ISSN 1070-4272, Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 2, pp. 196−198. © Pleiades Publishing, Ltd.

, 2011.
Original Russian Text © A.I. Demidov, I.A. Markelov, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 2, pp. 200−202.

PHYSICOCHEMICAL STUDIES
OF SYSTEMS AND PROCESSES

Thermodynamics of Interaction of Iron Oxides

and Carbon Monoxide
A. I. Demidov and I. A. Markelov

St. Petersburg State Polytechnical University, St. Petersburg, Russia

Received September 12, 2010

Abstract—Computations of equilibrium mole fraction of carbon monoxide in the gas phase in an interaction of
iron oxides and carbon monoxide were conducted.
DOI: 10.1134/S1070427211020054

Thermodynamics of Fe–O–C system is of great in- xCO2 1 – xCO

= —— = ———. (1.1)
terest for a thermodynamic substantiation of recovery xCO xCO
regimes of iron ore and of iron and cast iron production
[1–4]. As a rule experimental dependences of an equilibri- The mole fraction of carbon monoxide in the gas phase
um mole fraction of carbon monoxide in the gas phase on was get by relationship (1.1):
temperature for reactions (2)–(4) were used in an analysis
1
of recovery of iron oxides by carbon monoxide: xCO = ——— . (1.2)
1 + Kp
3Fe2O3 + CO = 2Fe3O4 + CO2, (1) The computations demonstrated that obtained depen-
dences of the equilibrium mole fraction of carbon mon-
Fe3O4 + CO = 3FeO + CO2, (2)
oxide in the gas phase on the temperature for reactions
FeO + CO = Fe + CO2, (3)
(2) and (3) were not consistent with the experimental data
[4] if stoichiometric compound FeO was taken as iron (II)
1/4Fe3O4 + CO = 3/4Fe + CO2. (4) oxide (Fig. 1). Thus, in the subsequient computations we
assumed that a wustite composition in equilibrium with
Reaction (4) proceeds at temperature below 843 K. both iron and magnetite corresponds to formula Fe0.947O
Simultaneous determination of the equilibrium mole and equation (2) and (3) (at wustite participation) were
fraction of carbon monoxide for reaction (1) was not written in the following form:
performed due to its very small content in the equilibrium 0.947 3
gas phase [2, 3]. ——– Fe3O4 + CO = ——– Fe0.947O + CO2, (2')
0.788 0.788
By thermodynamic data [5, 6] calculations of equilib-
rium mole fraction of carbon monoxide in the gas phase Fe0.947O + CO = 0.947Fe + CO2. (3')
for reactions (1)–(4) were performed. The equilibrium
constants of reactions (1)–(4) are similar by the form and The results of calculations of the equilibrium constants
represent a ratio of carbon dioxide pressure to carbon and the molar fraction of carbon monoxide in the gas
monoxide one. phase for reactions (1), (2'), (3'), (4) in the temperature
range 298–1600 K are listed in the table. The table data
ΔGT° pCO2 Ptotal/xCO2 show that the values of the equilibrium mole fraction
Kp = exp – —— = —— = –———–
RT pCO Ptotal/xCO of carbon monoxide in the gas phase for reaction (1) is

196
 THERMODYNAMICS OF INTERACTION OF IRON OXIDES 197

(3')

(2')

Fig. 2. Dependence of the equilibrium mole fraction of carbon

Fig. 1. Dependence of the equilibrium mole fraction of carbon
monoxide in the gas phase xCO (%) for reactions (2)–(4) on
temperature T (K). Experimental data for reaction: (I) (2), (II)
(3), the same for Fig. 2.
characterized by the value of order of 10–5, and therefore,
the dependence of the equilibrium mole fraction of carbon
oxide (II) in the gas phase on the temperature in Fig. 2
for reaction (1) equilibrium is not shown.
Figure 2 shows that the dependences of mole fraction
of carbon monoxide in the gas phase for equilibria of
monoxide in the gas phase xCO (%) for reactions (2'), (3'), (4)
on temperature T (K).
reactions (2'), (3'), (4) intersect at temperature about
850 K. Below this temperature, the magnetite recovery
by carbon monoxide to iron occurs, and at a higher tem-
perature magnetite is first reduced to wustite and then
with increasing concentration of carbon oxide (II) in the
gas phase wustite is reduced to iron. With increasing
temperature the molar fraction of carbon monoxide in the
gas phase for equilibria of reactions (3'), (4) increases, the
equilibria shift to the left towards the initial substances,

Values of the equilibrium constants of reactions (1)–(4) and mole fractions of carbon monoxide in the gas phase

Reaction

Т, K (1) (2') (3') (4)

ln Kp xCO, % ln Kp xCO, % ln Kp xCO, % ln Kp xCO, %

298.15 23.05 – 0.19 0.45 –0.19 0.55 1.35 0.21
300 22.94 – 0.56 0.36 –0.46 0.61 1.35 0.21
400 18.56 – 0.85 0.30 –0.66 0.66 0.96 0.28
500 15.88 – 1.09 0.25 –0.82 0.69 0.68 0.34
600 14.11 1.0 × 10–6 1.30 0.21 –0.95 0.72 0.44 0.39
700 12.89 3.0 × 10–6 1.48 0.19 –1.06 0.74 0.24 0.44
800 12.05 6.0 × 10–6 1.65 0.16 –1.16 0.76 0.06 0.49
900 11.47 1.0 × 10–5 1.80 0.14 –1.25 0.78
1000 10.93 1.8 × 10–5
1100 10.45 2.9 × 10–5
1200 10.03 4.4 × 10–5
1300 9.68 6.2 × 10–5
1400 9.38 8.4 × 10–5
1500 9.12 1.1 × 10–4
1600 8.88 1.4 × 10–4

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 2 2011

198 DEMIDOV, MARKELOV
for reaction (2') the values of the molar fraction of carbon
monoxide in the gas phase decrease, the equilibrium shifts
to the reaction products.
It should be noted that the obtained computation
values of the mole fractions of carbon monoxide for
reaction (3') are good consistent with experimental data
[4]. Presumably an increase in the deviations of calcu-
lated values from experimental data for reaction (2') at
high temperatures is due to the changing composition
of nonstoichiometric FexO, which is in equilibrium with
magnetite [7].
CONCLUSIONS
The obtained dependences of the equilibrium mole
fraction of carbon monoxide in the gas phase on the
temperature for reaction of the interaction of iron oxides
with carbon monoxide are consistent with experimental
data when assuming that wustite composition, which is
in equilibrium with both iron and magnetite, corresponds
formula Fe0.947O.
REFERENCES
1. Baikov, A.A., Sobranie trudov. T. 2. Trudy v oblasti
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 2 2011
metallografi i (metallovedeniya), teorii metallurgicheskikh
protsessov obshei i fizicheskoi khimii (Collection of Papers,
vol. 2, Papers in Area of Metallurgy, Theory, Metallurgical
Processes, General and Physical Chemistry). Moscow: Izd.
Akad. Nauk SSSR, 1948. 592 p.
2. Schenck, H., Introduction to the Physical Chemistry of Steel-
making, British Iron & Steel Research, Association,1945.
3. Esin, O.A. and Gel’d, P.V., Fizicheskaya khimiya piro-
metallurgicheskikh protsessov. Ch. 1. Reaktsii mezhdu
gazoobraznymi i tverdymi fazami (Physical Chemistry of
Pyrometallurgical Processes, Pt. 1, Reaction between Gas-
eous and Solid Phases), Sverdlovsk, 1962.
4. Domennoe proizvodstvo: Sprav. izd. T. 2, Podgotovka rud i
domennyi protsess (Blast-Furnace Manufacture: Handbook,
Vol. 2. Ore Treatment and Blast-Furnace Processes), Veg-
man, E.F., Ed., Moscow: Metallurgiya, 1989.
5. Barin, I., Knacke, O., and Kubaschewski, O., Thermochemical
Properties of Inorganic Substances, New York: Springer–
Verlag, 1973.
6. Barin, I., Knacke, O., and Kubaschewski, O., Thermo-
chemical Properties of Inorganic Substances, Suppl., Berlin:
Springer–Verlag, 1977.
7. Diagrammy sostoyaniya dvoinykh metallicheskikh sistem:
Sprav. (Diagrams of Binary Metal Systems, Handbook),
Lyakisheva, N.P., Ed., Moscow: Mashinostroenie, 1997.