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Fluid Phase Equilibria 260 (2007) 295299

The ternary system H2OFe(NO3)3Co(NO3)2

isotherms 0 and 15 C
B. EL Goundali, M. Kaddami
Equipe de Physico-Chimie des Procedes, Laboratoire des Procedes de Valorisation des ressources naturelles,
des materiaux et environnement, Faculte des Sciences et Techniques de Settat, B.P: 577 route de Casablanca, Settat, Morocco
Received 9 March 2007; received in revised form 16 July 2007; accepted 19 July 2007
Available online 24 July 2007

Abstract
The solidliquid equilibria of the ternary system H2 OFe(NO3 )3 Co(NO3 )2 were studied by using a synthetic method based on conductivity
measurements.
Two isotherms were established at 0 and 15 C, and the stable solid phases which appear are the iron nitrate nonahydrate (Fe(NO3 )3 9H2 O), the
iron nitrate hexahydrate (Fe(NO3 )3 6H2 O), the cobalt nitrate hexahydrate (Co(NO3 )2 6H2 O) and the cobalt nitrate trihydrate (Co(NO3 )2 3H2 O).
2007 Elsevier B.V. All rights reserved.
Keywords: Phase diagram; H2 OFe(NO3 )3 Co(NO3 )2 ; Ferric nitrate; Cobalt nitrate; Ternary system

1. Introduction
Ferrites are technologically important materials because of
their interesting properties, extensively used in modern electronic tehnologies [15], microwave absorbers [6], chemical
sensors [79], catalysts [1013] and biomedical applications
[14]. Among these ferrites, cobalt ferrite CoFe2 O4 are very
promising materials for magneto-optical recording, high recording density, high coercivity, moderate saturation magnetization,
chemical stability, mechanical hardness [1519]. This ferrite is
also interesting owing the electronic and magnetic properties as
well as the potential applications in ferroelectromagnet devices
[20].
Within the framework of the international research consisting
of the development of these materials by soft chemistry technique, we undertook the study of the ternary system based on
water, iron and cobalt of nitrates salts.
The metallic nitrates form a family of compounds which are
very soluble in water and lead to complex mixtures and solid
solutions presenting a very good dispersal of the metallic elements at the atomic scale. The warming-up of these precursors to
moderated temperatures lead to homogeneous metallic oxides.

Corresponding author.
E-mail addresses: b.elgoundali@yahoo.fr (B. EL Goundali),
mkaddami@yahoo.fr (M. Kaddami).
0378-3812/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2007.07.048

We have studied the solidliquid equilibria for the ternary

system H2 OFe(NO3 )3 Co(NO3 )2 at atmospheric pressure and
at different temperatures.
2. Bibliography
2.1. Binary system H2 OCo(NO3 )2
The H2 OCo(NO3 )2 binary phase diagram has been established by Funk in 1900 [21], and by Wilcox and Bailey
in 1927 [22], at temperatures between 26 and 91 C. The
cobalt nitrate hydrates Co(NO3 )2 3H2 O, Co(NO3 )2 6H2 O and
Co(NO3 )2 9H2 O have been observed.
The system is characterized by the existence of three invariant
transformations (Table 1).
2.2. Binary system H2 O-Fe (NO3 )3
In our knowledge, the only available experimental data for
the H2 OFe(NO3 )3 binary system are the values of the solubility of iron nitrate in water measured by Malquori et al. [23],
within the range 040 C. The formation of the nonahydrate
Fe(NO3 )3 9H2 O is reported.
In a study of the H2 OFe(NO3 )3 HNO3 ternary system at
25 C [24], Malquori reported the formation of the two hydrates
Fe(NO3 )3 6H2 O and Fe(NO3 )3 9H2 O.

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B. EL Goundali, M. Kaddami / Fluid Phase Equilibria 260 (2007) 295299

Table 1
Binary system H2 OCo(NO3 )2 : invariant transformations

Table 2
Isotherm at 15 C of the system H2 OFe(NO3 )3 Co(NO3 )2

Temperature ( C)

Co(NO3 )2
(g%)

Invariant
points

Solid phases in equilibrium

Liquid phase composition

(mass fractions)

31.5
20.5
55

38
42.77
61.74

Eutectic
Peritectic
Peritectic

Ice + Co(NO3 )2 9H2 O

Co(NO3 )2 6H2 O + Liquid
Co(NO3 )2 3H2 O + Liquid

W [Fe(NO3 )3 ]

W [Co(NO3 )2 ]

0.000
0.022
0.067
0.077a
0.129
0.158
0.205
0.235a
0.245
0.298
0.335
0.369
0.387
0.402
0.430

0.487
0.463
0.429
0.427a
0.371
0.340
0.296
0.260a
0.245
0.170
0.125
0.082
0.070
0.042
0.000

2.3. Ternary system H2 OFe(NO3 )3 Co(NO3 )2

The ternary system wateriron nitratecobalt nitrate was
studied at 30 C [25]. Four solid phases were observed:
Fe(NO3 )3 .9 H2 O, Fe(NO3 )3 6H2 O, Co(NO3 )2 6H2 O and
Co(NO3 )2 3H2 O.
3. Experimental method
The curves of solubility are determined by a synthetic method
based on conductivity measurements [2628]. It practically consists to adding progressively a solvent to a saline mixture of
known composition, to measure the conductivity of the solution
at thermodynamic equilibrium and to represent the evolution
according to the quantity of liquid added. The obtained curves
present angular points and plateaux that correspond to phase
transformations. The analysis of series of miscellanies permits
to identify the liquidus curves and to determine the compositions of the invariant solutions and solid phases (anhydrous or
hydrated).
The identification of hydrates of iron and cobalt nitrate has
been conducted by the sets and the remainders method [29], of
which the principle is the following one: a mixture of known
composition (set S) is maintained at a constant temperature and
stirred during 1015 days. After decantation, the separated liquid
and solid phases were analyzed.
The solid, impregnated of the saturated solution, constitutes
the remainder (R).
The starting salts were iron nitrate nonahydrate
(Fe(NO3 )3 9H2 O) and cobalt nitrate hexahydrate (Co(NO3 )2
6H2 O). These were the products from riedel-dehaen, with
purity of the order of 9698%. The water used was bidistilled
and its conductivity is in the order of 6 s at 18 C.
4. Experimental results
4.1. Ternary system H2 OFe(NO3 )3 Co(NO3 )2
The ternary system H2 OFe(NO3 )3 Co(NO3 )2 has been
studied at 0 and 15 C. The obtained results are described graphically in the classic representation in which the reference mark
is an isosceles rectangle triangle whose right angle corresponds
to pure water. The salts compositions are expressed in mass
fraction.
4.1.1. Isotherm 15 C
The solid phases observed at 15 C are iron nitrate nonahydrate, iron nitrate hexahydrate, cobalt nitrate trihydrate

Phenomenon

Solid phases
in equilibrium

Liquidus

Liquid D
Liquidus

Liquid C
Liquidus

Liquid B
Liquidus

Co.6
Co.6
Co.6
Co.6 + Co.3
Co.3
Co.3
Co.3
Co.3 + Fe.6
Fe.6
Fe.6
Fe.6
Fe.6
Fe.6 + Fe.9
Fe.9
Fe.9

Notations: Fe.9, Fe (NO3 )3 9H2 O; Fe.6, Fe (NO3 )3 6H2 O; Co.6, Co

(NO3 )2 6H2 O; Co.3, Co (NO3 )2 3H2 O.
a Point obtained by extrapolation of liquidus curves.

and cobalt nitrate hexahydrate, their respective branches of

solubility are AB: Fe.9, BC: Fe.6, CD: Co.3 and DE:
Co.6.
The solubility values are gathered in Table 2 and are presented
in Fig. 1.
4.1.2. Isotherm 0 C
At this temperature, the same solid phases appear and their
respective branches of solubility are: AB: Fe.9, BC: Fe.6, CD:
Co.3 and DE: Co.6.

Table 3
Isotherm at 0 C of the system H2 OFe(NO3 )3 Co(NO3 )2
Liquid phase composition
(Mass fractions)
W [Fe(NO3 )3 ]

W [Co(NO3 )2 ]

0.000
0.021
0.040
0.057a
0.064
0.108
0.150
0.197
0.212a
0.237
0.282
0.318
0.355a
0.372
0.400

0.452
0.436
0.407
0.397a
0.389
0.346
0.301
0.262
0.255a
0.216
0.152
0.106
0.070a
0.043
0.000

Phenomenon

Solid phases
in equilibrium

Liquidus

Liquid D
Liquidus

Liquid C
Liquidus

Liquid B
Liquidus

Co.6
Co.6
Co.6
Co.6 + Co.3
Co.3
Co.3
Co.3
Co.3
Co.3 + Fe.6
Fe.6
Fe.6
Fe.6
Fe.6 + Fe.9
Fe.9
Fe.9

Notations: Fe.9, Fe(NO3 )3 9H2 O; Fe.6, Fe(NO3 )3 6H2 O;

Co(NO3 )2 6H2 O; Co.3, Co(NO3 )2 3H2 O.
a Point obtained by extrapolation of liquidus curves.

Co.6,

B. EL Goundali, M. Kaddami / Fluid Phase Equilibria 260 (2007) 295299

297

Fig. 1. Isotherm at 15 C of the ternary system H2 OFe(NO3 )3 Co(NO3 )2 . Notations: L: Liquid; Fe.9: Fe(NO3 )3 .9H2 O; Fe.6: Fe(NO3 )3 6H2 O; Co.6:
Co(NO3 )2 6H2 O; Co.3: Co(NO3 )2 3H2 O.

The solubility values are gathered in Table 3 and are presented

in Fig. 2.

5. Characterization
To control the nature of the solid phases in equilibrium
with different saturated solutions, some mixtures (M1 , M2 ,
M3 and M4 ) of compositions appropriately chosen have been
maintained separately at 15 C under gentle stirring for 15
days.

The obtained miscellanies are composed each of a liquid

phase in equilibrium with a solid phase.
The results of the chemical dosage of these phases are given
in Table 4.
The exploitation of these results according to the method of
the sets of Chretien [29], led to the representative points of each
hydrate for the various liquidus curves of the system (Fig. 3).
Finally, four solid phases were observed in the
H2 OFe(NO3 )3 Co(NO3 )2 ternary system at 15 C: iron
nitrate nonahydrate, iron nitrate hexahydrate, cobalt nitrate
trihydrate and cobalt nitrate hexahydrate.

Table 4
Ternary system H2 OFe(NO3 )3 Co(NO3 )2
Mixture (Mi )

M1
M2
M3
M4

Equilibrium
temperature ( C)

15
15
15
15

Method of the sets and the remainders.

Composition of Mi (Mass percentage)

Fe(NO3 )3

Co(NO3 )2

45
35
12.5
2.5

2.5
15
40
50

Phenomenon

Crystals
Crystals
Crystals
Crystals

Composition of the phase analyzed Ri (Mass percentage)

Fe(NO3 )3

Co(NO3 )2

55.25
62.50
05.00
01.27

0.75
3.13
62.35
56.51

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B. EL Goundali, M. Kaddami / Fluid Phase Equilibria 260 (2007) 295299

Fig. 2. Isotherm at 0 C of ternary system H2 OFe(NO3 )3 Co(NO3 )2 . Notation: L: Liquid; Fe.9: Fe(NO3 )3 9H2 O; Fe.6: Fe(NO3 )3 6H2 O; Co.6: Co(NO3 )2 6H2 O;
Co.3: Co(NO3 )2 3H2 O.

Fig. 3. Isotherm at 15 C of the ternary system H2 OFe(NO3 )3 Co(NO3 )2 The sets and the remainders method.

B. EL Goundali, M. Kaddami / Fluid Phase Equilibria 260 (2007) 295299

6. Conclusion
In this study, we have established the two isotherms 0 C
and 15 C for the ternary system H2 OFe(NO3 )3 Co(NO3 )2 .
Each isotherm includes four solubility branches corresponding
respectively to iron nitrate nonahydrate, iron nitrate hexahydrate,
cobalt nitrate trihydrate and cobalt nitrate hexahydrate.
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