Professional Documents
Culture Documents
Electrochemical properties
of some naturally occurring quinones
ABSTRACT
INTRODUCTION
EXPERIMENTAL
The investigation was carried out by thin-layer voltammetry. A cell with two
plane-parallel pyrolytic graphite electrodes with a total area of 2.26 cm2 was used.
The redox conversion of the quinones studied proceeds rather reversibly in the
whole range of pII. The voltammetric curves were quite reproducible in repeated
cycles. The ratio of the peak heights (,1,/,1,) was 1 & 0.1. The difference between
the peak potentials (AE, = a Ep -c I$,) did not exceed 20-25 mV. For example, in
the case of lawson the values of A&, were the following: 20 mV (pH I-95), 10 mV
(pH 6.35 and 9.7) and 8 mV (pH 12.0).
The electrochemical conversion of the quinones investigated is a~ornpa~~ by
their adsorption on the carbon electrode surface. in our experiments the electrodes
were equilibrated with the solution before the cavity of the thin-layer cell was filled
with the same solution. Thus, in the course of the experiment we obtained some
surplus of electricity above that calculated from the known values of cell volume
and concentration. The adsorbed species displayed reversible electrochemical reac-
tivity in the same range of potentials as the dissolved ones. The voltammetric curves
for all quinones had a quite symmetric shape but their width at mid-height slightly
exceeded the theoretical value for a two-electron process (45 mv). The appropriate
width of the anodic peak of lawson was 50 mV at pH 1.95 and 6.35 and 55 mV in
more basic media. The peak widths at Ed-heist for the other quinones were of the
same order. We suppose this widening of the peaks is due to the supe~osition of the
191
i?
0.3
03
,I OH
6
0.2
0.4
\ b%=-87mv
0
A-
2
-0,1
-0,z
-0,1 -\
\
\
+H+ \
\
-0,L \
\
+e- \
\
-0.E
PH
I t . I I I
-0.E
Fig. 1. pa-potential diagram for 2-hydroxy-1,4-naphthoquinone (lawson). The symbol AH stands for the
molecule of lawson shown in the figure. The dashed line (here and in the other figures) corresponds to
Hz /H * equilibrium.
redox conversion of the dissolved material and that of the adsorbed one. The
electrochemical activity of quinones in the adsorbed state was also confirmed by the
linear dependence of the peak height upon the scan rate from 1 mV/s to 25 mV/s
observed in solutions of low concentration, where the adsorbed form prevails. The
results obtained in our experiments are in contrast to those of Hubbard and
co-workers [4-71 who demonstrated that quinones adsorbed on platinum electrodes
are electrochemically inactive. This discrepancy may arise from the difference in
adsorptive properties of the electrode materials (platinum and pyrolytic graphite,
respectively).
The pH-potential diagrams of the quinones are shown in Figs. 1 to 3. As one can
see from Fig. 1, the diagram for lawson consists of four intercepts with different
slopes of the pH-potential line: - 58 mV (pH -C4.15), - 87 mV (4.15 c; pH < 8.47),
- 58 mV (8.47 < pH -C10.86) and - 29 mV (pH > 10.86). Accordingly, five differ-
ent forms of lawson may exist in aqueous solutions. Two of them are oxidized
forms, while the other three are reduced. The unchanged forms (AH and AH,) are
192
stable in the acid region. At pH > 4.15 the neutral oxidized form AH loses one
proton and an anion A- is formed. The stoichiometry of the reduction of this anion
depends upon the pH of the solution. In the pH range 4.15-8.47, anion A-
undergoes a three-proton and two-electron reduction, producing a neutral leuco-
form, AH,. At pH > 8.47 the reduced forms, namely AH; (pH x 10.86) and AH’-
(pH > 10.86) are negatively charged:
(AH*-)
TABLE 1
Redox equilibria in the lawson system
TABLE 2
Acid-base equilibria in the lawson system
Transfer a Reaction pK
1-2 AHGA-+H+ 4.15
3-4 AH,FtAH; +H + 8.47
4-5 AH; a AH2- +H+ 10.86
a Numbers correspond to Fig. 1.
OH
+3H++4e- = 2
0- OH
(AH.A-) (2W)
In the acid and neutral regions both the oxidized (AH) and reduced (AH,) forms
of juglon are uncharged.
According to Friedheim [8] one more leuco-compound may exist in basic
medium, namely a doubly-charged anion AH*- (pK,&, = 10.6). In our investiga-
tions this form has not been detected in solutions of pH up to 12.
In the case of juglon no well-defined dependence of the midpoint potential on
concentration was observed in the whole range of pII. This may be explained by
assuming that the adsorptivities of the oxidized and the reduced forms are rather
close. Even in solutions of pH > 8.6, in which the oxidized form is supposed to be a
dimeric one and thus a dependence of E,,, upon the concentration would be
expected, we found no such dependence in the range from 0.09 mM up to the limit
of solubility (- 0.4 mM). In more dilute solutions, accurate values of E, were not
available due to the distortion of the peak shape by the simultaneous reduction of
residual amounts of oxygen present in the solution. The independence of E, of the
concentration in solutions of pH > 8.6 seems to be accounted for by the strong
adsorption of electroactive species on the carbon surface. Thus the surface coverage
is close to unity even in solutions of the low conc~tratio~ studied. The data
194
94
HO 0
0,3
AH-A-
0.2 2
QI
-0,1
-42
Fig. 2. pH-potential diagram for 5-hydroxy-1,4-naphthoquinone (juglon). The symbol AH stands for the
molecule of juglon shown in the figure.
quoted in Tables 3 and 4 for the standard redox potentials and the pK values refer
to the concentration range from 0.09 mM up to the limit of solubility of juglon.
There are some discrepancies between the values obtained by Friedheim [8]
(T = 20” C) and our data, cited in parentheses: E O’ = 0.428 V (0.417 V); ET’ =
TABLE 3
TABLE 4
Transfer a Reaction PK
l-2 2AH*AH*A-+H+ 8.60
2AH,$2AH; +2H + 6.96
3-4
TABLE 5
Redox equilibria in the plumbagin system a
a Data refer to equal amounts of the oxidized and reduced forms on the electrode surface.
b Numbers correspond to Fig. 3.
TABLE 6
Transfer a Reaction PK
1-2 2AH@AH.A-+H+ 9.01
3-4 2AHse2AH; +2H + 6.83
4-5 2 AH; F? AH; .AH*- +H+ 12.10
!? CH,
93
0.2
2AH AH-A-
O,i
\ 4 2
\
0 _ 1, 2AH, .29mV
'1 3
\
\
-0, I \
\ +H+ -44mV
-0,2 k
-0,s
-0.4
0 2 4 6 8 lo 12 14
Fig. 3. pH-potential diagram for 2-methyl-5-hydroxy-1,4naphthoquinone (plumbagin). The symbol AH
stands for the molecule of plumbagin shown in the figure.
196
0.033V (0.008 V);pK,, = 8.0(8.6) and pK,,, = 6.6(6.96). However, the data of
Zuman [lo] on pK,, (8.7) and p&i (7.0) are in close agreement with our values.
Plumbagin is practically insoluble in aqueous media. Thus there is no point in
referring the measured E, values to the concentration in solution. In our experi-
ments only a very thin film of quinone of about 1 to 2 monolayers, tightly bound to
the surface, was involved in the electrochemical conversion. All the remaining
quinone deposited on the electrode surface was electrochemically inactive. Because
of the insolubility of plumbagin all the values of E " as well as pK cited in Tables 5
and 6~refer to conditions of equal surface concentration of the appropriate con-
jugated forms.
The pH-potential diagram of plumbagin is given in Fig. 3. Regions of stability of
five different forms of this compound may be seen. Two of them are oxidized forms,
while the three others are reduced. In solutions of pH > 9 the oxidized form exists
as a dimer. Its reduction in weak basic medium (pH < 12.1) proceeds with the
formation of the anion AH;, whereas at higher pH values a dimeric form,
AH; . AH2-, is produced in the overall reaction:
(AH.A-) ( AH;.AH*-)
The results obtained show that all the compounds investigated have a complex
redox behaviour in aqueous solutions. It is interesting to note that non-substituted
1,4naphthoquinone undergoes a simple two-proton, two-electron reduction in the
whole range of pH (E o'= 0.470 V) [3]. Introduction of electron-donor substitutes
such as methyl and hydroxy groups not only decreases the value of the standard
redox potential of l,Cnaphthoquinone, but also affects the structure of the
pH-potential diagram appreciably.
REFERENCES