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J. CHEM. SOC. FARADAY TRANS., 1993, 89(14), 2451-2456 245 1
Alkali-stable Iron Complexes as Mediators for the Electrochemical
Reduction of Dispersed Organic Dyestuffs
Thomas Bechtold,* Eduard Burtscher," Angelika Amann and Ortwin Bobleter
Institute for Textile Chemistry and Textile Physics of the Leopold-Franzens-University of lnnsbruck,
Hochsterstrasse 73,A-6850 Dornbirn , Austria
Several complexones and amino compounds have been investigated as to their ability to form alkali-stable
coordination compounds with iron, which can be used as mediators for the indirect electrochemical reduction of
dispersed organic dyestuffs with different structures. A characterisation of the reducing efficiency can be
obtained when the cathodic current maxima of the mediator solution containing the dyestuff is compared with
the cathodic peak current without the reducible vat dye.
Published on 01 January 1993 on http://pubs.rsc.org | doi:10.1039/FT9938902451
In the textile industry the use of vat dyes, indigo and sulfur
dyestuffs is of great importance for cellulosic textiles. About
30% of the textile products manufactured from cellulosic
fibres are coloured with such dyes. In the application of these,
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powerful reducing agents must be used in order to reduce the
dispersed oxidised dyestuff particles. In the reduced form
these particles are dissolved in alkaline aqueous solutions,
and then the dye shows a great affinity for the cellulosic fibre.
After the adsorption of the dyestuff an oxidation step leads to
the insoluble oxidized, well fixed form.
The reducing agents in technical use today are mainly
Na,S,O, , organic sulfinates, organic ketoalcohols or carbo-
hydrates such as glucose.' The main disadvantage of these
reducing agents is that their reduced form cannot be regener-
ated. In particular, the surplus reducing agent causes severe
problems in the textile waste-water treatment.
In the literature an attempt to solve the reduction prob-
lems by means of a direct electrolytic process is described.2 It
was, however shown that only an indirect electrolysis process
has the potential for a technical replacement of the one-way
reducing chemical^.^
Bechtold et ~ 1 have found that the coordination com-
. ~ 9 '
pounds of iron with triethanolamine and diethanolamine can
be used as mediators for the indirect reduction of dispersed
organic dyestuffs. The reduced forms of these complexes, espe-
cially the more stable complexes with triethanolamine as
ligand, are well suited to reducing the dispersed dyestuffs.
A general reaction scheme for such an electrochemical
process can be established as follows:
Fe3+L+ e- + F e 2 + L
Fe2+L + D y e e F e 3 + L + Dye'-
2 Dye'- s Dye2- + Dye
Dye'- + Fe2+L+Dye2- + Fe3+L
Dye2- =Dye + 2e-
In the first reduction step the iron complex is cathodically
reduced [eqn. (l)] in a reversible electrochemical p r o ~ e s s . ~
The reduced complexes diffuse from the electrode towards the
dyestuff particles. At the surface of the dispersed particle a
one-electron charge transfer occurs [eqn. (2)]. Since the dyes
investigated require two electrons for the reduction of each
molecule, the primary formation of a radical anion is sup-
posed according to the reaction mechanism of Cu' ions with
1-bromoanthraquinone in aqueous solution.6 Two radical
anions are assumed to give one fully reduced molecule and to
regenerate one molecule in its oxidized form [eqn. (3)], in
agreement with the reaction path observed by the direct elec-
trochemical reduction of anthraquinones.'** In a further pos-
sible reaction mechanism a second electron transfer from a
reduced mediator to a radical anion cannot be excluded,
which also gives one fully reduced dyestuff dianion as a reac-
tion product [eqn. (4)]. In an additional reaction the equi-
librium between the fully reduced dyestuff molecules and the
insoluble oxidized form of the dye is built up [eqn. (5)].
Although a theoretical treatment of the complex reactions
was not attempted, a qualitative discussion gives valuable
information on the reaction mechanism. Eqn. (1)-(5) give no
indication as to which requirements a ligand has to fulfill.
The following experiments, however, show that fewer ligands
can be applied practically than was previously expected.
The general requirements for a ligand to form coordination
compounds that are usable as mediators are: (i) the forma-
tion of stable coordination compounds with Fe" and Fe"' in
an alkaline medium, (ii) reversible charge transfer from Fe"'
to Fe", whereby minimal dissociation of the complex occurs,
(iii) sufficient negative redox potential in alkaline solution, at
least -600 mV for indigo, or better -1OOO mV us.
Ag I AgClI3 mol dm-' KCl, to reduce all vat dyestuffs com-
monly used in the textile industry, (iv) a high rate of electron
transfer from the cathode to the oxidized Fe'" complex, (v) a
large number of catalytic cycles (possibility for multiple reuse
of the dyeing liquor) and (vi) rapid electron transfer from the
reduced form of the mediator to the oxidized dyestuff.
In this work the results are given of a large number of
screening experiments on the ability of the so-called
'complexones' '3'' to act as ligands and the characterization
of the alkali-stable iron coordination compounds that are
(1) suitable as mediators.
(2)
To obtain more information about the reaction mechanism
of the redox reactions between the iron complexes and the
(3) dispersed dyestuffs, photometric investigations using a stirred
flow apparatus were performed. After optimization of the
(4) concentrations of the dyestuffs and of the iron" complexes
(5) used as reducing agents, the progress of the reduction step
was studied by varying the steady-state conditions in the
photometric celI.
Experimental
The different ligands, the NaOH and the Fe2(S0,),.6H20
(22% Fe content) used were of analytical grade. The dye
systems investigated were technical products : indanthrene
yellow G (CI vat yellow 1) BASF, brillant indigo 4B-D (CI
vat blue 5 ) BASF, hydron blue 3R Stabilosol (CI sulphur vat
blue 43) Hoechst. Indanthrene yellow G is a dyestuff with
anthraquinoid structure (l),brillant indigo 4B-D is a techni-
cal preparation of 5,5,5',7'-tetrabromindigo(2). Hydron blue
 View Article Online

2452 J. CHEM. SOC. FARADAY TRANS., 1993, VOL. 89

3R consists of reaction products of carbazolindophenol with cipitated iron hydroxide, the solution was made up to 500
sodium polysulfide and its structure is not fully defined, but cm3. The dye component was dispersed separately
the existence of reducible disulfide groups must be accepted (indanthrene yellow G 0.5 g dmd3, brillant indigo 4B-D 2 g
as a fact (3)' ' dm-3, hydron blue 3R 0.5 g dm-3). The solutions to be
0 investigated were prepared by mixing the mediator solution
with an adequate volume of the dye stock solution.
The apparatus used for the experiments was a 264 A
Potentiostat (EG&G, Princeton, NJ) with a 303A HMDE-
electrode (small drop size, drop area 0.96 x lo-, cm2). A
platinum wire served as the counter-electrode. The cyclic
voltammograms were recorded on an X-Y recorder
1 (Rikadenki, Tokyo). All potentials were measured against an
Ag I AgCl I sat. KCl reference electrode. The scan rates re-
ported are given in mV s-'. The test solutions were aerated
for at least 4 min with N, to eliminate interfering oxygen.
The photometric experiments were performed with a
Published on 01 January 1993 on http://pubs.rsc.org | doi:10.1039/FT9938902451

0 H Br stirred flow apparatus working with a peristaltic pump. A

dispersion of the oxidized dyestuff (indanthrene yellow G 2.0
g dm-3, brillant indigo 4B-D 2.5 g dm-3, hydron blue 3R 5.0
Br g dm-3) and a freshly prepared solution of the iron@)
Ar H 0. 2 complex in alkaline solution (FeS04.7H,0 5 g dm-3,
1.8 x lo-, mol dm-3; Hedta 20 g dm-3, 0.04 mol dm-3;
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NaOH 8 g dm-3, 0.2 mol dm-3 or FeS04.7H,0 2.5 g

dm-3, 9 x mol dm-3; triethanolamine 20 g dm-3,
0.134 mol dm-3; NaOH 5 g dm-3, 0.125 mol dm-3) were
pumped into a mixing chamber (volume 1.4 cm3). The well
I stirred mixture was pumped into a flow-through cell (d = 1
7 7 mm), where the absorbance was measured from 350 to 700
nm. The photometer used was a Hitachi U-2O00 double-
beam spectrophotometer.

Results and Discussion

I I
H S
The results of the screening investigations of the different
I
3 complexones are show in Table 1. The main criteria for the
examination to find useful coordination compounds were
both the stability of the coordination compound in alkaline
The dyestuffs used were technical products, therefore the medium and a sufficiently low redox potential to reduce the
content of reducible dyestuff was determined by redox titra- dyestuff particles. The ligands which did not show both
tion. An adequate amount of dyestuff was added to 40 cm3 of properties were not tested on their ability to act as a medi-
a solution of FeS0,.7H20 (1.5 g dm-3, 5.4 x l o w 3mol ator with the CV technique.
dm-3), triethanolamine (10 g dm-3, 0.067 mol dm-3) and The redox potential of the suitable ligands is given by the
NaOH (8 dm-3, 0.2 mol dm-3). When the amount of added cathodic peak potential (E&, obtained from the CV experi-
dyestuff is held below the reducing capacity of the iron" ments. As the CV measurements were made with solutions
complex, a solution of the dyestuff in its reduced form is with an NaOH content of 8 g dmW3,the current peak poten-
obtained. By titration of this solution with K,[Fe(CN),] tials (EJC are given only in the case where solutions with suf-
(0.01 mol dm-3) the concentration of the dyestuff in the tech-
nical product can be determined and calculated as their
demand of reducing agent in moles per gram of dyestuff. Table 1. Results of the screening investigations on different
The reduction potentials of the fully reduced dyestuffs were 'complexones '
also determined by this method. Similar to the other vat dyes
stability of
the potentiometric curves do not show a well defined poten- iron@) complex
tial where the oxidation/reduction of the dyestuff proceeds. ligand (E,),/mV in alkaline solution
Therefore the redox behaviour of the investigated model dye-
stuffs is described by the potential limits within which the NTA -
P
oxidation/reduction proceeds : edta P -
Titriplex IV -
indanthrene yellow G : P
Titriplex V (DTPA) -
1.74 x mol (g dyestuff)- ', - 520 to - 550 mV Titriplex VI (EGTA)
P
-
P
brillant indigo 4B-D : Titriplex VII (Hedta) - 650 +
1.74 x mol (g dyestuff)-', -490 to -590 mV bicine - 850 +-
hydron blue 3R: glycine P
2.25 x mol (g dyestuff)- ', -470 to - 570 mV triethanolamine (TEA) - 1050 +
The mediator systems were prepared by dissolving the diethanolamine (DEA) - lo00 0
triethylenetetramine P -
Fe,(SO&.6H20 (1.6 x lo-, g, 3.14 x mol) in ca. 100
cm3 water. The NaOH (16 g, 0.4 mol or 22.12 g, 0.58 mol) p, Precipitation of iron(@hydroxides occurs under experimental con-
and the amino compound (0.06 mol) were added immediately ditions; -, to low iron-binding capacity; 0, small iron-binding
to this solution under stirring. After the dissolution of pre- capacity; + high iron-binding capacity.

J. CHEM. SOC. FARADAY TRANS., 1993, VOL. 89
ficiently high concentrations of Fe*'/Fe" complexes were
reached. The stability of the iron complexes is summarized in
Table 1 with three signs. The + sign means that concentra-
tions of at least 1 g dm-3 of FeSO, . 7 H 2 0 can be reached in
alkaline solutions. The 0 sign means that such iron concen-
trations can be reached in alkaline medium which allow
correct CV evaluations, while the - sign means that the iron
concentration in the alkaline solution is too low to allow a
correct interpretation of the results measured under the
experimental conditions used.
The results given in Table 1 show that only TEA, bicine,
Hedta and, with limited iron-binding capacity, DEA fulfil
the basic requirements for further investigation. It is remark-
able that all four ligands possess an N-(2-hydroxyethyl)amino
group, which seems to be a central structural unit for reach-
ing the extreme coordination properties necessary for coordi-
Published on 01 January 1993 on http://pubs.rsc.org | doi:10.1039/FT9938902451
nation compounds with sufficiently high stability constants in
alkaline solution.
For use as mediator a high number of catalytic cycles
should be possible in the indirect electrolysis process. The
reversibility of the charge-transfer reaction is a very impor-
tant property in such mediator systems. The linearity of the
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cathodic peak current (Ip)d of the coordination compounds in
the absence of reducible organic materials us. the square root
of the sweep rate proves the reversibility of the electron-
transfer reaction. Fig. 1 shows that very good linearity of (Ip)d
us. Jv is obtained. The CV experiments with the Hedta as
ligand are shown in Fig. 2.
Both complexes (bicine and Hedta) show a potential differ-
ence between the anodic current peak and the cathodic
current peak defined as (EP),- (Ep)cof 60 mV, which is char-
acteristic of a one-electron transfer step.
When such a redox system is reduced electrochemically,
regeneratable reductants are produced. The efficiency of
reduction of dye by mediator can be described by the
cathodic current peak maximum ( I & . When reducible
organic material is dispersed in a solution of such a reversible
redox system, the reduced form of the coordination com-
pound is able to act as mediator, when the reduction power
of the mediator is sufficient. As model systems for reducible
organic compounds, organic dyestuffs were used
[indanthrene yellow G (CI vat yellow 1) BASF, brillant
indigo 4B-D (CI vat blue 5 ) BASF, hydron blue 3R Stabilosol
(CI sulfur vat blue 43) Hoechst). The reduced forms of the
dyestuffs investigated are soluble in aqueous alkaline solution
and all have reduction potentials near -650 mV or some-
0.25 1 change in the shape of the CV curves and to an increase in
0.20
f 0.15
--%
-
h
\a
0.10
0.05
0 5 10 15 20 25
Jv/mV1/2 s- ' 1 2
Fig. 1 Dependence of the cathodic peak current (ZJd for a soiution
of Fe,(SO4),-6H,O (1.57 x lo-' mol dm-') in (a) Hedta (0.03 mol
drn-,) and (b) bicine (0.03 mol dm-3) in alkaline solution (NaOH 0.2
mol dm-3) on the square root of the scan rate
View Article Online
2453
0.4
0.3
0.2
4 0.1
3
0
:::p,
,
-0.4
-300 -400 -500 -600 -700 -800 -900 -1000
E/mV
Fig. 2 Cyclic voltammograms of Fe2(S0,),.6H,0 (1.57 x
mol dm-3) in the presence of Hedta (0.03 mol dm-,) in an aqueous
solution of NaOH (0.2 mol drn-j) at various scan rates: (1) 20, (2)
100, (3) 200, (4)500 mV s - '
what more positive, so that an indirect electrolytic reduction
with iron bicine and iron Hedta complexes are achievable.
CV experiments with the dyestuffs in the absence of iron com-
plexes showed no significant electrochemical activity of the
dispersed dyestuffs proving that a direct electrochemical
reduction cannot be achieved under the investigated condi-
tions.
The indirect electrolysis can be well characterised by means
of CV experiment^.'^*'^ In the presence of reducible material
the reduced mediator diffuses to the electrochemically inac-
tive organic particles, where electron transfer to the surface of
the dispersed material takes place. The regeneration of the
oxidized form of the coordination compound leads to a
the cathodic current peak, while the anodic current
maximum decreases (Fig. 3 and 4). In very few cases, e.g. at
low scan rates, does a similarity exist between the described
experiments and the CV curves of the classic EC,,, mecha-
nism under homogeneous conditions. This result can be
explained by several facts. (i) To obtain a clear pseudo-first-
order mechanism a relatively high excess of dispersed
material is necessary, which leads to interfering direct elec-
trode reactions caused by the reaction of the adsorbed dye-
stuff particles at the electrode surface, and by the auxiliaries
which are added to the technical product formulation to
assure the necessary fine distribution in water. (ii) The
reduced dyestuff molecule is soluble in the aqueous alkaline
solution and leaves the surface of the dyestuff particle,
thereby building up a reversible redox system. (iii) The full
reduction of the dyestuff requires two electrons; but the iron
complex provides only one electron for the reduction, so that
after the transfer of the first electron, either dispro-
portionation of two dyestuff radicals or a second electron
 View Article Online

2454 J. CHEM. SOC. FARADAY TRANS., 1993, VOL. 89

0.5 transfer has to take place to give a fully reduced dyestuff mol-
ecule. (iv) The reduction of the dye molecule yields soluble
products, so with progressive reduction time the surface,
shape and diameter of the original dispersed dyestuff particles
0.4
alter, thereby changing the reaction conditions.
A practicable characterization of the electrochemical activ-
ity of a tested mediator system is obtained from a compari-
0.3 son of the cathodic current maximum in the presence of
dyestuff (Ip)c with the cathodic current maximum of the
diffusion-controlled reduction ( I & . The so-called enhance-
ment factors, (Ip)c/(lp)d characterize the reaction velocity by
0.2 comparing the current maxima of the coordination com-
pound in relation to that of the mediator system without the
Q: dye.' The dependence of the enhancement factors measured
3 on the concentration of the added organic dyestuff and on
0.1 the scan rates of the CV experiments is shown in Fig. 5-8.
Published on 01 January 1993 on http://pubs.rsc.org | doi:10.1039/FT9938902451

The enhancement factors first increase with increasing dye-

stuff concentration, resulting from the enhanced discharge of
the reduced iron complexes, leading to an increase in the
0 cathodic current.
At low scan rates the concentration of the dyestuff is too
low to fulfil the requirements of a pseudo-first-order reaction.
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In these experiments a significant amount of dyestuff is trans-

-0.1 ferred into its reduced form. Furthermore, with progressive
reduction of the dyestuff the redox equilibrium between the
reduced dyestuff and the oxidised form interferes with further
dyestuff reduction. At high scan rates (200-500 mV s-') the
-0.2
electron-transfer reaction between the reduced iron complex
EImV
and the dyestuff [eqn. (2)], or according to the following reac-
tion [eqn. (3)], the assumed disproportionation of the dye-
Fig. 3 Linear sweep voltammograms of Fe,(SO,), .6H,O stuff radicals, the desorption of the reduced dyestuff molecule
(1.57 x rnol dm-3) in an aqueous solution of bicine Na-salt
(0.03 mol drn-,) and NaOH (0.2 mol dm-3) in the presence of indan- or the diffusion of the dyestuff dianion into the bulk becomes
threne yellow G (0.05 g dm-j) at various scan rates (1) 10, (2) 50, (3) the determining factor of the reaction rate. Therefore, espe-
200, (4) 500 mV s- cially in the experiments with high dyestuff concentrations,
0.20, large differences are observed between the enhancement
factor at high and at low scan rates. The results of selected
photometric investigations under steady-state conditions with
different dyestuffs and two iron complexes as reducing agents

0 0.1 0.2 0.3

[indanthrene yellow G]/g dm-3
Fig. 5 Enhancement factor (lp)J(Zp),, as a function of dyestuff con-
centration (indanthrene yellow G) at various scan rates in the system
Fe,(S04),.6H,0 (1.57 x mol dm-,), bicine (0.03 rnol dm-3)
and NaOH (0.2 mol drn-,). v/mV s - l : +, 10; *, 20; 0, 50; x , 100;
A, 500.
 View Article Online

J. CHEM. SOC. FARADAY TRANS., 1993, VOL. 89 2455

n
P

zn2
lj
na
v
\
Published on 01 January 1993 on http://pubs.rsc.org | doi:10.1039/FT9938902451

0
0 I

.,
I I I
Downloaded by Duke University on 26 December 2012

[hydron blue 3R stabilosol]/g dm-3 0 0.1 0.2 0.3

Fig. 6 Enhancement factor (Zp)c/Zp)d as a function of dyestuff con-
centration (hydron blue 3R stabilosol) at various scan rates in the
system Fe,(S04),-6H,0 (1.57 x lo-' mol drn-,), bicine (0.03 mol
drn-,) and NaOH (0.2 rnol drn-,). o/mV s-': 5 ; *, 20; x , 100;
A,500.
[hydron blue 3 R stabilosol]/g drn - 3
Fig. 8 Enhancement factor (IP)J(ZJdas a function of dyestuff con-
centration (hydron blue 3R) at various scan rates in the system
Fe,(S04),.6H,0 (1.57 x rnol drn-,), Hedta (0.03 mol drn-,)
and NaOH (0.29 mol drn-,). u/mV s-': a, 5 ; *, 20; x , 100; A,500.

are given in Fig. 9-11. Fig. 9 and 11 show the reduction of

dyestuffs with the iron" Hedta complex; in the experiment
shown in Fig. 10 the iron"-triethanolamine complex was
used.
By changing the flow of the metering pump from 18.8 to
0.45 cm3 min-', different reaction times (4.5-187 s) could be
realized in the mixing unit before entering the photometer.
After an optimization of the reaction conditions (e.g. concen-
trations of the reducing agent and dyestuff) different steady
states of the reduction reaction were investigated with the
photometer. In the case of indanthrene yellow G as well as of
brillant indigo 4B-D only two main components could be
detected. Besides the oxidized form of the dyestuff the fully
reduced dyestuff molecule is the only reaction product which
appears in detectable concentrations. The formation of the
proposed radical anion intermediate could not be observed in
the spectra, indicating that the disproportionation [eqn. (311
is much faster than the first reduction step according to eqn.
(2).
In the case of hydron blue 3R the absorbance decreases at
all wavelengths, owing to the cleavage of the chromophoric
system. The similarity of the absorption spectra of the oxi-
dized and reduced forms of the dyestuff makes interpretation
more difficult.

1.6
1.4
1.2
1 I n 4 \
8 1.0
s0 0.8
2 0.6
m
0.4
0.2
0
350 400 450 500 550 600 650 70
0
0 0.1 0.2 0.3 L/nm
[indanthrene yellow G]/g dm-3

.,
Fig. 7 Enhancement factor (Zp)J(Zp)d as a function of dyestuff con-
centration (indanthrene yellow G) at various scan rates in the system
Fe,(S04),-6H,0 (1.57 x lo-' mol drn-,), Hedta (0.03 mol dm-,)
and NaOH (0.29 mol dm-'). o/mV s-': 5 ; *, 20; x , 100; A,500.
Fig. 9 Absorption spectra of a solution containing FeSO4.7H,O
(2.5 g dm-, 9.0 x lo-, rnol drn-,), Hedta-trisodium salt (10 g
drn-,, 0.02 mol drn-,), NaOH (4 g drn-,, 0.1 mol drn-,) and indan-
threne yellow G (1 g drn-,) at different reaction times: (1) 4.5 s, (2)
16.1 s, (3) 32.2 s, (4) 64 s, ( 5 ) 187 s
 View Article Online
2456 J. CHEM. SOC. FARADAY TRANS., 1993, VOL. 89

is lower compared to the electrode reaction [eqn. (l)], there-

1.o 5
fore the redox catalyst demonstrates growing reversibility

0.8

8 0.6
A and decreasing enhancement factors are calculated at higher
scan rates. A current plateau, which is typical for electro-
chemical reactions with fast catalytic regeneration of the
reactants, is reached only at very low scan rates.
A detailed kinetic analysis based on the existing electro-
chemical data and photometric experiments becomes very
complex because the simultaneously occurring reactions have
0.2 not yet enabled a mathematical solution to be found.
The results prove that bicine and Hedta are well suited to
forming iron complexes which can act as mediators for the
0 -
350 400 450 500 550 600 650 71 indirect electrochemical reduction of dispersed dyestuffs.
While Hedta iron complexes are favourable mediators for the
I/nm
Fig. 10 Absorption spectra of solution containing, FeSO, .7H,O
reduction of indigo, sulfur vat dyes and vat dyes with low
(1.25 g dm-3, 4.5 x mol dm-3), triethanolamine (10 g dm-3, reduction potential, the bicine complexes can produce
Published on 01 January 1993 on http://pubs.rsc.org | doi:10.1039/FT9938902451

0.067 mol dm-3), NaOH (2.5 g dm-3, 0.063 mol dm-3) and brillant
indigo 4B-D (1 g dm-3) at different reaction times: (1) 4.5 s, (2) 8.2 s,
(3) 16.1 s, (4) 32.2 s, (5) 93 s
Summarizing the results given in Fig. 5-8 a discussion of
Downloaded by Duke University on 26 December 2012
reduction potentials of -850 mV and are therefore the more
universal reducing agents. Comparing these results with those
of the experiments using TEA and DEA,4 it is remarkable
that all ligands which fulfil the above cited requirements
contain an N-(2-hydroxyethyl)amino group in their molecu-
lar structure.

the relative rate constants is possible. Under the experimental The investigations on the electrochemical behaviour of the
conditions, especially at lower scan rates, the enhancement Hedta and the bicine complexes in the presence of dispersed
factors increase with higher dyestuff concentrations, so the organic dyestuffs show that the use of iron-amine complexes
velocity of the redox reaction between the reduced form of for indirect electrochemical reduction is a generally applic-
the mediator and the oxidised form of the dyestuff according able method. By selecting the necessary mediator system to
to eqn. (2) is rate determining. The lack of detectable reach the required reduction potential and adjusting the elec-
amounts of intermediate dyestuff radicals resulting from a trode material and surface, the reaction conditions can be
reaction according to eqn. (3) or (4) proves that none of these optimised fairly easily.
steps is rate determining.
Generally the enhancement factors decrease with increas-
ing scan rate and the CV curves become more similar to the The authors are indebted to the Fonds zur Forderung der
reversible case. As the electrode reaction of the mediator Wissenschaftlichen Forschung (Austria, P 7957-CHE) for
[eqn. (l)] is faster than the redox reaction according to eqn. financial support of this work.
(2) the influence of reoxidation of the mediator by the reac-
tion with oxidised dye molecules decreases at high scan rates
on the CV timescale. The reaction rate according to eqn. (2)
References
1 U. Baumgarte, Melliand Textilber., 1987,68, 189; 276.
1.4 2 E. H. Daruwalla, TextileAsia, 1975, 165.
3 T. Bechtold, E. Burtscher, D. Gmeiner and 0. Bobleter, Tex-
1.2 tilveredlung, 1990,25, 221.
4 T. Bechtold, E. Burtscher, D. Gmeiner and 0. Bobleter, J. Elec-
1 .o troanal. Chem., 1991,306, 169.
5 T. Bechtold, E. Burtscher, A. Amann and 0. Bobleter, Angew.
8 0.8 Chem., 1992,104,1046.
C
6 H. Zollinger, Color Chemistry, VCH, Weinheim, 1987.
5 0.6 7 S. I. Bailey, Chem. Aust., 1982,50, 202.
a 8 D. 0. Wipf, K. R. Wehmeyer and R. M. Wightman, J. Org.
% 0.4 Chem., 1986,51,4760.
9 B. J. J. Engbers and G. Dierkes, Textilpraxis Int., 1992,47, 365.
0.2 10 G. Andregg, in Comprehensive Coordination Chemistry, ed.
Geoffrey Wilkinson, Pergamon Press, Oxford 1987, vol. 2, p.
0
3J 400 450 500 550 600 650
I
777.
1 1 M. Schubert, 2. Angew. Chem., 1948, @A, 141.
I/nm 12 R. S. Nicholson and I. Shain, Anal. Chem., 1964,36,706.
Fig. 11 Absorption spectra of a solution containing FeSO, * 7H,O 13 E. Steckhan, Angew. Chem., 1986,98,681.
(2.5 g dm-3, 9.0 x mol dm-3), Hedta trisodium salt (10 g dm-3 14 H. Lund and J. Simonet, J. Electroanal. Chem., 1975,65,205.
0.02 mol dm-3), NaOH (4 g dm-3, 0.1 mol dmb3)and hydron blue
3R (1 g dm-3) at different reaction times: (1) 4.5 s, (2) 8.2 s, (3) 16.1 s,
(4)32.2 s, (5) 93 s Paper 2/05447G; Received 12th October, 1992