J, inorg, nucL Chem. Vol. 42, pp.

811413
Pergamon Press Ltd., 1980. Printed in Great Britain

SYNTHESIS AND THE THERMAL DECOMPOSITION OF

IRON(III) TRIS(OXALATO) FERRATE(III)
TETRAHYDRATE
T. K. SANYAL and N. N. DASS
Department of Chemistry, Dibrugarh University, Dibrugarh 786004, Assam, India

(First received 23 October 1978; in revised /orm 25 April 1979)

Abstract--The paper describes the synthesis and thermal decomposition of Fe[Fe(C2Oa)3]4H20 in air. The
compound is completely dehydrated at 170Cand some reduction in the inner sphere iron(Ill) occurs. At 290C, a
mixture of ferric oxide and ferrous oxalate is obtained. Beyond 420C, the decomposition is complete and final
residue is ferric oxide. A probable reaction mechanism is proposed.

IR studies. IR spectra of the gases evolved during the complete

decomposition of the complex were made using a 10cm cell
fitted with KBr windows and that of the complex and its decomposition products at different temperature were recorded in
Nujol Mulls with a SPECORD IR 75 spectrophotometer.
X-Ray diffraction photographs. X-Ray diffraction powder
photographs were taken using Co ks radiation.
Magnetic moment measurement. The magnetic moment of the
complex, Fe[Fe(C204)~]'4H20 was measured with a Gouy
balance, using HgCo(SCN)a as calibrant and molecular susceptibilities were corrected for the constituent atoms using Pascal's
constants.

INTRODUCTION
The complex iron(ll) tris oxalato ferrate(lI) is well
known[l]. A ferric oxalate having the composition
Fe2(C204)3"SH20 has also been reported[2]. It is a
canary yellow microcrystalline powder and does not give
the test for oxalate ion and shows only a weak reaction
of ferric ion with potassium iodide or thiocyanate. A
comprehensive review of metal oxalato complexes may
be found elsewhere[3]. The thermal decomposition of
the oxalato complexes of nickel, cobalt and copper has
been reported[4]. Thermal decomposition of tris oxalato
ferrate(lll) and analbgous tris oxalato complexes of Cr,
Co and Rh have also been extensively studied [5--8]. But
the complex iron(Ill) tris oxalato ferrate(III) does not
appear to have been studied.

EXPERIMENTAL

Preparation of the complex. Ferric hydroxide, prepared from

ferric chloride, was made free from chlorine. It was dissolved in
glacial acetic acid and heated on a steam bath. A yellow compound was precipitated by dropwise addition of a saturated
solution of oxalic acid in glacial acetic acid. The compound was
filtered off, washed with glacial acetic acid, dried and stored in
the dark over calcium chloride. The water was determined
gravimetricallyby ignition in a dynamic nitrogen gas atmosphere
and absorbing the water in a U tube filled with calcium chloride.
Anal. Calc. for FeFe(CzO4)3.4H20, Fe, 24.83%; C, 16.44%; H,
1.78%; H20, 16.15%. Found: Fe, 24.60%; C, 16.44%; H, 1.78%;
H~O, 16.30%.
DTA and TGA studies. The thermogravimetricanalysis (TGA)
and differential thermal analysis (DTA) were carried out in a
Paulik-Erdy system type MOM derivatograph fabricated by the
M/S Hungarian Optical Works, Budapest, operating at a heating
rate of 8C/rain. The amount of the substance used was 700 rag.
Calcined alumina (AR) was taken as inert reference substance.
The furnace atmosphere was air.
Reaction stoichiometry studies. 0.1 N tetra-n-butyl ammonium
hydroxide in isopropanol/methanol was added to a solution of
the compound in water to precipitate ferric hydroxide and the
amount of the uncomplexed iron was estimated. The filtrate was
evaporated on a steam bath and a brown compound was extracted and analysed for the inner sphere iron.
The complex was decomposed at different temperatures and
the products obtained were analysed. For decomposition, the
samples were heated in a tube surrounded by heating coil controlled by a Dimmerstat fitted with continuously variable auto
transformer, in an atmosphere of air. Temperature was measured
by Osaw vernier potentiometer through a thermocouple.
Conductometric studies. The conductivity measurement was
carried out with Philips conductivity bridge (PR 9500). Conductivity water was used throughout the experiment.

RESULTS AND DISCUSSIONS

Structure of the compound
The water analysis revealed that the compound should
contain four molecules of water of crystallisation per
molecule of the compound. The equivalent conductivity
at infinite dilution was calculated. The result indicated
that though the compound had predominantly a diionic
salt character some dissociation to produce free oxalate
could occur. This is a characteristic property of the tris
oxalate ferrate(III) complex [9]. In the IR spectrum of the
compound, the presence of strong bands at 1730, 1665
and 1610cm -t were due to vc=o asym. and at 1270cm -t,
due to vc=o sym. frequencies of the oxalato ~oup. The
vF~o band also occured at 570 and 560 c m - , whereas
bands at 490cm -t 430cm -I might be due to ring deformation and/or 8oco vibration, All these bands indicated
the presence of a coordinated oxalato group[10]. These
results suggest the formula of the compound is
Fe[Fe(C204)3].4H20. However, the association of some
of the water molecules with the coordinated oxalato
group cannot be excluded. The effective magnetic
moment of the complex was found to be 5.92B.M.,
which indicated high spin ferric species. The magnetic
moment of KaFe(C204)3 was reported to be 5.77 [12].

811

Weiglft loss and DTA studies

In the DTA curve (Fig. I), after a break at 120C, a
sharp endothermic peak with a ATmax of 170C was
found followed by a large exothermic peak with a ATma~
of 290C. After this at 24&C another exothermic peak
appeared accounting for the final decomposition. A
fourth smaller peak, also exothermic, was observed at
500C.
The water, carbon dioxide and carbon monoxide
evolved during the complete decomposition were
identified by IR spectroscopy [ l l ].
The break in the TG and DTA curves at 120C, in-

812

T.K. SANYALand N. N. DASS

29O*
~200

I000

D
8

BOO.

600

400
U
o

ZOO

Fig. 2. X-Ray diffraction powder photograph. (A) Final decomposition residue; (B) Ferric oxide.
I00

zoo

3oo

4oo
C

Fig. 1. Thermal decompositionof iron(llI) tris oxalato ferrate(IIl)

tetrahydrate in air. (A) DTA curve; (B) DTG curve; (C) Weight
loss curve; (D) Temperature scale.
dicated the loss of one molecule of water. This corresponded well with the weight loss data (found 4%,
theor. 4.02%). The endothermic peak at 17&C corresponded to 26.3% weight loss which might be accounted for by the evolution of three molecules of water
along with the decomposition in the complex. A green
compound was produced at this state, which might will
be a binuclear complex (Fe, found 33.1%, theor. 33.53%)
like [(CzO4)2Fe(II) . . . ( C 2 0 4 ) . . . Fe(II)(C204)2]6-, where
the two iron atoms may be reduced by one oxalate group
via charge transfer from the oxalate, as found in the
thermal decomposition of potassium tris oxalato ferrate(III) at 200C[7]. The broad band in the region 17501600 cm-t in the IR spectrum of the compound obtained
from the original complex after heating for 15 min at
170C, probably indicates the existence of oxalato
bridged iron atoms. In the case of other metal exalate
complexes comparatively distinct split bands usually
occur in this region[10].
The exothermic peak in the DTA curve at 290C
corresponded to 50.3% weight loss in the TG curve. The
product obtained was separated by hot water with
difficulty into two compounds, one reddish brown and
the other pale yellow. The reddish brown compound was

Fe[Fe(C204)3].4H20

,~c

identified as Fe~O3 (Fe, found 69.1%, theor. 69.7%). The

pale yellow compound gave on analysis Fe, 38.1% and
oxalate 61.8% compared to the theoretical value of Fe,
37.7% and oxalate 62.3% for ferrous oxalate. The IR
spectrum of the compound was found identical with that
of ferrous oxalate prepared by the method described by
Wendlandt and Simmons[13]. The formation of Fe20~
and FeC:O4 indicated that outer iron in the complex
formed ferric oxide and the inner iron was reduced to
Fe(II) forming FeC204.
The DTA peak at 420C corresponded to complete
breakdown of the complex. The weight loss indicated
was 68.4%. Immediately after this the TG curve showed
a slight rise. The final decomposition product was
identified as ferric oxide, the position and number of
lines in the X-ray diffraction photograph of the residue
exactly coincided with that of Fe203 (BDH) (Fig. 2).
The weight loss found at 420C corresponded to the
formation of FeO, which might be formed by the reduction of Fe203 by carbon monoxide evolved during the
decomposition of ferrous oxalate. The conditions were
favourable for this to take place since the two solids
FeC204 and Fe203 were intimately mixed in the ratio
9:5. However, FeO is not stable in air and is oxidised to
Fe203 by absorbing oxygen from the atmosphere, which
was indicated by the rise in the TG curve.
The small exothermic peak at 500C did not correspond to any weight loss. This might be due to some
change in the crystalline structure of the ferric oxide.

Stoichiometry o/the reaction

The TG indicated that the complex was not dehydrated
in a single stage. Of the four water molecules, one was
lost easily; the other three at a higher temperature, along
with some decomposition of the complex. This indicated
that all the water molecules were not held similarly in the
crystal lattice. The three similar molecules of water
might be attached by hydrogen bonding to the coordinated oxalate ring.
Our results suggest:

Fe[Fe(C204)3].3H20 + H20(v)

+ C02(g)

+ 3H20(v)

29o-c

+ l~CO(g) Abo~42(PC.+0

i~o-c ~~Fe2[(C204)2Fe... (C204)... Fe(C204)2]

) -~Fe203(s) +
)

FeC204(s) + 1~C02(g)

Fe203(s) + C02(g) + C0(g).

Synthesis and the thermal decomposition of iron(Ill) tris(oxalato) ferrate(Ill) tetrahydrate

The reduction of iron(Ill) in the coordinated sphere
must take place by electron transfer from an oxalate
ligand to the iron. This suggests the formation of a gridged
intermediate in which the two iron(Ill) atoms are
reduced by a single oxalate group.

Comparison with ferrous and ferric oxalate

Although the final decomposition product in the case
of ferric oxalate, as reported by Broadbent et a/,[6], is
the same as for our complex, the mode of decomposition
in the two cases is very different. The DTA of ferric
oxalate gave large exothermic double peaks with maxima
at 190 and 240C, whereas in the case of iron(Ill) tris
oxalate ferrate(lll) tetrahydrate, decomposition proceeded with absorption of heat at 170C followed by
decomposition with exothermic peaks at 290 and 420C.
At 290C, ferrous oxalate was obtained along with ferric
oxide. The DTA curve for further decomposition was
similar to that of ferrous oxalate, which has previously
been reported [61, excepting the fact that the final decomposition occured in our case at 420C, whereas in the case
of ferrous oxalate in air, it occurred at 235C[14]. It seems
that the presence of free Fe203 had a profound effect on
the thermal decomposition of the ferrous oxalate.
.4cknowledgements--The authors thank Mr. S. N. Dutta and Mr.
B. D. Chattaraj of R. R. L., Jorhat, Assam, for DTA, Dr. B.
Chaudhuri of Gauhati University, Assam, for X-ray diffraction
powder photographs, Dr. R. D. McDonald of CSIRO, Australia,
for micro analysis, Mr. P. Gogoi, IIF, Bombay for magnetic

813

moment data and the U.G.C. for the equipment grant to N.N.D.
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