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Monatsh Chem (2015) 146:14851493

DOI 10.1007/s00706-015-1410-2

ORIGINAL PAPER

Kinetic and mechanistic investigations and thermodynamic


quantities for different steps involved in the mechanism
of oxidation of procainamide by hexacyanoferrate(III) in aqueous
alkaline medium: a spectrophotometric study
M. D. Meti M. H. Lamani A. G. Naikar S. S. Sutar

S. T. Nandibewoor S. A. Chimatadar

Received: 20 May 2014 / Accepted: 2 January 2015 / Published online: 31 January 2015
Springer-Verlag Wien 2015

Abstract The kinetics of oxidation of procainamide by Graphical abstract


alkaline hexacyanoferrate(III) at a constant ionic strength
of 1.10 mol dm-3 has been studied spectrophotometrically O
N
at 25 C. The stoichiometric analysis indicates that one N
H + 2 [Fe(CN)6]3- + 3 H2O

mole of procainamide requires two moles of hexacyano- H 2N

ferrate(III). The reaction products are identified and


O
confirmed by IR, NMR, and GCMS spectral studies. The H 2N H
OH + + 2 C2H6 + 2 [Fe(CN)6]4- + 2 OH-
reaction is first order with respect to oxidant, Fe(CN)3-
6 and H NH2
H 2N
less than unit order with respect to procainamide and alkali 4-Aminobenzoic acid (E)-Ethene-1,2-diamine

concentrations. Increasing ionic strength and decreasing


dielectric constant of the medium increases the rate of
reaction. The added products did not have any significant Keywords Hexacyanoferrate(III)  Procainamide 
effect on the rate of reaction. Based on the experimental Kinetics  Oxidation  Thermodynamic parameters
results, a suitable mechanism is proposed and the following
rate law is derived and verified. Activation parameters are
evaluated with respect to the slow step of the mechanism
and thermodynamic quantities are also calculated. Vol- Introduction
tammetric behavior of procainamide is also made.
Procainamide is a pharmaceutical antiarrhythmic agent
used for the medical treatment of cardiac arrhythmias and
also used for both supraventricular and ventricular
arrhythmias indicated in the treatment of premature ven-
tricular contractions, ventricular tachycardia, atrial
fibrillation, and paroxysmal atrial tachycardia [1]. Pro-
cainamides major active metabolite is N-
acetylprocainamide (NAPA), which is approximately
equipotent with the parent drug as an antiarrhythmic agent
[2]. NAPA has an elimination half-life about twice that of
Electronic supplementary material The online version of this procainamide, and it can reach somewhat higher plasma
article (doi:10.1007/s00706-015-1410-2) contains supplementary
material, which is available to authorized users. levels during chronic procainamide administration [3].
Procainamide measurement in plasma is advocated as a
M. D. Meti  M. H. Lamani  A. G. Naikar  useful, if not mandatory, guide to therapy. The accepted
S. S. Sutar  S. T. Nandibewoor  S. A. Chimatadar (&)
therapeutic concentration range for procainamide hydro-
P. G. Department of Studies in Chemistry, Karnatak University,
Pavate Nagar, Dharwad 580003, India chloride (PAH) is 48 mg/dm3, but its major metabolite, N-
e-mail: schimatadar@gmail.com acetylprocainamide, which also has an antiarrhythmic

123
1486 M. D. Meti et al.

effect in humans, is found in similar concentrations in the (1) accumulate the kinetic data, (2) intermediate detection
plasma of patients who are undergoing therapy with pro- and product analysis, (3) concentration determination of all
cainamide. Therefore, therapy can be optimal only if both species present, (4) deciding on a method of following the
procainamide and N-acetylprocainamide are considered rate, (5) kinetic analysis, (6) determination of the mecha-
[4]. The chemical structure of procainamide hydrochloride nism, (7) design kinetic rate laws, (8) deduce
is shown in Fig. 1. thermodynamic parameters, and (9) characterize the pro-
Hexacyanoferrate(III) has been widely used to oxidize ducts. We have also studied the electrooxidation of
numerous organic and inorganic compounds in alkaline and procainamide by glassy carbon electrode.
acidic media. Literature survey reveals [5, 6] that alkaline
hexacyanoferrate(III) ion simply acts as an electron
abstracting reagent in redox reactions. However, [7] have Results and discussion
suggested different paths of oxidation of aldehydes, ketones,
and nitroparaffins by hexacyanoferrate(III). While [8, 9] Stoichiometry and product analysis
discussing the oxidation of formaldehyde, acetone, and ethyl
methyl ketone by hexacyanoferrate(III), they have suggested Different sets of reaction mixtures containing varying ratios
that the oxidation takes place via an electron transfer process of hexacyanoferrate(III) to PAH in the presence of constant
resulting in the formation of a free radical intermediate. In amount of OH-, KNO3 and at constant ionic strength of
alkaline medium, the redox potential [10] of the couple 1.10 mol dm-3 were allowed to react for about 5 h at 25 C
FeCN3 4
6 = FeCN6 is 0:450 V: under nitrogen atmosphere in a closed vessel. The remaining
Thus, the study of PAH becomes important because of concentration of hexacyanoferrate(III) was assayed by
its biological significance and selectivity towards the oxi- measuring the absorbance at 420 nm. The results indicated
dants. In view of the lack of literature on the oxidation of that two moles of hexacyanoferrate(III) reacted with one
PAH by hexacyanoferrate(III), and to explore the mecha- mole of procainamide as given in Scheme 1.
nistic aspects of hexacyanoferrate(III) oxidation in alkaline After the completion of the reaction, the reaction mix-
medium, we have studied the title reaction. The main ture was acidified, concentrated, and extracted with ether.
important objectives of the present kinetic investigation are The major products were identified as 4-aminobenzoic acid
and (E)-ethene-1,2-diamine, which was separated by col-
umn chromatography using hexane: ethyl acetate as eluent.
O . The IR spectrum of 4-aminobenzoic acid showed a sharp
HCl
band at 1,672 cm-1 which corresponds to carbonyl group
N
N stretching. The bands at 3,366 and 3,465 cm-1 are due to
H symmetric and asymmetric stretching of -NH2 group (suppl.
Fig. 1). The 1H NMR spectral analysis of 4-aminobenzoic
H2N
acid exhibited a doublet at 6.54 ppm due to aromatic protons.
Fig. 1 The chemical structure of procainamide hydrochloride One more doublet of aromatic protons resonated at 7.59 ppm

Scheme 1
O
N
N
H + 2 [Fe(CN)6]3- + 3 H2O
H 2N

O
H 2N H
OH + + 2 C2H6 + 2 [Fe(CN)6]4- + 2 OH-
H NH2
H 2N

4-Aminobenzoic acid (E)-Ethene-1,2-diamine

123
Kinetic and mechanistic investigations 1487

Fig. 2 GC-MS spectrum of the product 4-aminobenzoic acid showed base peak at 120 amu and molecular ion peak at 137 amu

(suppl. Fig. 2). The 13C NMR spectral analysis of 4-amino- Table 1 Effect of variation of hexacyanoferrate(III), procainamide,
benzoic acid exhibited a peak 167 ppm due to carboxylic and OH- on the oxidation of procainamide by hexacyanoferrate(III)
at 25 C and I = 1.10 mol dm-3
acid carbon. A signal at 153 ppm is attributed to aromatic
carbon adjacent to NH2 carbon a peak at 131 ppm is due to [Fe(CN)3- 4
6 ] 9 10 / [PAH] 9 103/ [OH-]/ kobs 9 103/
aromatic carbons, one more peak at 116.854 ppm is attrib- mol dm-3 mol dm-3 mol dm-3 s-1
uted to aromatic carbon adjacent to carboxylic group and 0.50 2.0 0.5 1.40
remaining two aromatic carbons resonated at 112.52 ppm 1.0 2.0 0.5 1.43
(suppl. Fig. 3). The GCMS analysis of 4-aminobenzoic acid 2.0 2.0 0.5 1.49
showed a base peak at 120 amu and molecular ion peak at 3.0 2.0 0.5 1.41
137 amu (Fig. 2). Another product (E)-ethene-1,2-diamine 5.0 2.0 0.5 1.37
was confirmed by its GCMS spectrum, which showed a 2.0 0.50 0.5 0.55
molecular ion peak at 58 amu (suppl. Fig. 4). 2.0 1.0 0.5 0.81
2.0 2.0 0.5 1.49
Reaction order
2.0 3.0 0.5 1.91
2.0 5.0 0.5 2.85
The reaction orders were determined from the slope of the
2.0 2.0 0.10 0.59
plots of log kobs vs. log(concentration) by varying the
2.0 2.0 0.30 1.05
concentrations of procainamide and alkali in turn while
2.0 2.0 0.50 1.49
keeping all other concentrations and conditions constant.
2.0 2.0 0.70 2.02
2.0. 2.0 1.00 3.47
Effect of [hexacyanoferrate(III)]

At constant concentration of procainamide, alkali and at reaction. This also indicates first order with respect to
constant ionic strength, I = 1.10 mol dm-3, the hexa- hexacyanoferrate(III).
cyanoferrate(III) concentration varied from 0.5 9 10-4
to 5.0 9 10-4 mol dm-3 (Table 1). The order with Effect of [procainamide]
respect to hexacyanoferrate(III) concentration was found
to be unity, since the rate constant kobs was constant at The substrate, procainamide concentration was varied in
different hexacyanoferrate(III) concentrations. The the concentration range of 0.5 9 10-35.0 9 10-3
pseudo-first order plots under these conditions were mol dm-3 at 25 C (Table 1), keeping all other conditions
almost parallel and linear over 70 % completion of the constant. The rate constant, kobs, increased with increase in

123
1488 M. D. Meti et al.

the concentration of procainamide. From the slope of the where u1 and u2 are volume fractions; and D1 and D2 are
plot of log kobs vs. log [PAH], the order with respect to dielectric constants of water and t-butyl alcohol as 78.5 and
procainamide concentration was found to be less than unity 10.9 at 298 K, respectively. For example, at u (t-butyl
(0.72). alcohol) = 10 %
D 78:5  90=100 10:9  10=100 71:74:
Effect of [alkali]
In the same way, the values of D were calculated at the
The effect of alkali concentration on the reaction was other percentage of t-butyl alcohol. The solvent did not
studied in the range 0.11.0 mol dm-3 (Table 1) at con- react with the oxidant under the experimental conditions.
stant concentrations of procainamide, hexacyanoferrate(III) The solvent composition, t-butyl alcohol/water of the
and at constant ionic strength of 1.10 mol dm-3 at 25 C. reaction mixture was varied up to u (t-butyl
The rate constant increased with increase in the alkali alcohol) = 30 %. On decreasing the dielectric constant of
concentration. The order was found to be less than unity the reaction medium, an increase in the rate was observed,
(0.79). and the plot of log kobs vs. 1/D was linear with a positive
slope (Fig. 3).
Effect of ionic strength and dielectric constant
Effect of added products
At constant concentration of reactants and keeping other
conditions constant as well, the ionic strength was var- The effect of initially added products, hexacyanoferrate(II)
ied by varying the concentration of potassium nitrate and p-aminobenzoic acid did not have any significant effect
between 0.50 and 1.40 mol dm-3 and the rate was found on the rate of reaction.
to increase with increasing ionic strength. A plot of log
kobs vs. HI is linear with positive slope (Fig. 3). The Test for free radicals (polymerization study)
effect of dielectric constant was studied by varying the
t-butanol/water volume fraction u in the reaction mix- The intervention of free radicals in the reaction was exam-
ture with all other conditions being maintained constant. ined as follows: The reaction mixture, to which a known
Since dielectric constants of aqueous t-butanol mixtures quantity of acrylonitrile scavenger had been initially added,
are not available in literature, they were computed from was kept for 5 h in a nitrogen atmosphere. On diluting the
the values of pure liquids [11]. The dielectric constants reaction mixture with methanol, no precipitate resulted,
of the reaction medium at various composition of t-butyl indicating the absence of free radicals in the reaction.
alcohol/water were calculated using the following
equation: Effect of temperature
D u1 D1 u2 D2 ;
The rate of reaction was measured at different temperatures
15, 25, 35, and 45 C under varying alkali and procain-
1/D x 10 2
amide concentrations. The rate was found to increase with
1.0 1.4 1.8
0.8 the increasing temperature. The rate constant, k, of slow
1.5 step, K1, the value of first equilibrium step and K2, the
value of second equilibrium step of Scheme 1 were
0.6 obtained from the slopes and intercepts of the plots of 1/
kobs vs. 1/[PAH] and 1/kobs vs. 1/[OH-] at four different
1.1
1+log kobs

temperatures and are given in Table 2. The data were


3+log kobs

0.4 subjected to least square analysis. The enthalpy of activa-


tion, DH# and entropy of activation, DS# were obtained by
0.7 Eyring equation in both cases [12]
0.2  6 
kB T kB T 6
expDG =RT exp DH TDS =RT ;
6
k
h h
1
0.3 0.0
0.6 0.8 1.0 1.2 1.4 1.6
where k is the rate constant, kB is Boltzmanns constant,
I
h is Plancks constant, R is the gas constant, T is the
Fig. 3 Effect of ionic strength and dielectric constant on the absolute temperature and DG# is the Gibbs energy of
oxidation of procainamide by alkaline hexacyanoferrate(III) activation. The linear form of Eq. (1) is

123
Kinetic and mechanistic investigations 1489

Table 2 Activation parameters and thermodynamic quantities for the oxidation of procainamide by hexacynaoferrate(III) in alkaline medium
with respect to the slow step of Scheme 3
(A) Effect of temperature and activation parameters
Temperature/K k 9 103/s-1 Parameters Values

288 1.19 Ea/kJ mol-1 59 2


298 3.70 DH#/kJ mol-1 56 6.3
308 5.78 DS#/J K-1 mol-1 -123 21
318 13.4 DG#/kJ mol-1 93 0.52
log A 8 0.2
(B) Effect of temperature on first and second equilibrium step of Scheme 3
Temperature/K K1/dm3 mol-1 K2 9 10-3/dm3 mol-1

288 0.18 4.48


298 0.28 3.37
308 0.49 2.30
318 0.74 1.66
(C) Thermodynamic quantities with respect to K1 and K2
Thermodynamic quantities Values from K1 Values from K2

DH/kJ mol-1 37 -26


DS/J K-1 mol-1 113 -19
DG298/kJ mol-1 3.2 -20

k DH 6 DS6 kB first cycle was generally recorded. However, no peak was


ln  ln : 2 observed in the reverse scan, suggesting that the oxidation
T RT R h
process is an irreversible one. In Fig. 4, (a) is bare electrode
The slope of the plot of log k/T vs. 1/T gives the value of and (b) is oxidation of PAH with buffer (pH 7.0).
enthalpy of activation, DH#. By using this value of DH#, The variation of the concentrations of the oxidant, sub-
and the rate constant at a particular temperature T, the strate, and alkali, while keeping other conditions constant,
value of entropy of activation, DS# was obtained by simple showed that the reaction is first order in oxidant, less than
rearrangement of Eq. (1). Using these values of DH# and unit order in substrate and alkali concentrations. The reac-
DS#, the free energy of activation DG# was obtained and tion between procainamide and hexacyanoferrate(III) has a
values are given in Table 2. A vant Hoff plot was drawn stoichiometry of 1:2. Based on the experimental results, a
for the variation of K1 and K2 with temperature, i.e., (log mechanism is proposed for which all the observed orders in
K1 vs. 1/T and log K2 vs. 1/T). The values of enthalpy of each constituent such as [oxidant], [reductant], and [OH-]
reaction DH, entropy of reaction DS, and free energy of may be well accommodated. Oxidation of procainamide by
reaction DG, were calculated, and these values are given in hexacyanoferrate(III) in alkaline media is a non-comple-
Table 2. A comparison of these values obtained for the mentary reaction with two moles of oxidant reacts with one
slow step shows that the reaction before the rate mole of substrate. Based on the experimental rate law, the
determining step is fairly fast as it involves low kinetic model is presented as Scheme 2.
activation energy. The mechanism (Scheme 3) involves combination of
alkali with procainamide to give the anionic form of pro-
Cyclic voltammetric behavior of procainamide cainamide in a prior equilibrium step, which is also
supported by the observed fractional order in [OH-] and
The electrochemical behavior of PAH at glassy carbon [PAH]. Hexacyanoferrate(III) then reacts with anionic form
electrode was investigated using cyclic voltammetry (CV) at of procainamide to give a complex (C). This complex
physiological pH 7.0. The cyclic voltammograms obtained (C) undergoes decomposition in a slow step to give 4-ami-
for 1.0 9 10-4 mol dm-1 PAH solution at a scan rate of nobenzoic acid, [Fe(CN)4- 6 ] and intermediate of N ,N -
1 1

50 mV/s exhibit a well-defined irreversible anodic peak at diethylethane-1,2-diamine. In a subsequent fast step this
about 0.9139 V at glassy carbon electrode. The results are intermediate of N1,N1-diethylethane-1,2-diamine decom-
shown in Fig. 4. The voltammograms corresponding to the poses to give (E)-ethene-1,2-diamine with elimination of

123
1490 M. D. Meti et al.

h i
ethane as a by-product. All these results were proposed in a
C K2 Anionic form of PAH FECN3
6 :
detailed mechanistic as shown in Scheme 3.
Since Scheme 3 is in accordance with the generally From Eqs. (3) and (4), we have
well-accepted principle of non-complementary oxidations h i
taking place in sequence of one-electron steps. Spectro- Rate kK2 Anionic form of PAH FECN3
6 : 5
scopic evidence for the complex formation between
oxidant and substrate was obtained from UVVis spectra of From the first step of Scheme 3, we have
hexacyanoferrate(III) (2.0 9 10-4 mol dm-3) and PAH
Anionic form of PAH
(2.0 9 10-3 mol dm-3) a mixture of both (suppl. Fig. 5). K1
A hypsochromic shift of about 10 nm from 275 to 265 nm PAH OH 
in the spectra of procainamide to mixture of hexacyano- Anionic form of PAH K1 PAH OH : 6
ferrate(III) and PAH was observed.
Substituting Eq. (6) in Eq. (5),
From Scheme 3, the rate [Eq. (13)] can be derived as
follows: Rate k K1 K2 PAHf OH f FeCN3
6 f : 7
dFeCN3
6 
Rate kComplex: 3 The total concentration of [Fe(CN)3-
6 ] is given by
dt
From the second step of Scheme 3, we have FeCN3 3
6 T FeCN6 f C

C FeCN3  3
6 f K1 K2 PAHf OH f FeCN6 f
K2 4 FeCN3 
Anionic form of PAHFECN3 6 f 1 K1 K2 PAHf OH f ;
6 

where [Fe(CN)3- 3-
6 ]f and [Fe(CN)6 ]T refer to free and total
3
[Fe(CN)6] concentration, respectively. Therefore, free
[Fe(CN)3-
6 ]f is given by

FeCN36 T
FeCN3
6 f : 8
1 K1 K2 S OH 
Similarly,
OH T OH f Anionic form of PAH C

OH T OH f K1 PAH OH 


K1 K2 PAH OH FECN3
6 

OH T
OH f :
1 K1 PAH OH  K1 K2 PAH OH FECN3

6 

In view of low concentration of [PAH] and [Fe(CN)3-


6 ]
Fig. 4 Cyclic voltammograms at the glassy carbon electrode in
phosphate buffer solution (pH 7): a in the presence bare pH 7; b in the used, the terms K1[PAH] and K1K2[PAH] [Fe(CN)3- 6 ] are
presence of procainamide (1.0 9 10-4 M) at the scan rate 0.05 V s-1 neglected compared to unity. Therefore,

Scheme 2
PAH + OH- Anionic form of PAH + H2O

Anionic form of PAH + [Fe(CN)6]3- Complex (C)

Complex (C) + 2 H2O Product + Intermediate + [Fe(CN)6]4-

Intermediate + [Fe(CN)6]3- Final Products + [Fe(CN)6]4-

123
Kinetic and mechanistic investigations 1491

Scheme 3
O O
N N
N K1 N
+ OH -
H + H 2O

H2N H 2N

O
N
N K2
3-
+ [Fe(CN)6] (Complex)4-
H 2N

k OH
(Complex)4- + 2 H2O + N + [Fe(CN)6]4- + OH-
slow H 2N
H2 N
4-Aminobenzoic acid N1,N1-Diethylethane-1,2-diamine

H 2N H
fast
N + [Fe(CN)6]3- + 2 H2O + 2 C2H6 + [Fe(CN)6]4- + 2 OH-
H2N
H NH2
1 1
N ,N -Diethylethane-1,2-diamine (E)-Ethene-1,2-diamine

OH f OH T : 9 kK1 K2 PAHT OH T FeCN3


6 T
Rate
1 K1 K2 PAH OH  K1 OH  K12 K2 OH 2 PAH
In the similar way, [PAH]f was also calculated as 11
follows:
In view of low concentration of [PAH] used, the terms
PAHT PAHf Anionic form of PAH C
K21K2 [OH-] [PAH] are neglected. Therefore,
PAHf K1 PAHOH  K2 Anionic form of PAH
kK1 K2 PAHT OH T FeCN3
6 T
 FeCN3
6 
Rate :
1 K1 K2 PAH OH  K1 OH  K12 K2 OH 2 PAH
PAHf K1 PAHOH  K1 K2 PAHOH 
12
 FeCN3
6 
Or
PAHT Rate kK1 K2 PAHT OH T
PAHf : kobs :

1 K1 OH  K1 K2 OH  
FeCN3
6  Fe(CN3 1 K1 OH  K1 K2 PAHOH 
6 
In view of low concentration of [Fe(CN)3-
6 ] used, the 12
terms K1K2[OH-] [Fe(CN)3-6 ] are neglected. Therefore,
Further Eq. (12) can be rearranged to Eq. (13), which is
PAHT suitable for verification.
PAHf : 10
1 K1 OH  1 1 1 1
: 13
Substituting Eqs. (8)(10) in Eq. (7) and omitting kobs k K1 K2 PAH OH  k K2 PAH k
subscripts T and f, we have
The effect of ionic strength and dielectric constant of
kK1 K2 PAHT OH T FeCN3
6 T medium on the rate explains qualitatively the reaction
Rate
1 K1 OH  1 K1 K2 PAH] OH  between ions having the same charge, as seen in

123
1492 M. D. Meti et al.

1/[OH ]/dm3 mol1 Experimental


0.0 0.5 1.0 1.5 2.0 2.5 3.0
3.0 2.0
Reagent grade chemicals and double distilled water were
used throughout the work. The stock solution of the oxidant
2.5
hexacyanoferrate(III) was prepared by dissolving potas-
1.5
sium hexacyanoferrate(III) (SISCO-CHEM) in water and
2.0
the concentration was ascertained by iodometric titration
1/kobs 103 /s

1/kobs 103/s
[15]. A stock solution of substrate 0.01 mol dm-3 pro-
1.5 1.0
cainamide (Sigma Aldrich) was prepared by dissolving
PAH in distilled water. Potassium hydroxide (s. d. fine-
1.0
Chem Ltd.), was used as the source of OH- to vary the
0.5
alkali concentration in the reaction media. The potassium
0.5
nitrate solution was prepared by dissolving potassium
nitrate in double distilled water and was used to maintain
0.0 0.0
0.0 2.0 4.0 6.0 8.0 10.0 12.0
the ionic strength in the reaction medium.
1/[PAH] x 103/dm3 mol1
Equipments and spectral measurements
Fig. 5 Verification of rate law [Eq. (12)] in the form of Eq. (13)
For kinetic measurements, a Peltier Accessory (tempera-
ture control) attached Varian CARY 50 Bio UVvis.
Scheme 3. The thermodynamic quantities for the spectrophotometer (Varian, Victoria-3170, Australia) was
different equilibrium steps in Scheme 3 can be used. For product analysis, the QP-2010S Shimadzu gas
evaluated as follows. The [PAH], [OH-] were varied chromatograph mass spectrometer, Nicolet 5700-FT-IR
at four different temperatures. According to Eq. (13), spectrometer (Thermo, U.S.A) were used; 1H NMR spectra
other conditions being constant, plots of 1/kobs vs. were recorded on a 300 MHz spectrometer (Bruker, Swit-
1/[PAH] and 1/kobs vs. 1/[OH-] should be linear and zerland). 13C NMR was recorded on a 400 MHz
are found to be so (Fig. 5). From the slopes and spectrometer (Bruker, Switzerland) in DMSO-d6 with TMS
intercepts, the values of K1, K2, and k were calculated as an internal standard.
at different temperatures (Table 2). vant Hoff plot was Electrochemical measurements were carried out on a
made for the variation of K1 and K2. For example at 25 CHI 630D electrochemical analyzer (CH Instruments Inc.,
C (log K1 vs. 1/T and log K2 vs. 1/T), the values of USA). The voltammetric measurements were carried out in
enthalpy of reaction DH, entropy of reaction DS, and a 10 cm3 single compartment three-electrode glass cell
free energy of reaction DG were calculated for the first with Ag/AgCl as a reference electrode, a platinum wire as
and second equilibrium steps of Scheme 3. These values counter electrode, and a 2 mm diameter glassy carbon
are given in Table 2. A comparison of the DH value electrode as a working electrode (part no. CHI101). For pH
(37 kJ mol-1) from K1 of first step with that of DH# measurements, an Elico pH meter model LI120 was used.
(56 kJ mol-1) obtained for rate determining step shows
that the reaction before the rate determining step is fairly Kinetic measurements
fast as it involves low activation energy [13]. A high
negative value of DS# (-102 J K-1 mol-1) suggests that Kinetic measurement was carried out at 25 0.1 C and at
intermediate complex (C) is more ordered than the constant ionic strength, I = 1.10 mol dm-3. Reactions
reactants [14]. were initiated by mixing previously thermostated solutions
of hexacyanoferrate(III) and procainamide which also
contained the required amount of potassium hydroxide and
Conclusion potassium nitrate. The kinetics was followed under pseudo-
first order conditions with PAH in excess. Progress of
Spectroscopic investigation and oxidation of procainamide reaction was followed by measuring the absorbance of
by hexacyanoferrate(III) in aqueous alkaline media have hexacyanoferrate(III) in the reaction mixture at 420 nm in
been studied. Rate constant of slow step and other equi- a 1 cm cell placed in the thermostated compartment of a
librium constants involved in the mechanism are evaluated Varian carry 50 Bio UVVis spectrophotometer. At this
and activation parameters with respect to slow step of wavelength, all other materials concerned have negligible
reaction were computed. The mechanism described here absorbance. Application of Beers law under reaction
are consistent with all experimental results. conditions had been verified between 1.0 9 10-4 and

123
Kinetic and mechanistic investigations 1493

0.30 polishing, the electrode was rinsed thoroughly with milli-


pore water. After this mechanical treatment, the GCE was
0.25
placed in buffer solution and various voltammograms were
0.20 recorded until a steady state baseline voltammogram was
Absorbance

(a) obtained. The GCE was first activated in phosphate buffer


(a)
0.15 (pH 7.0) by cyclic voltammetric sweeps between 0.2 and
1.6 V until stable cyclic voltammograms were obtained.
0.10
Then, the electrodes were transferred into another 10 cm3
(j) of phosphate buffer (pH 7.0) containing proper amount of
0.05
(j) PAH and cyclic voltammograms were recorded between
0.00 0.2 and 1.6 V, with a scan rate of 50 mV s-1.
320 350 380 410 440 470 500
Wavelength/nm

Fig. 6 UV-Vis spectral changes during oxidation of procainamide by


References
hexacyanoferrate(III) at 25 C; [Fe(CN)3- -4
6 ] = 2.0 9 10 , [PAH] =
2.0 9 10-3, [OH-] = 0.5 mol dm-3, and I = 1.10 mol dm-3 with 1. Stearns FM, Trevose PA (1981) Clin Chem 27:2064
scanning time interval of 1.0 min 2. Dutcher JS, Strong JM, Lucas SV, Lee WK, Atkinson AJ (1977)
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