ANALYTICAL SCIENCES SEPTEMBER 2002, VOL.

18 1
2002 © The Japan Society for Analytical Chemistry

Electrochemical Behavior of 2-Halogenated Derivatives of

N,N-Dimethyl-4-aminoazobenzene at Mercury Electrode
Mustafa UÇAR,*† A. Osman SOLAK,* and Necati MENEK**

*Ankara University, Faculty of Science, Department of Chemistry, Tandog˘an, 06100 Ankara, Turkey
**Ondokuz Mayıs University, Faculty of Science and Arts, Department of Chemistry,
55139 Kurupelit-Samsun, Turkey

The electrochemical behavior of 2-halogeno-N,N-dimethyl-4-aminoazobenzene derivatives was investigated using

various polarographic and voltammetric methods. The peak potentials of these derivatives were observed to shift towards
negative values along with an increase in the pH. A reduction of the azo linkage took place via two electrons at pH > 4,
but four electrons at pH < 4 in aqueous–ethanol mixtures. The standard rate constants were determined with (Laviron
technique) or without (Nicholson technique) taking the adsorption phenomena into account. The diffusion coefficients
were calculated from the cyclic voltammetric data using a method developed by Garrido. The amount of adsorbed
substances and transfer coefficients for the electron transfer were also determined. A mechanism for the electrode
reaction is proposed. These compounds can be quantitatively determined between 1  10–5 M and 1  10–7 with DPP and CV.

(Received May 29, 2002; Accepted July 8, 2002)

voltammetry and constant-potential electrolysis.

Introduction
Aromatic azo compounds have attracted great interest in recent
years due to their carcinogenic potency 1 and their use in textile2
and pharmaceutical industries as dyes and coloring agents. 3
They are also starting materials in the synthesis of many organic
compounds.4,5 Early investigations on the polarographic
reduction of azobenzene and substituted azobenzenes have been
discussed briefly.6
The electrochemical behavior of azo compounds in acidic and
basic media was investigated using constant-potential
coulometry, differential pulse polarography, ac polarography,
sampled current polarography, cyclic voltammetry, and linear
sweep voltammetry.7–12
Although the electrochemical behavior of these compounds in
both aqueous and non-aqueous media has been widely studied,
there has been no systematic study concerning the effect of
adsorption on the electrochemistry and kinetics of these
compounds in the literature. Adsorption plays an important role
in their behavior. The only mention of this effect appeared in
studies by Florence,13 Pezzatini and Guidelli,14 and Uçar et al.9,12
This paper mainly concerns the electrochemical behavior and
mechanism of various 2-halogeno-N,N-dimethyl-4-
aminoazobenzene derivatives in the presence of adsorption
using methods developed by Laviron15 and Garrido.16 Data
without taking adsorption phenomena into account using the
Nicholson17 method are also given. Also, the surface excess
concentration, transfer coefficients, standard heterogeneous rate
constants (ks) and the number of electrons transferred to 2-
halogeno-N,N-dimethyl-4-aminoazobenzene derivatives (I, II,
III) were determined using chronocoulometry, cyclic
†
To whom correspondence should be addressed.
E-mail: ucar@science.ankara.edu.tr
The general structure of the investigated 2-halogeno-N,N-
dimethyl-4-aminoazobenzene derivatives is
where X = Cl (I), Br (II), I (III).
Experimental
Apparatus
Polarographic measurements were carried out with a
BAS100B Electrochemical Analyzer equipped with a BAS100B
Cell Stand, a PAR 303A static mercury drop electrode (SMDE)
and a PAR Model 305 stirrer. All solutions were deaerated for
10 min with pure nitrogen, deoxygenated with a vanadium
chloride solution, concentrated HCl and amalgamated zinc, and
blanketed thereafter. The pH values of the solutions were
recorded by an ORION 720A pH-meter. The buffer solutions
used were the Britton–Robinson (BR) type with pH values of 2 –
12. Polarographic and voltammetric experiments were carried
out with an SMDE in a three-electrode cell equipped with a Pt
wire auxiliary and Ag/AgCl reference electrodes. Cyclic
voltammetric and chronoamperometric experiments were
performed by hanging a mercury drop electrode (HMDE)
having a surface area of 0.0145 cm2. Constant-potential
electrolysis was carried out using a mercury pool electrode with
a surface area of 19.6 cm2. The number of electrons was
calculated from the amount of charge passed (Q = nFN) after
68.15 min of electrolysis, the time for the current to drop by
about 1% of its initial value. All of the measurements were taken
at the laboratory temperature (25 ± 1˚C) and no maximum
2 ANALYTICAL SCIENCES SEPTEMBER 2002, VOL. 18
Fig. 1 Cyclic voltammograms of 1.67  10–5 M 2-I-N,N-dimethyl- 4-
aminoazobenzene in (a) acidic (pH 2.00), (b) basic media (pH 6.83)
[EtOH:BR = 1:5 /, scan rate = 100 mV/s, with HMDE and
Ag/AgCl reference electrode)].
Fig. 2 Change in the half-wave potentials (E1/2) of 1.67  10–5 M 2-
halogeno-N,N-dimethyl-4-aminoazobenzene derivatives with the pH
[EtOH:BR = 1:5 /, scan rate = 10 mV/s, drop time: 1 s with SMDE
and Ag/AgCl reference electrode)].
suppressor was used.
Reagents
Acetic acid (BDH, Analar), phosphoric acid (Merck), boric
acid (Riedel) ammonium metavanadate (Merck), and sodium
hydroxide (Merck) were used without further purification. The
water used in the preparation of the solutions was distilled and
deionized by an ELGASTAT water purification system.
The aromatic azo compounds used were synthesized
according to the literature18 and their purities were checked with
mp determination, as well as UV, IR and NMR spectroscopy.19
Results and Discussion
Characterization of the electrode reaction
2-Halogeno-N,N-dimethyl-4-aminoazobenzene derivatives
were found to give two reduction waves in both acidic and basic
media. However, the second peaks are too ill defined to take
into account for quantitative and qualitative purposes. The
cyclic voltammograms of 2-I-N,N-dimethyl-4-
aminoazobenzene obtained in both acidic and basic media are
Fig. 3 Change in the limiting current of 1.67  10–5 M 2-halogeno-
N,N-dimethyl-4-aminoazobenzene with the pH [EtOH:BR = 1:5 /,
scan rate = 10 mV/s, drop time = 1 s with SMDE and Ag/AgCl
reference electrode].
Fig. 4 Change in the ip,c in the 2-halogeno-N,N-dimethyl-4-
aminoazobenzene derivatives with the concentration in a basic
medium with DPP [EtOH:BR = 1:5 /, scan rate = 100 mV/s, with
HMDE, pH 4.9 and Ag/AgCl reference electrode)].
given in Figs. 1a and 1b as examples. The first cathodic peak is
due to a reduction of the –N=N– group to –NH–NH– in a basic
medium, and the breakage of the –NH–NH– bond in an acidic
medium. The second cathodic peak is most probably due to the
catalytic hydrogen wave, as mentioned in the literature. 12,20,21
The first reduction peak of 2-I-N,N-dimethyl-4-
aminoazobenzene was observed at Ep,c = –72 mV in an acidic
medium (pH 2.00) and Ep,c = –455 mV in a basic medium (pH
6.83). An anodic peak appears corresponding to the first
reduction peak of 2-halogeno-N,N-dimethyl-4-
aminoazobenzene derivatives above a pH value of 4.0. The
reduction peak potentials shift to negative values as the medium
becomes more basic.
The E1/2–pH graphs of sampled current polarographic
experiments for all derivatives were found to be linear (Fig. 2).
The observed shift in E1/2 with decreasing pH to more positive
values can be explained by a preliminary protonation of the azo
group, leading to a decrease in the electron density in the region
of the bond between two nitrogen atoms, thus easing the
reduction. This dependence indicates that there is a proton
transfer in the electrode reactions.
The limiting currents of N,N-dimethyl-4-aminoazobenzene
derivatives with the pH give an S-shaped curve (Fig. 3). It can
also be seen from Fig. 3 that the limiting current observed in an
acidic medium is roughly twice as large as that in a basic
ANALYTICAL SCIENCES SEPTEMBER 2002, VOL. 18 3

Table 1 Change of the peak potentials and the peak currents

belonging to the first reduction waves of 2-chloride-N,N-
dimethyl-4-aminoazobenzene derivatives with the concentration
in an acidic medium (pH 5.5)

DPP CV
C/10–7 mol L–1
Ep/mV ip10–7 Ep,c/mV ip,c10–7 A
A
16.7 –270 0.76 –299 2.63
33.3 –250 1.44 –285 3.88
83.3 –250 2.86 –279 7.34
133 –260 3.91 –288 9.97
167 –270 3.58 –320 11.3

EtOH:BR = 1:5 / (EtOH:BR), and Ag/AgCl reference electrode.

Correlation coefficients (R) for C(mol/L)–peak current (A) graphs:
0.976 for DPP and 0.995 for CV.
Fig. 5 Variation of the cathodic peak currents with 1/2 for 1.67 
10–6 M 2-halogeno-N,N-dimethyl-4-aminoazobenzene derivatives pH
 5.00.
medium, which can be explained by a change in the number of
exchanged electrons upon a transition from an acidic solution to
an alkaline solution. This is in complete accordance with the
literature.9,12,21–23
The effect of the concentration is shown in Fig. 4. The current
increases with the concentration in a linear fashion at lower
concentration values. It becomes almost constant at higher
concentrations (1  10–5 M), which may be attributed to an
adsorption phenomenon. The linear increase in the current with
the concentration at a lower concentration range creates the
possibility of a quantitative determination of these compounds
using differential pulse polarography.
The dependence of the peak heights (DPP and CV tech.) on
the concentration of the depolarizer is linear between 1.67 
10–5 to 1.67  10–7 M. These results are given in Table 1.
The Nicholson–Shain criteria17 (i.e. a plot of the current
function against the logarithm of the scan rate) revealed that the
reduction of the –N=N– bond is quasi-reversible for all of the
derivatives investigated, and that the degree of reversibility Fig. 6 Variation of the ip,a/ip,c ratio with 1/2 for 1.67  10–6 M 2-
changed from one derivative to another. This conclusion was halogeno-N,N-dimethyl-4-aminoazobenzene derivatives pH  5.00.
further verified by the fact that the difference between the half-
wave potential of SCP (E1/2) and the peak potential of DPP (Ep)
was more than 25 mV. The half-wave potentials were observed
to change with the drop time, which indicates that the system is that the adsorption phenomenon has effects. 24,25 Also, the linear
not reversible. The graph of the potential against log(id–i)/i is shape of ip,c/C vs. the C graph at low concentrations (Fig. 7) and
supposed to be linear in a reversible case with a slope of 59/n the decrease in the current function (ip,c/C1/2) with an increasing
mV. The slope of this linear graph is more than 59/n mV, scan rate are further indications of adsorption.24,25
indicating irreversibility, which may arise from slow electron The adsorptions of 2-halogeno-N,N-dimethyl-4-
transfer, adsorption or chemical complications. As can be seen aminoazobenzene derivatives on a mercury surface were clearly
from Figs. 5 and 6, the cathodic peak current increased with an observed when the scan rate was increased at 30 V/s.
increase in 1/2. The ip,a/ip,c ratio tended to 1.24 These
results Surface concentration measurements
show that the system is not reversible; moreover, these results The surface concentrations of the adsorbed molecules of 2-
are consistent with a quasi-reversible behavior. 24 Cathodic peak halogeno-N,N-dimethyl-4-aminoazobenzene derivatives were
current increased with an increase in 1/2 and the ip,a/ip,c ratio studied by chronocoulometry. The surface excess  values
tended to be unity.24 were determined using Q–t1/2 graphs. The extrapolation of the Q–
t1/2 graph of the supporting electrolyte and a solution containing
Effect of adsorption N,N-dimethyl-4-aminoazobenzene derivatives to t1/2
2-Halogeno-N,N-dimethyl-4-aminoazobenzene derivatives = 0 point gives us the Qdl and Qt=0 values, respectively. The Qads
are large-molecule compounds. That is why one has to values are calculated from Qads = Qt=0 – Qdl. The surface excess
determine whether an adsorption phenomenon is present and values are then obtained from Qads = nFA.26
affects the electrode reaction. The most useful electroanalytical
technique to investigate adsorption phenomena is cyclic
Q = 2nFAC (Dt/)1/2 + Qdl + nFA, (1)
voltammetry; there are a few ways to determine adsorption
using this technique.24
Here, Qdl is the charge due to the double layer,  is the amount
The log ip vs. log  plots are given for each compound. The
of adsorbed reactant and the other symbols have their usual
slopes of these graphs are greater than 0.5 and approximately
meanings. The amount of reactant adsorbed on the mercury
0.9 ± 0.01 for all of these derivatives. These results indicate
4 ANALYTICAL SCIENCES SEPTEMBER 2002, VOL. 18

Table 2 Diffusion coefficients, amount of reactant adsorbed on the mercury surface ( , mol cm–2), standard rate constants (ks) values
in 1:5 / EtOH:BR buffer, C = 1.67  10–5 M 2-halogeno-N,N-dimethyl-4-aminoazobenzene derivatives in acidic media (pH 5.08)
Cottrella Garridob Nicholsonc Lavirond

Compound Diffusion coefficient

(D) (cm2 s–1) Diffusion coefficient ks ks  e (mol cm–2)
D  ts/N1/2 (D) (cm2 s–1) (cm s–1) (cm s–1)   ts/N1/2
D  ts/N1/2 ks  ks 
ts/N1/2 ts/N1/2
2-Cl-4-N,N 2.10  10–5  7.76  10–6  10.41  10–3  2.5  10–1  1.31  10–11 
5.25  10–6 5.02  10–7 2.18  10–3 1.5  10–2 3.28  10–12
2-Br-4-N,N 1.77  10–5  1.83  10–6  6.50  10–3  2.3  10–1  1.79  10–11 
4.43  10–6 1.28  10–7 1.37  10–3 1.4  10–2 4.48  10–12
2-I-4-N,N 1.73  10–5  7.92  10–6  2.97  10–3  1.8  10–1  2.40  10–12 
4.33  10–6 5.13  10–7 6.24  10–4 1.1  10–2 6.01  10–13
EtOH:BR = 1:5 /, and Ag/AgCl reference electrode. a. Calculated from Cottrell slope (Eq. (2)), the data were determined by the use of
i–t–1/2 plots in the diffusion region (pulse amplitude 250 ms, E1 = –400 mV and E2 = –900 mV). b. Calculated from Eq. (3), considering
adsorption (tp = 15 s). c. Calculated from Eq. (4), ignoring adsorption. d. C = 1.67  10–7 M, calculated from Eq. (5), considering
adsorption (for confidence interval of 95%, mean  value for the cathodic peak is 0.30). e. Qdl = 3.3  10–9C (Eq. (1)), (pulse amplitude
250 ms, E1 = –400 mV and E2 = –900 mV).

controlled conditions using the Cottrell equation. The

experimental Cottrell slopes were determined from a
chronoamperometric i vs. t–1/2 plot. In the case of adsorption,
the following equation derived by Garrido et al. at 25˚C is
applicable:16

ip = 1.06  106n2ACD1/2t
p 1/2, (3)

where a Langmuir-type of adsorption was assumed with a non-

Fig. 7 Change of the ip,c/C ratio of 2-halogeno-N,N-dimethyl-4-
aminoazobenzene derivatives with the concentration in a basic
medium [EtOH:BR = 1:5 /, scan rate = 100 mV/s, with HMDE and
Ag/AgCl reference electrode)].
surface (, mol cm–2) is given in Table 2. Foresti et al.27
determined the maximum adsorption of azobenzene in water +
ethanol to be 2.5  10–10 mol cm–2. However, they carried out
their study in the presence of surface-active reagents.
Determination of standard rate constants
The standard rate constants of 2-halogeno-N,N-dimethyl-4-
aminobenzene derivatives were calculated by two different
methods. One of these methods, namely the Nicholson method,
assumes a diffusion-controlled current. The other method, by
compact monolayer film of the adsorbed molecules on the
mercury surface. Here, tp is the adsorption time from the
beginning of the life of the drop until Ep is reached. The other
symbols have their usual meanings.
The values in basic media, where adsorption has a significant
effect, were found to be lower and more reasonable than those
obtained for the uncomplicated case using the Cottrell equation
(Table 2). Hence, in all equations to calculate the standard rate
constants, diffusion coefficients found by the Garrido methods
were used (Table 2).
In acidic media, it was observed that the difference between the
values of the diffusion coefficients determined by the Cottrell
and Garrido methods was not significant. This shows that
adsorption has a smaller effect in acidic media.
Nicholson method
The ks value of the electron-transfer reaction was also
determined by using a technique developed by Nicholson 17 in
1965, using
nF

Laviron, assumes an adsorption at the electrode surface. In the  DO  RT

k s
former methods, calculating the diffusion coefficients is  DR  (4)
necessary. If the potential applied to the electrode falls into the =  nF DO ,
diffusion-controlled region, the current is given by the Cottrell RT
equation,
where the  values were determined from a working graph
nFACD
i = —— 1
—1/2
/2
—1/2— , (2) given by Nicholson, and DO/DR was taken as unity. The change
 t of EP  n vs. the ks values was found to reach a limiting value
at high scan rates in both acidic and basic media (Table 2).
which is very useful to determine the diffusion coefficients. This method requires a continuous equilibrium condition upon
However, it is only applicable for those cases where electrode the electrode surface, and is not suitable for very high or very
reactions are diffusion-controlled and do not have any low scans rates. It is applicable for a peak separation of 60 –
adsorption or chemical complications. Therefore, all of the 220 mV.
diffusion coefficients were elucidated under diffusion-
ANALYTICAL SCIENCES SEPTEMBER 2002, VOL. 18
Laviron method
Since the adsorption phenomenon was found to have an
effect, the rate constants were determined using a method
developed by Laviron, which takes the effect of adsorption into
account.15 The ks values were calculated using
n F EP
logks =  log (1– )+(1– )log  –log —R—T  –  (1– ) — — —— ,
nF 2.3RT
(5)
The  value was determined from the slope of the Ep,c vs. log 
graph, which is equal to 2.53RT/nF for the cases Ep,c > 200/n
mV. The number of electrons (n) transferred was taken as two
for a basic medium and four for an acidic medium, as
mentioned above. The ks values, determined by these two
different methods, are tabulated in Table 2. The standard rate
constant determined by the Nicholson method was found to be
different from those determined by the Laviron method, which
indicates the presence of adsorption (Table 2). The halogene
atoms are easily deformed and can act as electron bridges in
some electrode reactions, resulting in a change in the values of
the charge-transfer coefficients.
All of these methods were used under the conditions to which
they respectively apply. In other words, the standard rate
constants for the Nicholson methods were determined at high
concentrations where adsorption had no effect, while the rate
constants determined by the use of the Laviron method were
those obtained under the conditions where the adsorption
phenomenon was operative (i.e. at low concentrations).
Mechanism of the electrode reaction
The number of electrons transferred determined by constant-
potential-coulometry. Bulk electrolysis was continued until the
current dropped to about 1% of its original value. The results
indicate that the number of electrons transferred was about 4 for
an acidic medium (pH 5.1, Ep,c = –600 mV, n = 3.74 ± 0.3) and
2 for a basic (pH 9.82 Ep,c = –1000 mV, n = 1.73 ± 0.3)
medium, respectively, which is in good compliance with other
studies.9,12,23,25,28 The effects of adsorption were minimized by
using high concentrations and low scan rates. The reduction of
the 2-halogeno-N,N-dimethyl-4 aminoazobenzene derivatives
was found to be quasi-reversible due to the fact that Ep is
larger than 59/n (mV), which increased with the scan rate, and
the shift of the cathodic peak potential (Ep,c) towards negative
values with an increasing scan rate. The case of 2  10–51/2
< ks
< 0.31/2 corresponds to a quasi-reversible situation. The
ks
values obtained in this study fall into this range.
The ill-defined second peak is most probably due to a
catalytic hydrogen wave.12,20,21 This conclusion is based upon the
fact that the peak current decreases and the E1/2 value shifts to a
negative potential with increasing pH, while the peak currents
become stabilized after a certain pH value, and suppression of the
peak after the addition of surface-active compounds, such as
TritonX-100. These are the most important features of catalytic
hydrogen waves.
Accordingly, the electrode reaction mechanism of 2-
halogeno-N,N-dimethyl-4-aminoazobenzene derivatives in
acidic and basic media is given in Scheme 1.
There was no anodic peak observed for the reduction of 2-
halogeno-N,N-dimethyl-4-aminoazobenzene derivatives in
acidic media (pH < 4), which verifies this mechanism. Since all
of the steps in this mechanism take place at the same potential,
there occurs a single reduction peak corresponding to the
transfer of four electrons. This reaction stops at the first step in
5
Scheme 1
basic media with two-electron transfer.9,12,23,25,28 A TLC analysis
of the bulk electrolysis products gave similar results to the
literature.23,25 The polarographic reduction products of azo
compounds have also been analyzed by TLC23 and HPLC.29
Acknowledgements
The authors are grateful to Ankara University Research Fund
for its financial support of this work under Grant No: CHE 95-
25-00-04. The authors thank Dr. Mehmet Toy for the supplying
the azo compounds.
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