Inorganic Materials, Vol. 39, No. 10, 2003, pp. 1088–1091. Translated from Neorganicheskie Materialy, Vol.

39, No. 10, 2003, pp. 1260–1263.

Original Russian Text Copyright © 2003 by Lykasov, Pavlovskaya.

Phase Equilibria in the Fe–Na–O System

between 1100 and 1300 K
A. A. Lykasov and M. S. Pavlovskaya
South Ural State University, pr. Lenina 76, Chelyabinsk, 454080 Russia
e-mail: mar@fizchim.susu.ac.ru
Received December 27, 2002

Abstract—EMF measurements in electrochemical cells with an oxygen-ion-conducting solid electrolyte

were used to assess the equilibrium oxygen pressure as a function of temperature in a broad composition
range in the Fe–Na–O system and to map out the 1070-, 1170-, and 1270-K sections of the Fe–Na–O phase
diagram. The thermodynamic model proposed for solid solutions of Na in wüstite made it possible to estab-
lish a relation between the equilibrium oxygen pressure, the composition of the wüstite solution, and tem-
perature.

INTRODUCTION designed divided-gas-space electrochemical cell,

The Fe–Na–O system has not yet been studied
experimentally in sufficient detail. As reported in [1–3],
the stable compounds existing in this system between
1070 and 1270 K are NaFeO2 (orthoferrite), NaFe5O8
(ferrite), and NaFe2O3. The system was also shown to
contain two solid-solution series, based on wüstite
(FeOx–NaFeO2) and magnetite (Fe3O4–NaFe5O8). The
Na solubility in wüstite at 1270 K was reported to be
19 wt %, as determined by chemical analysis and x-ray
diffraction [1–3]. The homogeneity range of Na-substi-
tuted wüstite has not been located with certainty. Igushi
et al. [4] studied wüstite solid solutions in limited
ranges of compositions and oxygen partial pressures by
equilibrating the solid solutions with mixtures of H2
and water vapor of controlled composition. Data on the
properties of the spinel solid solution are not available
in the literature. The phase diagram of the Fe–Na–O
system was reported to contain two regions in which
three condensed phases are in equilibrium with the gas
phase [1–3]:
the most Na-rich wüstite solution + spinel solution +
NaFe2O3;
NaFe2O3 + NaFeO2 + spinel solution.
According to Balkhi et al. [3], NaFe2O3 is interme-
diate in structure between wüstite and α-NaFeO2.
Above 1320 K, NaFe2O3 dissociates into NaFeO2 and
Na-substituted wüstite. NaFe2O3 is unstable in air: at
room temperature, it slowly hydrolyzes.
The thermodynamic properties of substances in the
Fe–Na–O system are difficult to study experimentally
because of the high sodium vapor pressure: at high tem-
peratures, Na vaporization may alter the bulk composi-
tion of the sample and impede equilibration of the sys-
tem. To obviate this difficulty, we used a purpose-
which allowed the sample to be isolated in the isother-
mal zone of the reactor. The design of the cell was
described in detail elsewhere [5, 6].
EXPERIMENTAL
Samples for this investigation were prepared by
solid-state reactions. The bulk composition of the sam-
ples was Fe1 – cNacOy , where c is the Na/(Fe + Na)
molar ratio, and y is the O/(Fe + Na) molar ratio (degree
of oxidation).
We used two preparative procedures. In one of them,
we fired powder mixtures of extrapure-grade carbonyl
iron calcined at 950 K, analytical-grade Fe2O3, and
NaFeO2. Sodium orthoferrite was presynthesized by
firing a 1 : 1 mixture of analytical-grade Na2CO3 and
Fe2O3 powders in air at 1070 K for 10 h. The resultant
material was single-phase, as checked by x-ray diffrac-
tion (XRD). By this procedure, we prepared samples
with constant y and varied Na content.
The other procedure involved two steps:
(1) preparation of wüstite with the preset oxygen
content, y = y0, from carbonyl Fe and analytical-grade
Fe2O3 powders;
(2) preparation of samples from wüstite and sodium
orthoferrite.
The compositions of the samples (c and y) obeyed
the equation
y = y0 + 2(1 – y0)c
(tie line between FeO y0 and NaFeO2).

0020-1685/03/3910-1088$25.00 © 2003 MAIK “Nauka /Interperiodica”

 PHASE EQUILIBRIA IN THE Fe–Na–O SYSTEM 1089

Ö, mV XII E, mV
1 6 XI
2 7 X
200 3 IX
4
5 VIII
VII 150

150 VI

V
125
IV

100 1 7 13
III
2 8 14
3 9 15
II 100
4 10 16
I 5 11 17
50 6 12

1100 1200 1300 1100 1200 1300

í, ä
Fig. 1. Temperature-dependent emf across cell (1) for sam-
ples with y0 = 1.064: (I) c = 0.02, y = 1.07; (II) c = 0.04, y =
1.065; (III) c = 0.06, y = 1.065; (IV) c = 0.1, y = 1.054;
(V) c = 0.05, y = 1.098; (VI) c = 0.16, y = 1.046; (VII) (1) c =
0.21, y = 1.094; (2) c = 0.15, y = 1.103; (3) c = 0.15, y =
1.115; (4) c = 0.25, y = 1.084; (5) c = 0.20, y = 1.075;
(VIII) c = 0.20, y = 1.157; (IX) c = 0.35, y = 1.014; (X)
(6) c = 0.30, y = 1.07; (7) c = 0.35, y = 1.103; (XI) c = 0.30,
y = 1.115; (XII) c = 0.35, y = 1.11.
í, ä
Fig. 2. Temperature-dependent emf across cell (1) for S + W +
NaFe2O3 three-phase samples: (1) c = 0.10, y = 1.256;
(2) c = 0.20, y = 1.075; (3) c = 0.25, y = 1.084; (4) c = 0.21,
y = 1.039; (5) c = 0.30, y = 1.015; (6) c = 0.15, y = 1.17;
(7) c = 0.10, y = 1.17; (8) c = 0.0752, y = 1.25; (9) c = 0.175,
y = 1.049; (10) c = 0.20, y = 1.034; (11) c = 0.20, y = 1.042;
(12) c = 0.18, y = 1.051; (13) c = 0.20, y = 1.069; (14) c =
0.25, y = 1.052; (15) c = 0.15, y = 1.103; (16) c = 0.15, y =
1.19; (17) c = 0.30, y = 1.047.

After firing and emf measurements, the compo-
sitions of the samples were checked by chemical ana-
lysis.
In temperature-dependent emf measurements, we
used the electrochemical cell
Pt|Fe, FeO ( reference ) | ZrO 2 + Y 2 O 3
(1)
| Fe 1 – c Na c O y | Pt.
RESULTS AND DISCUSSION
Figure 1 shows the temperature-dependent emf of
samples with Û0 = 1.064. The slope of the lines depends
on the phase composition of the samples: for single-
phase samples, the slope is far more gradual than that
for mixtures of Na-substituted wüstite and a spinel
solution. With increasing temperature, the emf across
the cell increases, independent of phase composition.
Since the equilibrium oxygen partial pressure over the
reference electrode rises with temperature, the same
temperature dependence of p O2 is observed for the
samples. With increasing c in the wüstite solution, the
emf across cell (1) rises. Consequently, the equilibrium
oxygen pressure over the wüstite solution,
0 4FE
log p O2 = log p O2 + ---------------------, (2)
2.303RT
increases with Na content. In Eq. (2), E is the measured
0
emf across cell (1), and p O2 is the equilibrium oxygen
partial pressure over the equilibrium mixture of Fe and
wüstite (over the Fe, FeO reference electrode).
Figures 2 and 3 show the temperature-dependent
emf across cell (1) for three-phase samples: S + W +
NaFe2O3 and S + NaFeO2 + NaFe2O3. For such sam-
ples, the emf across the cell depends on temperature
and not on the bulk composition of the samples. We
obtained the following least squares equations for the
temperature-dependent emf:
E = 0.324T – 250.044 ± 5 mV (3)

INORGANIC MATERIALS Vol. 39 No. 10 2003

1090 LYKASOV, PAVLOVSKAYA

Ö, mV The experimental data were used to plot the compo-

sition dependences of the emf across cell (1) (Fig. 4).
The E(y) curves have a complex shape. The first break
in curves 3–5 and the single break in curves 1 and 2 rep-
200
resent the boundary between the Na-substituted wüstite
field and the W + S two-phase region. The next break in
curves 3–5 is associated with the transition to the three-
phase field W + S + NaFe2O3. For three-phase samples
at constant temperature, the equilibrium oxygen pres-
sure and, hence, the emf across cell (1) are independent
of the bulk sample composition. Accordingly, E does
not vary with y. The phase compositions inferred from
emf measurements agree with XRD data (obtained on
1 quenched samples).
2
150 3 The above results were used to map out the FeO–
4 Fe3O4–NaFeO2 phase diagram. The 1270-K isotherm is
5 displayed in Fig. 5. The oxygen-rich phase boundary of
6
7 Na-substituted wüstite was located from the position of
8 the first break in curves 1–5 in Fig. 4. The position of
9 the second break in curves 3–5 was used to construct
the boundary between the two-phase region W + S and
the three-phase region S + W + NaFe2O3.
1100 1200 1300
í, ä The position of the oxygen-rich phase boundary of
the wüstite solid solution was refined from the intersec-
Fig. 3. Temperature-dependent emf across cell (1) for S + tion of the oxygen isobars passing through the Na-sub-
NaFeO2 + NaFe2O3 three-phase samples: (1) c = 0.30, y =
1.121; (2) c = 0.25, y = 1.141; (3) c = 0.20, y = 1.207; (4) c =
stituted wüstite field and the tie lines lying in the W + S
0.30, y = 1.114; (5) c = 0.30, y = 1.07; (6) c = 0.30, y = 1.07; two-phase region. The isobars were calculated by the
(7) c = 0.35, y = 1.103; (8) c = 0.35, y = 1.01; (9) c = 0.20, equation
y = 1.17.
24 800 ( c + x ) ( 2 – c + x )
log p O2 = 12.102 – ---------------- + -----------------------------------------
-
(1 + x)
T 2
Ö, mV
160
119 430 ( 2x + c )
" ×  60.594 – ------------------- – --------------------  43.445 – ----------------
140
85 175
 T  1–c  T 
120 (5)
2 2
100 x 2c 2c E 22
+ 2 log ------------ – -------------------2 – -------------------2 --------------------
-
80 1 + x ( 1 + x ) ( 1 + x ) 2.303RT
5 4 3 2 1
60
40 4c ( 1 – c ) E 12 8c ( 2x + c ) b 2
– ---------------------2- --------------------
- + -------------------------- --------------------
-,
20 (1 + x) 2.303RT 1 – c 2.303RT
0
1.00 1.05 1.10 1.15 1.20 1.25 Û derived in the subregular ionic solution approximation
[5, 6].
Fig. 4. Plots of the emf across cell (1) vs. oxygen content for
samples with c = (1) 0.025, (2) 0.05, (3) 0.075, (4) 0.10, and The Na solubility in wüstite was found to vary little
(5) 0.15.
in the temperature range studied: c = 0.162 at 1070 K
and c = 0.164 at 1270 K.
for the three-phase equilibrium S + W + NaFe2O3 (Fig. 2), Over the entire Na-substituted wüstite field, y
exceeds unity. With increasing Na content, y decreases,
E = 0.325T – 220.327 ± 5 mV (4) approaching unity. The most oxygen-rich wüstite is in
equilibrium with the spinel phase Fe3 – zNazO4. The
for the three-phase equilibrium S + NaFeO2 + NaFe2O3 composition of the spinel phase was determined using
(Fig. 3). tie lines passing through the S + W two-phase region.

INORGANIC MATERIALS Vol. 39 No. 10 2003

 PHASE EQUILIBRIA IN THE Fe–Na–O SYSTEM 1091

Û first time used to assess the equilibrium oxygen pres-

Fe3O4
NaFe5O8
sure as a function of temperature in a broad composi-
tion range in the Fe–Na–O system and to map out the
1.30 1070-, 1170-, and 1270-K sections of the Fe–Na–O
phase diagram.
S+NaFeO2
The thermodynamic model proposed for solid solu-
1.25 tions of Na in wüstite made it possible to establish a
relation between the equilibrium oxygen pressure, the
composition of the wüstite solution, and temperature.
1.20 W+S

ACKNOWLEDGMENTS
1.15 This work was supported by the Russian Foundation
1 2 3 for Basic Research, project no. 01-03-96419.

1.10 S+
S+W+ REFERENCES
+ NaFe2O3 NaFeO2+
+ NaFe2O3 1. Claude, J.M., Balkhi, A.M.El., Jeannot, F., et al.,
1.05 W Système Fe–Fe2O3–NaFeO2: I. Solubilité du sodium
6
4 5 dans la wüstite pour p O2 = 1.2 × 10–15 bar à 1000°C,
W + NaFe2O3
Fe + W NaFe2O3 NaFeO2 Met. Sci. Rev. Met., 1975, vol. 72, no. 7/8, pp. 599–603.
1.00 2. Balkhi, A.M.El., Zann, M., Gleitzer, C., and Aubry, J.,
0 0.1 0.2 0.3 0.4 Ò
Le système Fe–Fe2O3–NaFeO2: Domaine et propriétés
de la wüstite sodée, Met. Sci. Rev. Met., 1976, vol. 73,
Fig. 5. 1270-K section of the FeO–Fe3O4–NaFeO2 phase
no. 12, pp. 761–768.
diagram. W = wüstite solution; S = spinel solution; the thin
solid lines represent tie lines in two-phase regions; the 3. Balkhi, A.M.El., Zann, M., and Gleitzer, C., Préparation
dashed lines represent isobars in the Na-substituted wüstite et propriétés d’un oxyde de sodium–ferrite(II, III):
field; log ( p O /Pa ) = (1) 17.757, (2) 17.651, (3) 17.493, NaFe2O3, J. Solid State Chem., 1976, vol. 18,
2
pp. 293−297.
(4) 19.55, (5) 18.945, (6) 18.311.
4. Igushi, Y., Amahiro, Y., and Hirao, J., Equilibrium
between FeO–M2O (M = Li, Na) Solid Solution and
At the low-oxygen phase boundary, wüstite is in Oxygen in Gas Phase at 1273 K, Nippon Kinzoku Gak-
kaishi, 1986, vol. 50, no. 3, pp. 282–287.
equilibrium with a metallic phase consisting predomi-
nantly of Fe. 5. Lykasov, A.A., Thermodynamics of Wüstite Solutions,
Doctoral (Chem.) Dissertation, Chelyabinsk: Chelyab-
insk State Technical Univ., 1991.
CONCLUSIONS 6. Lykasov, A.A., Karel, K., Men’, A.N., et al., Fiziko-
khimicheskie svoistva vyustita i ego rastvorov (Physico-
EMF measurements in electrochemical cells with an chemical Properties of Wüstite and Its Solutions), Sver-
oxygen-ion-conducting solid electrolyte were for the dlovsk: Ural. Nauchn. Tsentr Akad. Nauk SSSR, 1987.

INORGANIC MATERIALS Vol. 39 No. 10 2003