CHEM. RES.

CHINESE UNIVERSITIES 2009, 25(2), 138142

Novel Photoinitiated Synthesis, Characterization, Thermal

Kinetics, and Mechanism of Complex of Potassium
Hexacyanoferrate with Imidazole
MAJID Kowsar*, AHMAD Siraj and MALIK Mukhtar Ahmad
Department of Chemistry, National Institute of Technology, Hazratbal Srinagar-190 006, India
Abstract Photoinitiated substitution complex of [Fe(CN)6]4 with imidazole has been synthesized and characterized.
On the basis of elemental analysis, the empirical molecular formula of the complex is K4[Fe(CN)5(C3H4N2)]4H2O.
The substitution of aquo ligand produced as a result of photoexcitation by imidazole has been confirmed by various
spectroscopic thechniques like UV-Vis, FTIR, NMR, and SEM techniques. The characteristic FTIR and NMR absorption peaks for different entities present support the assigned formula. The presence of cyanide and imidazole ligands is shown by FTIR absorption peaks at 2046 cm1 due to (CN) and at 1447 and 1619 cm1 due to (C=N)
and (C=C) stretching vibration of the aromatic ring of imidazole, hence, confirming the assigned formula and photoinitiated substitution process. 1H NMR also shows the peaks for aromatic hydrogen confirming again the presence
of imidazole in the complex, further supporting the successful photoinitiated process. The water outside the coordination sphere has been confirmed from FTIR peaks and thermal analysis. Thermal kinetics and mechanistic studies have
also been carried out by TG and DSC. Thermodynamics parameters such as activation energy(Ea), preexponential
factor(A), and entropy of activation(S#) have been calculated for each step via different methods like Doyles, Coats,
and Redfern and Arrehenius.
Keywords Photochemistry; Potassium hexacyanoferrate; Imidazole; Photosubstitution; FTIR
Article ID 1005-9040(2009)-02-138-05

Introduction

Different reports on thermal behavior of Fe(II)

and Fe(III) complexes have been found in the literatures[13]. Garmendia et al.[4] have synthesized and
characterized the complex of Fe(II) with hexaflouroacetanato and 2,2-biimadazole thermally. Prasad[5] has
investigated the ligand exchange reaction of hexacyanoferrate(II) with N-methylpyrazium ion in a potassium hydrogen phthalate buffer medium at (25.0
0.1) C.
UV irradiation in the ligand field bands of
hexacyanoferrate(II) in an alkaline medium results in
the substitution of cyanide ligands by water[68] followed by other thermal steps, which result in the loss
of other cyanide groups with the subsequent formation
of stable products with ligands like 2,2-bipyridyl,
1,10-phenanthroline, etc.[912] These materials also
known as hybrid materials have found innumerable
application in technological, medical, and industrial
fields[13,14]. Metal complexes with ligands judiciously
selected have been used as diagnostic tools, being utilized in image modulations like gamma ray scintigra
*Corresponding author. E-mail: kowsarmajid@yahoo.co.in
Received March 7, 2008; accepted August 21, 2008.

phy, positron emission tomography(PET), and magnetic resonance imaging(MRI) to cure a number of
diseases like heart, brain disorders, and cancer[15]. This
has prompted us to investigate the photocomplexation
of [Fe(CN)6]4 with imidazole. The choice of imidazole as ligand is because of its being efficient ligand.
Imidazole and its derivatives have been reported to
form complexes with various transition metal atoms
like Cu, Zn, etc.[1,16] The ligand is also biologically
important as it is present as a side chain in amino acid
histidine, which plays a vital role in the structure and
binding function of hemoglobin. Imidazole has become an important part of many pharmaceuticals.
Synthetic imidazoles are also present in many fungicides, antifungal, antiprotozoal, and antihypertensive
medications. Imidazole is part of the theophylline
molecule found in tea leaves and coffee beans,
which stimulates the central nervous system. It is
present in the anticancer medication mercaptopurine,
which combats leukemia by interfering with DNA
activities.
Organic-inorganic hybrid materials have received

No.2

MAJID Kowsar et al.

considerable attention because of the potential of

having mixed organic and inorganic features. Organic-inorganic hybrids of imidazole complexes of Pd(II),
Cu(II), and Zn(II) in the form of crystals and liquid
crystals have been investigated[17]. Hybrid-metal
Ni/Co hexacyanoferrate has been prepared in the form
of thin films on electrode surfaces and bulk precipitates(bulk powder). These hybrid films have been
shown to possess unique electrochemical properties,
long term stability, and promising charge storage/transport capabilities[18]. Various methods have
been used to synthesize these hybrid materials.
Keeping in view the flexibility of potassium
hexacyanoferrate for its photoinitiated substitution
process, the scope of the complex for the formation of
the hybrid material, and the importance of imidazole,
we here report the novel synthesis and characterization of a hybrid material of potassium hexacyanoferrate with imidazole. The complex was characterized
by various spectroscopic techniques like UV-Vis,
FTIR, NMR, and SEM. Thermal kinetics and mechanistic studies have been investigated by carrying out
TG and DSC, and thermodynamic parameters have
been calculated using different integral methods.

2
2.1

Experimental
Materials and Methods

Potassium hexacyanoferrate and Imidazole were

of A. R. grade.
All the solutions were prepared in doubly distilled water.
2.2

2.3

139

Physical Measurements

Determination of C, H, and N was carried out by

elemental analyzer. UV-Vis spectra were recorded
using a double beam spectrophotometer UV-190.
FTIR spectra were recorded using a Perkin-Elmer
FTIR spectrophotometer in the 4000500 cm1 range
using KBr disc. NMR study was carried out on a
dpx200 spectrometer using methyl alcohol as a solvent. A surface study of the complex was taken by
means of a Hitachi SEM Model S-3600N. TG and
DSC were conducted using a Perkin-Elmer(Pyris Diamond) thermal analyzer. The scanning was carried
out at a rate of 10 C/min from ambient to 1000 C.
Inert atmosphere was introduced by purging nitrogen
at a rate of 200 mL/min. An aluminum pan was used
as a reference.

Results and Discussion

3.1

UV-Vis Characterization

Photo excitation of hexacyanoferrate(II) in

imidazole results in the substitution of cyanide ions by
imidazole. The photoexcitation is followed by further
complexation with imidazole, which has been confirmed by recording UV-Vis spectra before and after
irradiation.
UV-Vis spectrum of unirradiated sample of
[Fe(CN)6]4 and imidazole shows a single peak with a
maximum absorbance at near 560 nm, whereas in the
case of irradiated sample, two absorption peaks are
observed at 360 and 500 nm, respectively(Fig.1).

Synthesis of Complex

The complex was synthesized by irradiating

K4[Fe(CN)6] and imidazole solution of 0.1 mol/L
strength in 1:1 ratio under UV radiation till the color
of the solution changes to deep yellow. Irradiation was
carried out for 0.5 h and the product formed in the
reaction vessel was isolated and dried over fused
CaCl2. The complex isolated is a solid powder with a
light yellow color. The complex is soluble in water
unlike other photoinitiated products reported[1921].
The complex formed was analyzed for C, H, and N,
and the empirical formula for the complex was found
to be K4[Fe(CN)5(C3H4N2)]4H2O. The observed
percentages of C, H, and N are 19.95%, 1.80%, and
20.46%, respectively, against the calculated percentages of C 19.91%, H 2.40%, and N 20.33%.

Fig.1

3.2

UV-Vis spectra of the complex before(a) and

after(b) irradiation

FTIR Characterization

The FTIR bands observed for the complex(Fig.2)

confirms the formation of metal-imidazole complex
showing characteristic peaks at 3586 cm1(w), 3524
cm1(s), and 3456 cm1(w) assigned to symmetric and

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CHEM. RES. CHINESE UNIVERSITIES

asymmetric vibrations of water. Presence of water is

also confirmed from the absorption peaks at 1619 and
1648 cm1, which are assigned to bending vibrations
of water. The presence of water outside the coordination sphere is also confirmed by recording TA, which
shows the weight loss equivalent to four moles of water at a temperature range of 20150 C. The expulsion of water at this temperature range shows its
presence outside the coordination sphere.

Vol.25

the presence of imidazole in the complex. One singlet

at 7.0 corresponds to the two equivalent olefinic
protons attached to the two adjacent carbon atoms of
the ring. The singlet at 7.6 corresponds to the olefinic proton, which is flanked around the two N atoms.
As it is more deshielded due to two N atoms, the
presence of imidazole in the complex is confirmed.
3.4

SEM Characterization

SEM image of the complex is shown in Fig.4,

which also confirms the formation of it as a stable one.
The morphology of the picture shows a uniform rock
like structure.

Fig.2

FTIR spectrum of the complex

The presence of cyanide group is shown by a

characteristic sharp CN stretching band at 2046
cm1. The CN stretching band of the free ion in
KCN is observed at 2080 cm1, which is shifted to
lower frequency by coordination, for coordination
usually weakens the ligand bond next to the coordinate bond[22]. Thus, in this case, the ligand stretching
vibration is shifted to the lower frequency region by
about 40 cm1. The band at 1057 cm1 also results
from the stretching vibration of CN. Presence of
sharp absorption band at 586 cm1 corresponds to the
symmetric vibration of FeCN. FeN coordinate
bond stretching vibration is confirmed by the presence
of weak absorption band at 660 cm1. The absorption
bands at 1448 and 1620 cm1 correspond to the
(C=N) and (C=C) vibration of the aromatic ring
of imidazole. A CH stretching vibrations of
aromatic ring is also confirmed by the band at 3125
cm1.
3.3

1
1

H NMR Characterization

Fig.4

3.5

SEM image of the complex

Thermogravimetry Studies

The thermogram of the complex is shown in

Fig.5. TG and DTG are shown by the curves a and b
DTA is shown by curve c. The complex undergoes
thermal decomposition process in two steps. The first
step initiated from 20 C undergoes a mass loss of
14.76% up to 150 C, corresponding to the loss of
four moles of water. The calculated mass loss for the
four moles of water is 14.93%. The temperature range
for this decomposition confirms the presence of water
outside the coordination sphere. Further decomposition starts at 200 C and ends at 960 C with a DTG
maximum at 811 C and an observed mass loss of
73.33% against a calculated mass loss of 73.44% due
to the loss of the rest of moieties like K, CN, and
imidazole. The residue left behind is Fe, which is jus-

H NMR study of the complex(Fig.3) confirms

Fig.5
Fig.3

H NMR spectrum of the complex

The TG(a), DTG(b) and DTA(c) curves for the

complex

No.2

MAJID Kowsar et al.

tified by its decomposition temperature. The observed

mass loss of the residue is 11.6% against the calculated 11.65% and also supports the decomposition
process.
DSC of the complex also shows two exothermic
peaks. The temperature range of TG and DTA are
comparable. The H values for the two stages are 203
Table 1

141

and 317 mJ/mg, respectively, justifying the thermal

decomposition mechanism and calculated thermodynamic parameters.
3.6

Kinetic Parameters

Kinetic parameters calculated for different steps

are shown in Table 1.

Activation energy, frequency factor and entropy of activation for K4[Fe(CN)5(C3H4N2)]4H2O

Ea/(kJmol1)

Stage

DTG
maximum
temperature/K

Doyle

I
II

408
973

56.12
88.66

Coats and
Redfern
56.52
133.35

A/s1
Arrhenius

Doyle

85.74
88.66

6.02 1033
5.11019

By using the Doyles equation[23],

lgT/w(Ea/4.6T +lgA/RH)
where T is t/RH, w the weight of the sample at time t,
Ea the activation energy, A the frequency factor, and T
the temperature in Kelvin, R the gas constant, H the
heating rate. The plot of lg T/w vs. 1/T gives a straight
line for a first order reaction. From the best fit equation obtained from programmer grapher, activation
energy(Ea) is obtained as the slope of the relation,
Ea=4.6slope and pre-exponential factor(A) from the
intercept of the plot. The entropy of activation(S#) is
obtained from the following equation:
A=kTs/hexp(S#/R)
where k is the Boltzmans constant, h the Plancks
constant, and T the DTG peak temperature. The Coats
and Redfern[24] equation is given:
lg[ln(1)/T2]=lgAR/HEa(12RT/Ea)Ea/2.3RT
where is the fraction decomposed at time t, Ea the
activation energy, H the heating rate, R the gas constant, and A the preexponential factor. A plot of
lg[ln(1)/T2] vs. 1/T for above equation is linear for
each stage of the decomposition of the complex. The
activation energy Ea and the frequency factor A are
obtained from the slope and intercept of best fit equation of the plot, respectively. With the help of Arrehenius[25] equation, the kinetic parameters was determined by equation
dx/dt =kxn
where x is the amount of sample undergoing reaction,
n the order of reaction, and k the specific reaction rate.
The best fit equation of lgk vs. 1/T gave slope and intercept from which values of Ea and A were calculated[Fig.6(A) and (B)].
The values of Ea, A, and S# for each particular
stage of the thermal decomposition process of the
complex given in Table 1 are comparable. The posi-

Coats and
Redfern
2.04 1010
446.68

S# /(JK1mol1)
Arrhenius

Doyle

5.241029
1.61016

5.8 1021
2.09107

Coats and
Redfern
1.99102
1.831010

Arrhenius
5.11017
6.5102

tive value of S# indicates that the activated complex

has a disordered structure than reactants and the reaction is faster than normal one[26].

Fig.6

Plots of lgT/w vs. 1/T(Doyles treatment, a),

lg[ln(1)/T2] vs. 1/T(Coats and Redfern, b)
and lgk vs. 1/T(Arrehenius treatment, c) for
the first(A) and second(B) decomposition step
of the complex

It is also evident that the activation energy is

minimum for the first step and maximum for the
second step and the corresponding value of the entropy of activation is also minimum for the first step and
maximum for the second step. Lower activation energy in the first stage corresponds to the release of water
molecules from outside the coordination sphere,
which needs lower energy. In the second stage, maximum moieties are removed, and the significant mass
loss at a higher temperature range justifies the higher
value of activation energy. The ligands like cyanide
and imidazole are removed at later stage attributing
towards their greater stability.

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CHEM. RES. CHINESE UNIVERSITIES

Vol.25

[5] Prasad S., Transition Metal Chemistry, 2003, 28, 1

Conclusions

The photoinitiated synthesis of complex of potassium hexacyanoferrate with imidazole has successfully been accomplished. The substitution of aquo
ligand by imidazole has been confirmed by UV-Vis
spectra, FTIR, and 1H NMR. SEM shows the formation of hybrid complex with a stable structure. Thermal decomposition of the complex takes place in two
steps.

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Acknowledgments
The authors are grateful to Prof. R. K. Wanchoo,
Director, National Institute of Technology, Srinagar
for his kind support, encouragement, and financial
assistance for carrying out this work. The services
from USIC, PU, Chandigarh and USIC, IIT, Roorkee
are also acknowledged.

[16] Jin S., Chen W., Inorg. Chem. Acta, 2007, 360,3756
[17] Lee C. K., Ling M. J., Lin I. J., Dalton Transaction, 2003, 4731
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