a t e ( $ 2 0 6 s - ) , o r the c o r r e -
sponding acids o r acid anions. S u l f o x y l a t e or sulfoxylic
acid, S ( O H ) e , is u n l i k e l y to be the species Yo as the
S in this c o m p o u n d is in a l o w e r valence state t h a n
that of S in SOs or H S O s - and is v e r y u n s t a b l e (23).
A first possibility for consideration is that, initially,
a f t e r short periods of cathodic holding, SO2 can, in
fact, be to some e x t e n t r e o x i d i z e d b a c k to I-IsSO4 (or
SOs) in an anodic sweep, but, d u r i n g l o n g e r times of
reduction, ~h.c, SO2 can be r e d u c e d f u r t h e r to d i t h i o -
n i t e ion, SsO42-. This could be then r e o x i d i z e d on the
following anodic sweep to the species Yo t h a t can be
r e - r e d u c e d in the cathodic p e a k IIIc. Thus Yo w o u l d
be SOs and Z $204 s - again.
A chemical simulation e x p e r i m e n t w i t h addition of
dithionite (as Na2S204) was u n p r o d u c t i v e as the
$2042-, or the c o r r e s p o n d i n g acid, is i m m e d i a t e l y Fig. 8. Cyclic-voltammograms at 70 mV sec -1 for Pt in 98%
decomposed b y 98% H2SO4 to SOs, and some HsS a n d H2S04 with dithionate added on the anodic sweep at 0.48V Eft-
colloidal S. O n l y the characteristics of a d d e d SO2 are Curve 1, initial anodic sweep i vs. V profile without holding and
observed. $204 s - a p p e a r s t h e r e f o r e to be too u n s t a b l e without addition of $2062-. Curve 2 (beyond 0.48V), after addi-
to be a l i k e l y i n t e r m e d i a t e giving rise to Y as SO2. tion of 10 - 4 mol $2062- (no change). Curves 3, 4, 5 i vs. V pro-
The e l e c t r o l y t i c o x i d a t i o n of SO2 or SO,~2 - to di- files for successive potential sweeps after completion of 1, 2 follow-
thionate, however, is r e p o r t e d in t h e e a r l y l i t e r a t u r e ing addition of the dithionate.
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 2266 J. Electrochem. Soc.: E L E C T R O C H E M I C A L SCIENCE AND TECHNOLOGY N o v e m b e r I98i

It should be noted t h a t most of the t h i o - o x y - a c i d s currents o b s e r v e d in this r e g i o n and I I I a (Fig. 4) a f t e r

of S, a n d their anions, a r e u n s t a b l e in acid m e d i u m b u t cathodic holding. Thus the surface oxide m o n o l a y e r
$20~ 2 - is k n o w n to be the l e a s t u n s t a b l e (23). It does, f o r m e d at P t n o r m a U y gives an i n c r e a s i n g l y n e g a t i v e
however, decompose in H2SO4 w i t h evolution of SO2, (AR/R) signal w i t h increasing positive potential.
as was o b s e r v e d in the p r e s e n t e x p e r i m e n t s . Since this I[
F i g u r e 9 shows how ( A R / R ) varies w i t h p o t e n t i a l in
SO2 could f o r m Yo on the anodic sweep, w h a t e v e r Yo II
is, another s i m u l a t i o n e x p e r i m e n t was c a r r i e d out anodic and cathodic sweeps following cathodic holding.
b y cycling the electrode only o v e r the p o t e n t i a l r a n g e The p o t e n t i a l r a n g e is the same as t h a t in Fig. 4, so
up to the onset of surface oxidation (0.48V) (Fig. 8), t h a t b o t h the regions w h e r e e x t r a anodic currents
i.e., over the range w h e r e Yo could be r e d u c e d on a fol- pass in I I I a , + I a § IIa, a n d the r e g i o n w h e r e the
lowing cathodic sweep, b u t w h e r e no oxidation p e a k s cathodic p e a k IIIc arises are covered in this diagram.
for a n y species such as SO2 f o r m e d f r o m some d e c o m - F i g u r e 9 shows t h a t the g e n e r a l shape of the
position of a d d e d $20~ 2- w o u l d be observed. S~Os2 - (AR/R) vs. V r e l a t i o n s r e m a i n s the s a m e w h i l e the
II
was a d d e d a n d again gave, u n d e r these conditions, a chemisorbed r e a c t i v e species p r o d u c e d on cathodic
reduction p e a k on the cathodic cycle, similar to t h a t holding is r e m o v e d b y successive a n o d i c / c a t h o d i c
observed in the e x p e r i m e n t s on reduction of HaSO4 or cycling, b u t the i n t e n s i t y of the ( A R / R ) signal falls
with a d d e d SO2 or H S O a - . II
These results suggest t h a t the i n t e r m e d i a t e Yo could as less of the species r e m a i n s on the electrode. In the
be $2062- (or H S 2 0 6 - o r dithionic acid) or, m o r e anodic direction, the reflectivity features of surface
likely, $2062- in an a d s o r b e d state. We n e x t consider oxidation are not lost despite the d e v e l o p m e n t of e x t r a
(b), c h e m i s o r b e d species. oxidation charge ( ~ 4.20 C m -2, Fig. 5) o v e r the
surface oxide f o r m a t i o n region. This suggests [cf. Ref.
Possible chemisorbed species.~Not all the f e a t u r e s (7, 8, 11, 13)] that the a d s o r b e d species g e n e r a t e d b y
of the r e d u c t i o n b e h a v i o r of H2SO4 can be accounted cathodic holding a n d oxidized in the following sweep,
for s i m p l y in terms of plausible, "stable" chemical is in a state i n t i m a t e l y connected w i t h the d e v e l o p -
i n t e r m e d i a t e s such as dithionite or dithionate species, m e n t of the surface oxide film as w e have i m p l i e d
even if t h e y are chemisorbed. It has a l r e a d y been e a r l i e r in discussing the cyclic v o l t a m m o g r a m s a n d
m e n t i o n e d t h a t t h e lack of an effect of electrode r o - the isopotentiaI point observed therein.
tation r a t e on the anodic i vs. V profile observed a f t e r
r e d u c t i o n of the H2SO4 to SO2 for times ~h,c indicates Relation to surface oxide ~ormation and reduct~on.~
t h a t a species in a c h e m i s o r b e d state is d e r i v e d from The d i m i n u t i o n of the surface oxide r e d u c t i o n p e a k
SO2 (X) and s a t u r a t i o n coverage can be a t t a i n e d as as l a r g e r e x t e n t s of r e d u c t i o n of H2SO4 a r e allowed
m e a s u r e d b y the subsequent o x i d a t i o n c u r r e n t profile to take place (Fig. 4) d u r i n g cathodic holding, p r o b -
( I I I a -F I I a ) . This opens up a n u m b e r of possibilities a b l y arises because the surface o x i d e participates,
for the i d e n t i t y of species Yo, or Z, o t h e r than in d u r i n g the anodic sweep a f t e r holding, in the oxidation
terms of k n o w n chemical i n t e r m e d i a t e s of the k i n d of SO2 or of a r e d u c e d a n d / o r chemisorbed (7-13, 24)
considered above. form, to $2062- or to other a d s o r b e d species such as
Some insight into the n a t u r e of the chemisorbed - S - O (9), so that less oxide is f o r m e d d u r i n g the
species that e v i d e n t l y m i g h t be involved in the r e - time of t h a t anodic sweep. The e x p e r i m e n t w h e r e
duction of H2SO4 can be gained f r o m the w o r k o f cathodic holding was carried out at the s t a t i o n a r y a n d
L a l et al. (7-10) and of Lou~'ka (11-13) who studied
chemisorbed S - c o n t a i n i n g species at Pt, d e r i v e d from .66~ I NOISS LEVEL
H2S and SO2 in aqueous medium. Both L o u c k a (11,
13) and Lal et al. (7, 8) concluded that an o x y g e n a t e d
S species arose in c h e m i s o r p t i o n from e i t h e r SO2 o r
H2S solutions (9) at P t w h e n the P t surface was s u b -
j e c t e d to a n anodic sweep. B r i d g e d a n d l i n e a r " P t - S - O "
species (valencies and b o n d i n g not defined) w e r e p r o -
posed, based on c y c l i c - v o l t a m m e t r y e x p e r i m e n t s on -4.9s 98 % H2SO4 D,c
sw~EEP
0.SM aq H2SO4 solutions containing SO2 and H2S. ANO CATHO0~SWEEP
D o u b l y and singly b o u n d S and $2 species p r o d u c e d
in successive r e d u c t i o n stages from SO2 w e r e also •
postulated. Species such as " P t - S - O " w o u l d be q u a l i - I I f L --./ I , I
0.02 0,42 O,B2 1.22 0.82 0,42 0.02
rr
t a t i v e l y consistent w i t h the o b s e r v a t i o n t h a t the r e - POTENTIAL(V, E H)
duction peaks in the "surface oxide" region, o b s e r v e d v I NOISE LEVEL(2OSWEEPS)
in the p r e s e n t work, a r e r e l a t e d in some coupled w a y
(
to the r e d u c t i o n process IIIc n e a r e r the H region, as
indicated b y the isopotential point (Fig. 6). W h e n -I.6~
the species X and some d e r i v e d oxidized form Yo is
p r o d u c e d on the electrode, the b o u n d surface oxide -3.32

reduction charge on the following cathodic sweep is

diminished, b u t the charge associated w i t h the " r e - -4,98 0.1M aq. HzSO4
r e d u c t i o n " process at IIIc is increased. The process -6,64
OXIDE
IIIc can e v i d e n t l y p r o d u c e a p r o d u c t which is d e s o r b e d REDUCTON
as indicated b y the e x p e r i m e n t s at a r o t a t e d e l e c t r o d e I I I, , I , ]
0.02 0.42 0.82 1,22 0.82 0.42 0.02
(Fig. 7). This p r o d u c t is u n l i k e l y to be r e g e n e r a t e d POTENTIAL(V, E M)
SO2 since the results show t h a t at p o t e n t i a l s n e a r t h e
cathodic side of the p e a k IIIc, SO2 is s t r o n g l y adsorbed. Fig. 9. Relative reflectivity (AR/R) profiles for Pt in 9 8 %
Possibly the step IIIc involves reduction of the p r e v i - II
H2SO4 as a function of potential (sweep rate 70 mV sec - 1 , 298 K)
ously a d s o r b e d species to H2S. A t the m o m e n t the at Pt in the presence of the adsorbed species generated by cathodic
n a t u r e of the various chemisorbed species r e m a i n s holding for 60 sec and in its absence during a repetitive sweep or
speculative. during its decline after holding. Designations as in Fig. 2(a). Curve
A n a t t e m p t was m a d e b y means of r e l a t i v e reflec- 1, behavior on repetitive cycling, as in Fig. 2(a); curve 2, after 60
t i v i t y m e a s u r e m e n t s to distinguish q u a l i t a t i v e l y be- s~c holding at cathodic end af sweep, one cycle; curve 3, third cy-
tween the surface oxide species g e n e r a t e d in the r e - c]e after the 60 sec cathodic holding; lower curve for 0.1M aq
gions Ia, IIa, and the species associated w i t h the e x t r a H2SO4 for comparison.

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 VoL 128, No. 11 I-I~SOt R E A C T I V I T Y 2269

r o t a t e d electrode, showing t h a t rotation had no effect

f':
on anodic c u r r e n t s o b s e r v e d on the s u b s e q u e n t anodic
sweep, implies t h a t $2062- or S - O - s p e c i e s are being , i (Q)
20 ::.
f o r m e d in an a d s o r b e d state, thus competing w i t h i\ ~"~ ~. " 18.7M HeSO4 (conc.)
f o r m a t i o n of some of the surface oxide t h a t w o u l d ~,.~,~ k ~/' ~,,~, ..... 17.5M H2SO4
otherwise h a v e been p r o d u c e d on the anodic s w e e p
as in Fig. 2 w i t h o u t a n y r e d u c t i o n of H2SO4. The c o m -
plete absence of an o b s e r v a b l e u p d r e g i o n for t t at
P t (Fig. 2a) indicates that strong a d s o r p t i o n of H2SO4
molecules a n d / o r H S O 4 - ions is o c c u r r i n g as well.
oo
9 I ~ .......~
~.-0.2
a
-0.0
4 . . . .

"'~"-,,.~-...:~.,~..
o.s ~
. .
. 2. .

XPotentoi l
.

(V,EH)

The conclusions concerning $2062- or S - O - a d s o r p -

tion a r e s u p p o r t e d b y the b e h a v i o r o b s e r v e d w h e n the ..-- / .... ~ ....... ~

p o t e n t i a l is held constant for some t i m e at the end of ~S 2ol-- .. ,... "

the anodic sweep, following slow r e d u c t i o n of tteSO4
d u r i n g cathodic holding: then a n o r m a l q u a n t i t y (cf.
Fig. 2) of surface oxide becomes again observable. I t
was also concluded b y G e r o n o v et al. (25), that r e -
duction of SO2 at Pt, in this case in CH~CI%T, leads to
f o r m a t i o n of an a d s o r b e d species t h a t r a p i d l y t r a n s -
forms into a p a s s i v a t i n g film of dithionate (sic; p r o b -
a b l y dithionite in t h e i r case).
Role of water.--Following the w o r k d e s c r i b e d above
in "98%" H,~SO4, some e x p e r i m e n t s w e r e p e r f o r m e d
w i t h controlled additions of w a t e r to give c o n c e n t r a -
tions of 0.275, 0.55, a n d 1.IOM of a d d e d H20 in t h e
98% H2SO4. As shown in the series of i vs. V profiles
in Fig. 10, addition of w a t e r allows some u p d of H
to arise before significant H2 evolution currents a p -
pear. Also, in the presence of a d d e d water, cathodic
holding, followed b y an anodic cathodic sweep, p r o -
duces less of the r e d u c e d and r e o x i d i z a b l e species as
the w a t e r content is increased. E v e n t u a l l y n o r m a l b e -
havior of an aqueous H2SO4 solution is recognized
w h e r e r e d u c t i o n effects are in'significant.
Since, w i t h r e l a t i v e l y s m a l l additions of water, the
r e d u c t i o n reaction is c o n s i d e r a b l y diminished, y e t the
concentration of H2SO4 is still ca. 17M, this b e h a v i o r
suggests t h a t the r e d u c t i o n to SO2 and a n o t h e r i n t e r -
m e d i a t e does not t a k e place from m o l e c u l a r H2SO4 b u t
possibly from the s m a l l concentration2 of H2S207 t h a t
is p r e s e n t at e q u i l i b r i u m w i t h H2SO4 molecules (2).
The a d d e d w a t e r of course, even at the highest con-
centration of 1.1M could o n l y produce 1.1M of e x t r a
H30 + and H S O 4 - ions, i.e., ca. 5.8 real percent, so
t h a t most of the H2SO4 r e m a i n s as u n - i o n i z e d m o l e -
cules.
Behavior at A u . - - I n o r d e r to e x a m i n e if the r e d u c -
tion of H2SO4, or HeSeO7 contained in it, is a simple
e l e c t r o n - t r a n s f e r process or one r e q u i r i n g c h e m i s o r p -
tion and eIectrocatalysis, the b e h a v i o r of a gold elec-
t r o d e in 98% HeSO~ was e x a m i n e d comparatively.
A n e x c e l l e n t c y c l i c - v o l t a m m e t r y profile is o b t a i n e d
at Au, with no evidence of i m p u r i t y effects [cf. Ref.
(5, 16)], confirming the high degree of p u r i t y of
B.D.H. A r i s t a r H2SO4. The g e n e r a l f e a t u r e s of this
curve for A u are s i m i l a r to those for A u in aqueous
H2804. Cathodic holding for up to 2 min at the same
p o t e n t i a l as at P t r e v e a l e d a b s o l u t e l y no indication of
a n y r e d u c t i o n of the HeSO4. The subsequent anodic
and cathodic sweeps were identical with those u n d e r
r e p e t i t i v e cycling conditions. U n d e r the same condi-
tions as at Pt, addition of SOs (as SO,32-) also gave no
r e a c t i o n currents, e i t h e r in anodfc or cathodic sweeps.
This is c o n t r a r y to w h a t has been found in aqueous
solutions (24) and the absence of such an effect h e r e
m u s t be a t t r i b u t e d p r e s u m a b l y to the strong a d s o r p -
tion of H2SO4 [cf. Ref. (5)] at Au a n d the differeng
effective cathodic r a n g e of potentials t h e r e f o r e in-
volved. A d s o r p t i o n and r e a c t i v i t y of S (as S 2 - ) at A u
a r e also k n o w n (26).
It is t h e r e f o r e to be concluded t h a t the reaction of
H2SO4 r e d u c t i o n observed at P t is associated w i t h the
~However, the rotation e x p e r i m e n t s m e n t i o n e d o n p. 2265 o n
behavior at the rotated Pt e l e c t r o d e w o u l d n o t s u p p o r t t h i s con-
clusion unless the r o t a t i o n effect is m o r e c o n n e c e d w i t h spin-off
of SO.~, restricting f u r t h e r reduction a n d / o r chemisorptian to Y.
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h ."/ ~.~ - ~,,: o
'Ollt i1 \ .....
I ~] 0.2 O,6 1D " - " ~ 1 . 4
I0~~~ .~ M enii~<VE
' H)
Fig. 10. Cyclic-voltammetry i vs. V profiles for Pt in 98% H2SO4
with small additions of extra water. Sweep rate 58 mV see-i;
298 K. (a) Anadic/cathodic cyclic-voltammograms without cathodic
holding. (b) Behavior after cathodic holding for 20 sec or, sepa-
rately, anodlc holding for 20 sea Concentrations of HzSO4, after
additions of water, as indicated.
catalytic and a d s o r p t i v e p r o p e r t i e s of this m e t a l and
t h a t H2SO4, o r H2S207, is not easily r e d u c e d in an
e l e c t r o n - t r a n s f e r process not i n v o l v i n g chemisorption
and electrocatalysis.
Conclusions
98% H2SO4 can be r e d u c e d at P t electrodes n e a r
the s t e a d y potentiM of a h y d r o g e n electrode in t h e
same solution. Chemical simulation e x p e r i m e n t s d e m -
o n s t r a t e t h a t the i d e n t i t y of the initial p r o d u c t of the
o b s e r v e d slow reduction of H 2 S O 4 i s S O 2 o r H S O 3 - . A
chemisorbed species d e r i v e d f r o m SO2 is oxidized in a
following anodic sweep not back to H2SO4 or SO3 but
to an a d s o r b e d i n t e r m e d i a t e Yo that is r e d u c e d b a c k to
a species that is r e l a t i v e l y easily d e s o r b e d into solution
at the end of a subsequent sweep n e a r the H2/H +
s t e a d y potential. S i m u l a t i o n e x p e r i m e n t s show, t h a t it is
possible that the species (Yo) d e r i v e d from SO2 is di-
thionate or dithionic acid, p r o b a b l y stabilized in some
state b y adsorption at the P t electrode. I t is most l i k e l y
t h a t chemisorbed intermediates, d e r i v e d f r o m SO2, or
f r o m the a d d e d $2062-, which are not n o r m a l stable
compounds, are involved.
No reduction of 98% H2SO4 or e l e c t r o a c t i v i t y of
SO2 (or H S O 3 - ) is o b s e r v e d at A u u n d e r the same
conditions as at Pt. By comparison, therefore, the
observation of reactions w h i c h t a k e place at P t indi-
cate that an electrode surface, w h e r e electrosorption
and electrocatalysis can occur, is r e q u i r e d for the ini-
tial stage of r e d u c t i o n of H2SO4 to SO~..
Acknowledgments
G r a t e f u l a c k n o w l e d g m e n t is m a d e to the Natural
Sciences and E n g i n e e r i n g Research Council of Canada
for s u p p o r t of this work. One of us (D.M.N.) a c k n o w l -
edges a Leave of Absence for Specialization f r o m
the L a b o r a t o r y of PhysicochemicaI Separations, C e n t r e
for M a r i n e Research, R u d e r Boskovlc Institute. Zagreb,
Yugoslavia. We t h a n k Mr. J. C. K u in o u r l a b o r a t o r y
for c a r r y i n g o u t the reflectivity e x p e r i m e n t s .
 2270 J. EIectrochem. Soc.: ELECTROCHEMICAL SCIENCE AND TECHNOLOGY November 1981

Manuscript submitted Sept. 12, 1980; revised manu- 14. J. O. Zerbino, N. R. Tacconi, A. J. Calandra, and
script received May 12, 1981. A. J. Atria, ibid., 77, 379 (1977); A. J. Calandra,
N. R. de Tacconi, and A. J. Arvia, ibid., 49, 145
Any discussion of this paper will appear in a Discus- (1974); N. R. de Tacconi, A. J. Calandra, and
sion Section to be published in the June 1982 JOURNAL. A. J. Arvia, ibid., 51, 25 (1975); N. R. de Tacconi,
All discussions for the June 1982 Discussior; Section A. J. Calandra, and A. J. Arvia, ibid., 57, 267, 325
should be submitted by Feb. 1, 1982. (1974). See also F. Colom, A. de la Plaza, and R.
Publication costs of this article were assisted by the Gancedo, Anal. Quire., 71, 985 (1975).
University o$ Ottawa. 15. E.g., see F. G. WiLl and C. A. Knorr, Z. Elektro-
chem., 64, 258 (1960).
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1. B. E. Conway and D. M. Novak, J. Phys. Chem., lowska, and E. E. Criddle, Anal. Chem., 45, 1331
81, 1459 (1977); see also B. E. Conway and D. M. (1973).
Novak, J. Electroanal. Chem. Inter]acial ELectro- 17. M. W. Breiter, Z. Elektrochem., 60, 37, 119 (1956);
chem., 99, 133 (1979). ,, see also S. B. Brummer, J. I. Ford, and M. J,
2. R. J. Giltespie and E. A. Robinson, in Non-Aqueous Turner, J. Phys. Chem., 69, 3424 (1965).
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Chap. 4, Academic Press, New York (1965). Faraday Trans. I, 69, 1090 (1973).
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This Journal, 125, 1256 (1978). W. B. A. Sharp, J. Electroanal. Chem. InterJacial
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157, 1174 (1964). (1968).
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Reactions of Scratched Copper Electrodes in

Aqueous Solutions
G. T. Burstein* and R. C. Newman 1
Department of Metallurgy and Materials Science, University of Cambridge, Cambridge CB2 3QZ, England

ABSTRACT
The behavior of copper electrodes scratched under potential control in
aqueous electrolytes is presented. In alkaline solution the metal surface shows
the presence of two distinct types of oxidized monolayer, ascribed to CuOH
and Cu20, each formed over a unique potential range well below the revers-
ible potential for bulk Cu20 formation. The Cu20 monolayer is a necessary
precursor to passivation of the metal, and in sulfuric acid solution only the
CuOH monolayer is observed. This monolayer acts as an intermediate laver in
both the dissolution and passivation processes and probably also exists during
steady-state hydrogen evolution. Addition of ammonia to alkaline electrolytes
modifies the CuOH monolayer, probably by incorporation of NHs, rendering
formation of Cu20 more difficult.

Determination of the kinetics of reaction between
scratched metal electrodes and aqueous electrolytes
gives quantitative information on fast electron transfer
steps (1-6). The scratched iron electrode (1) reacts
very rapidly to form an Fe(I) species adsorbed to com-
plete coverage to the metal surface. Given the nominal
composition of FeOH, this monolayer is affected by
some anions in the electrolyte such as C1- and H2PO4-
(2). Silver has been shown to react anodically with
the formation of single adsorbed monolayers of AgOH
and Ag20 (3, 4). These monolayers are formed at po-
* E l e c t r o c h e m i c a l Society A c t i v e M e m b e r .
1 Present address: B r o o k h a v e n N a t i o n a l L a b o r a t o r y , U p t o n , N e w
Y o r k 11973.
Key words: eouper anode, c o p p e r p o l a r i z a t i o n , s c r a p e d c o p p e r ,
underpotential monolayers.
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tentials well below the reversible potential for bulk
Ag20 formation and the behavior is in complete accord
with results obtained from fast potential sweeping and
potential pulsing experiments on polished silver sur-
faces (3). Thus, at least in the case of silver, these
underpotential reactions are not uniquely a property
of the heavily cold-worked scratch surface. Further,
at pH 14, scratched silver shows a small potential
range in which no oxidation reaction oecurs: Under
these conditions it is possible to determine the zero
charge potential of the unreacted metal surface (3, 7).
The fast electron transfer reactions that occur from
scratched surfaces have been used to interpret the
rate of stress-corrosion cracking in some systems (5,
6, 8). The relevance of bare surface reaction kinetics