Mechanism of L-ascorbicacid oxidation and dehydro-L-ascorbicacid reduction

on a mercury electrode. I. Acid medium

JUANJOSERUIZ,ANTONIO
ALDAZA
, ~N D MANUELDOM~NGUEZ

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Departamento de Quimica Fisica, Facultad de Ciencias, Universidad de Sevilla, Spain

Received January 21, 1977

JUANJosh RUIZ,ANTONIO
ALDAZ,and MANUEL
DOM~NGUEZ.
Can. J. Chem. 55,2799 (1977).
A polarographic study of the oxidation mechanism of L-ascorbic acid and of the reduction
mechanism of dehydro-L-ascorbic acid was carried out in an acid medium.
For L-ascorbic acid, the oxidation process involves a two electron transfer and obeys the
overall reaction
AH2 + B 2e 2H+
The polarographic curve shows that the limiting current is governed by diffusion. On the
rising portion of the wave, the two electron oxidation process consists of two consecutive one
electron transfers, the second being the rate determining step (rds). The reaction orders, together with the Tafel slopes, were calculated.
The reduction of dehydro-L-ascorbic acid at the limiting current is kinetically controlled and
involves a two electron transfer. The reaction kinetic pathways were studied and the reaction
orders and Tafel slope were calculated. It is deduced that, for low overvoltages, the second one
electron transfer is the rate determining step.

+ +

JUANJosb RUIZ,ANTONIO
ALDAZet MANUEL
DOM~NGUEZ.
Can. J. Chem. 55,2799 (1977).
On a effectue, dans un milieu acide, une etude polarographique du mecanisme d'oxydation
de I'acide L-ascorbique et du mecanisme de reduction de I'acide dthydro-L-ascorbique.
Pour I'acide L-ascorbique, le processus d'oxydation implique un transfert de deux tlectrons
et est soumis a la reaction gtnerale

La courbe polarographique montre que le courant limitant est gouvernt par la diffusion. Sur
la portion montante de la vague, le processus d'oxydation a deux tlectrons implique deux
transferts successifs d'un tlectron, le deuxieme ttant l'ttape detern~inantede la vitesse de la
rtaction. Les ordres de la rtaction ainsi que les pentes de Tafel ont t t t calcults.
La rtduction de I'acide dthydro-L-ascorbique, a courant limitant, est contrBlke cinktiquement et implique un transfert de deux tlectrons. On a ttudie les chemins reactionnels cinttiques
et on a calcult les ordres de la reaction et la pente de Tafel. On en dtduit qu'a de bas survoltages,
le deuxieme transfert d'un Clectron est l'ttape dtterminante de la vitesse de la rtaction.
[Traduit par le journal]

Introduction
Several studies have been carried out (1-4) on
the electrochemical oxidation of L-ascorbic and
dehvdro-L-ascorbic acids on a mercurv electrode.
However, as far as we know, there exists no
detailed study on the mechanism of these reactions. The aim of this study is, therefore, to
determine the reaction mechanism for the two
acids using direct current polarography.
Experimental
Apparatus
The i-E curves were registered either automatically or
traced point by point using a PO4 Radiometer with the

'Present address: Departamento de Investigaciones

Quimicas, Centro Coordinado del C.S.I.C., Universidad
Autbnoma, Canto Blanco, Madrid 34, Spain.

damping circuit completely suppressed. The potentials

were measured vs. s.c.e. with a Beckman -~esearch
potentiometer, which was also used as a pH-meter.
Electrolysis was carried out with an Amel potentiostat,
model 541.
Cells and Electrodes
The polarographic measurements were carried out
using a thermostated Radiometer V519 cell. A saturated
calomel reference electrode was used. The working
electrode was a mercury capillary with the following
characteristics: m = 2.005 mg/s, t = 4.32 s, open circuit,
in our buffered solution at p H 1.80 and h = 40 cm.
Electrolysis was carried out using a mercury electrode
as a working electrode and a platinum auxiliary electrode.
Solutions, Products, and Measurements
All reagents used were Merck p.a. grade. As a supporting electrolyte solution, a buffered solution was used
with the following components and concentrations:
0.04 M acetic acid, 0.04 M phosphoric acid, 0.04 M

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2800

CAN. .I.CHEM. VOL. 5 5 , 1977

ammonium nitrate, and 0.2 M NaOH which were mixed

in varying proportions according to the p H desired. The
ionic strength was adjusted with NaN03 to 0.2 M for the
ascorbic acid study and to 0.5 M for the dehydro-Lascorbic acid study.
All measurements were carried out in an atmosphere of
nitrogen and at a temperature of 25 k 0.05"C.
The Mapson and Partridge technique (5) was used to
identify products by paper chromatography.
The Tafel curves were taken on the rising portion of the
polarographic wave ( i / i , i , < 0.2) and, to avoid depleting
the solution, the maximum current for plotting the
polarographic curve point by point was taken with each
first drop (6).

Results
General Behaviour
The L-ascorbic acid oxidizes over the DME
producing either one or two polarographic waves
depending on the p H of the solution. The first
wave is visible throughout the p H range 2-14,
whilst the second is only visible from p H 8. Only
the first wave was studied to p H 7.
The dehydro-L-ascorbic acid gives a stable
reduction in an acid medium (pH 0.5-6), Fig. 2,
only for solutions much more concentrated than
those norn~allyused in polarography ; e.g. for a
concentration of 4 x lo-' M currents of less
than 1 pA are obtained. This is due to the fact
that the acid in solution forms a polarographically active hydrate (1).

FIG. 1. First wave of L-ascorbic acid. Concentration

M. p H = 5.24.

5 x

Microcoulometric Measurements
The number of electrons taking part in the
overall reaction was calculated from the decrease
of the limiting current with the time of electrolysis (7). The average value obtained was 1.8.
Polarographic Behaviour
In the case of L-ascorbic acid, the limiting
current is independent of the p H whilst El,,
varies with the pH. The values of the slopes of
the linear sections were - 59 and - 27 mV/H+
decade.
El is independent of the concentration of the
L-ascorbic acid. The logarithmic analysis of the
polarographic wave gave straight lines with a
slope of 30 mV per decade that are practically
independent of the pH.
The limiting current is controlled by diffusion
as: log i,,, vs. log h (corrected for the back
pressure) is linear with a slope of 0.5; i,,, has a
temperature coeflicient of 1.1% per "C, and is
proportional to the concentration of the Lascorbic acid in the bulk of the solution.
In the case of dehydro-L-ascorbic acid, the
limiting current is independent of the p H and the
variation of El,, with the p H is shown in Fig. 4.
The values of the slopes were -44 and -72
mV/H decade.
The limiting current is controlled kinetically
(i,,, independent of h and with an elevated temperature coefficient).

FIG. 2. Wave of dehydro-L-ascorbic acid. ConcentraM. p H = 2.81.

tion 4 x

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RUIZ ET AL.

FIG.3. L-Ascorbic acid. Variation of E l l , with pH.

Tafel Curves and Reaction Orders

(a) Influence of pH. With L-ascorbic acid, the
Tafel curves are independent of the p H and their
slopes have an average value of 34 mV per
decade.
The reaction orders with respect to the H +
concentration are :

FIG.4. Dehydro-L-ascorbic acid : variation of El

with pH.

,,

the depolarizing agent was 1 in the case of both

acids and was independent of the potential at
which measurements were taken.

The order is independent of the potential in

the area where Tafel's law is obeyed.
For dehydro-L-ascorbic acid, the Tafel slopes
are equally independent of the p H with a mean
value of 43 mV. The reaction orders with respect
to the H + concentration are:

Electrolysis and Identification of Products

The first product of the oxidation of L-ascorbic
acid was identified by paper chromatography of
a solution of L-ascorbic acid at p H 4 which had
undergone electrolysis at a controlled potential.
From the chromatogram, two zones were
observed with the R , characteristics (0.07 weak
and 0.49 strong) of dehydro-L-ascorbic acid. As
the position of the weak zone coincides exactly
with that assigned to 2,3-diketogulonic acid, it
can be assumed that there is a rupture of the
lactone ring of the dehydro-L-ascorbic acid
during the period of the electrolysis or during
the chromatography.

(b) Influence of the concentration. The reaction order with respect to the concentration of

Conclusion
In previous papers (2-4) it appeared to be
established that the overall oxidation mechanism of L-ascorbic acid takes place through a
reversible transfer of charge followed by a rapid
chemical reaction of the product formed with
water to form a very stable hydrate.
Our polarographic results confirm that the first

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2802

CAN. J. CHEM.

FIG.6. L-Ascorbic acid: reaction orders.

FIG.5. L-Ascorbic acid: representation of Tafel's law.

wave of L-ascorbic acid is produced by a polarographically reversible two electron transfer

(Tomes slope 30 mV/H+ decade) in which two
protons intervene in the interval p H 2-5 (slope
- 59 mV/H+ decade) and another between p H
5-9 (slope -27 mV/H' decade). Thus, the
overall reaction in the p H 2-9 interval would be:

substituting AH, by AH- for pH's larger than

the pKl of L-ascorbic acid.
The presence of a free radical (8) in the oxidation process of L-ascorbic acid clearly indicates
that the transfer of two electrons is realized
electron by electron.
With the aforementioned conclusions, the
mechanism can be represented by the following
reaction kinetic pathways, as shown in Fig. 7
where reaction 1 represents the dissociation of
H + from the carbon 3, reactions 2 and 3 repre-

sent the one electron transfers with the formation

of a free radical. Reactions 4 and 5 represent the
normal hydration mechanism of carbonyl
groups (9).
Assuming reaction 3 as being the rds and
applying the approximation of equilibrium state,
the value of the anodic current intensity on the
rising portion of the wave can be expressed as
(taking the electrokinetic potential to be negligible) :

Cr
exp ((2 - ~ ) F E / R T )
KICH + C"

where C, is the total concentration of L-ascorbic

acid in the bulk of the solution; C, is the concentration of the H + ions; Kl and K, are the
equilibrium constants of reactions 1 and 2;
k , is the rate constant of the rate controlling
step. Table 1 gives a comparison between the
theoretical values deduced in the aforementioned
reaction kinetic pathways and the experimental

RUIZ ET AL.

do

HO-C-C,

I1

/O

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[I] HO-C-CH

k,

II

/o

-0-C-CH

k-1

(1

/O

121 -0-C-CH
I

+ Ht

- - - .- - - .- -.
A/ Oi

//O

HO-C-C,

fiO

HO-C-C,

/,

I '0-C-C,;

k2&:
I/ --jO
L - .- - .- ..-7
I-o-c
-- f c ~
k-2
1

+ H + + le-

HOCH

HOCH

CH20H

CH20H

FIG.7. L-Ascorbic acid: reaction kinetic pathways.

TABLE
1. Comparison between theoretical values (based on mechanisms in
Fig. 7) and experimental results
Value
-

Parameter
Tafel slope
Order with respect to
L-ascorbic acid concentration
Order with respect to H + ion

Theoretical
(b cz 0.5)

Experimental

39 mV

34 mV

1
-2 for Kl c< CH
- 1 for K, >> C,

-1.9 (pH2-4)
-0.9 (pH 6-9)

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CAN. J. CHEM. VOL. 5 5 , 1977

//O

HOC-C\

I1

[5] -0C-CH

/o
I

k5

H+

FIG.8. Dehydro-L-ascorbic

k-5

11

HOC-CH

/o

acid: reaction kinetic pathways.

results (where p is assumed to have a value of

0.5).
As is logical, in the case where pK, is less than
the p H of the medium, the reaction:
AH2 F?. AH-

//O

HOC-C\

+ H+

should not be taken into account.

The close agreement between the experimental
and theoretical results clearly indicates that the
oxidation process takes place as shown in Fig. 7.
Dehydro-L-ascorbic Acid
The polarographic study shows that the reduction process includes a chemical stage which
precedes the electron transfer and which controls

the reaction rate at those potentials corresponding to the limiting current.

The electron transfer is not a reversible process
as no linearity is observed in the plot E vs. log
i/(iL - i).
The low value of iL (< 1 FA) compared with
the dehydroascorbic acid concentration (4
x
M) indicates that the preceding reaction
is shifted towards the formation of an electrochemically inactive substance. This substance
could be the compound produced during the
hydration of one of the two carbonyl groups of
the dehydroascorbic acid (1, 2).
From these results and granted that, in this
case, it is virtually impossible for a simultaneous

RUIZ ET A L

TABLE2. Comparison between theoretical values (based on mechanisms in

Fig. 8) and experimental results

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Value
Parameter

Theoretical

Experimental

Tafel slope
Order with respect to dehydroL-ascorbic acid concentration
Order with respect to H + ion

- 39 mV

-43 mV

1
1 for l>>KICH
0 for l<<KICH

1 . 1 (pH0.5-5)

TABLE3. Comparison between theoretical values (based on mechanism in Fig. 9)

and experimental results
Value
Parameter

Theoretical

Experimental

-39 mV

-43 mV

1
2 for 1>>(1+K2K3)K1CH

Tafel slope
Order with respect to dehydroL-ascorbic acid concentration
Order with respect to H + ion

two electron transfer to take place by the tunnel

effect (the probabilities being extremely low),
reduction mechanism is proposed as shown in
Fig. 8, where reactions 1 and 2 represent the
dehydration of the carbonyl group, 3 and 4 the
one electron transfers, and 5 the recon~bination
with the H + ion to form L-ascorbic acid.
Assuming reaction 4 as the rds, the function
i = f(E) in the rising portion of the wave would
be :
[2]

i = 2Fk41C1K2K3

CTCH
1 K l K 2 KlCH
x exp (-(1
P)FE/RT)

+
+

where C, = total concentration of L-ascorbic

acid, CH = concentration of hydrogen ions,
K,, K2, K3 = equilibrium constants, k3 = rate
constant.
Table 2 shows the close agreement between the
theoretical and experimental results and permits
us to assume that our mechanism is correct.
Near p H 5 a variation in the slope of the
El,, vs, p H plot (Fig. 2) is observed together
with a change in reaction order with respect to
the H + ion which varies from 1.1 to 2. A potentiometric titration of dehydro-L-ascorbic acid
gives a first point of complete neutralization at
p H 5.3. It is assumed that this is caused by the
rupture of the lactone ring of the dehydro-L-

ascorbic acid and produces the 2,3-diketogulonate anion according to (9). Therefore, after
this pH, the dehydro-L-ascorbic acid in solution
is in the form of the 2,3-diketogulonate and the
first reaction of the reduction mechanism would
be as shown in Fig. 9.

coo-

HO. I

HO,

HOCH

FIG. 9. First reaction on the reduction mechanism of

the dehydro-L-ascorbic acid for p H > 5.

Once the dehydro-L-ascorbic acid is formed,

the subsequent reactions will occur as before.
Assuming, once again, the last transfer reaction to be the rds, the i-E function is now
expressed by:

x exp (-(1

+ P)FE/RT)

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CAN. J . CHEM. VOL. 5 5 , 1977

Table 3 shows the complete agreement between

the theoretical and experimental results.

4. C. CATTANEO
and G. SARTORI.Gazz. Chim. Ital. 72,
351 (1942).
5. L. W. MAPSONand S. M. PARTRIDGE.
Nature, 164,

Acknowledgements
This study was supported by the Comisi6n
Asesora de Investigacibn Cientifica Ttcnica,
Madrid.

(1949).
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and E. GILEADI.J . Electroanal.
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8. A. ALDAZand A. M. ALQUIE.J. Electroanal. Chem.
47,532 (1973).
9. C. K . INGOLD.Structure and mechanism in organic
chemistry. 2nd ed. Cornell Univ. Press, Ithaca. 1969.
p. 1014.

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75,2473 (1953).
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and T. WASA.Bull. Chem. Soc.
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