08

Oxidation of Iron, Silicon and Manganese

AkMB Rashid
Professor, Department of MME
BUET, Dhaka

Today’s Topics

 Oxidation of iron
 Oxidation and reduction of silicon
 Oxidation and reduction of manganese
 Oxidation of Iron

 Oxidation of iron according to the reaction

[Fe] + [O]wt% = (FeO)

is the most important since it controls

• FeO content of slag and oxygen content of steel

• Oxidation potential of slag
• Loss of iron in slag and hence affects productivity

 In addition to the above,

FeO also helps in dissolution of lime in slag
3/21

[Fe] + [O]wt% = (FeO)

𝑎𝐹𝑒𝑂 𝑎𝐹𝑒𝑂 6150
𝐾 = = 𝑙𝑜𝑔 𝐾 = − 2.604
𝑎𝐹𝑒 x ℎ𝑂 𝑎𝐹𝑒 x 𝑓𝑂 x [𝑂] 𝑇

• Since Fe in steel is almost pure, 𝑎𝐹𝑒 ≈ 1.

• For Fe-O system, the oxygen activity shows a small deviation
from ideality: log 𝑓𝑂 = −0.17 [𝑂]

𝑎𝐹𝑒𝑂 𝑎𝐹𝑒𝑂 T, °C [O]sat

𝑂 x 10−0.17[𝑂] = = 6150/𝑇−2.604
𝐾 10 1550 0.185
−6320 1600 0.233
𝑙𝑜𝑔 [𝑂]𝑠𝑎𝑡 = + 2.734 1650 0.285
𝑇

• Increase in T  increases oxygen dissolved in molten iron [O] in contact with pure FeO.
 Control of temperature is important to limit the dissolution of oxygen in molten iron
4/21
  In steelmaking, FeO is present along with CaO, MgO, SiO2, MnO
 activity of FeO is influenced by other solute oxides

𝑎𝐹𝑒𝑂 = 𝛾𝐹𝑒𝑂 x (𝐹𝑒𝑂)

γFeO = activity coefficient of FeO, which depends on slag composition.

In CaO-SiO2-FeO system
• as CaO/SiO2 ratio increases, aFeO increases
• physically it means that CaO replaces FeO from FeO.SiO2.

The following expression is used to express aFeO: 𝛾𝐹𝑒𝑂 = 0.514 (𝐹𝑒𝑂)0.2665

Consider a slag with (FeO) = 0.5

saturation concentrations of oxygen
is about half of the saturation value
aFeO = 0.31; [O] = 0.072
calculated from the [O] relation
5/21

Oxidation and Reduction of Silicon

• Silicon can be melted with iron in any proportions

with a noticeable quantity of heat.

• Solutions of silicon in iron showed a pronounced

negative deviation from Raoult's law
 bonds existing between silicon and iron
 silicon is present in iron alloys with a composition close to FeSi

• The dissolution reaction: [Si] = [Si]1wt%

Activities in liquid Fe–Si alloys at 1600°C DG° = – 28000 + 5.54T

0 −6100
𝑙𝑜𝑔 𝛾𝑆𝑖 = + 1.21
𝑇
6/21
• Silicon is present in all steelmaking slags as SiO2.
• Equilibrium between silicon and oxygen in the steelmaking process :
𝑎𝑆𝑖𝑂2
[Si]1wt% + 2[O]1wt% = (SiO2) 𝐾 = 2
ℎ𝑆𝑖 x ℎ𝑂

If Henrian behaviour is assumed for silicon and oxygen

in iron, then for silica saturated slags (𝑎𝑆𝑖𝑂2 = 1) :
2
1
𝑆𝑖 x 𝑂 =
𝐾
30110
log 𝐾 = − 11.4
𝑇

• The product of [Si] and [O] is constant up to 15% Si

 Lowering activity of oxygen by silicon is compensated
Influence of silicon on oxygen content
by an increase in the activity of silicon by oxygen of iron in equilibrium with solid silica

[Si]1wt% + 2[O]1wt% = (SiO2)

Conditions favourable for silicon oxidation : 𝑎𝑆𝑖𝑂2
𝐾 =
ℎ𝑆𝑖 x ℎ𝑂 2
• Low temperature
30110
log 𝐾 = − 11.4
• Low 𝑎𝑆𝑖𝑂2 in slag – a basic slag favours silicon oxidation. 𝑇

For a typical BOF slag, 𝑎𝑆𝑖𝑂2  5x10–4. Calculations at 1600 °C yields

2
5x10−4
𝑆𝑖 x 𝑂 = ≅ 10−8
4.74x104

Assuming [O] = 0.08% at turndown, [Si] at equilibrium = 1.6x10–6 % (extremely low !!)

 virtually all Si present in iron should get oxidised and goes to slag
in primary steelmaking

8/21
Effect of Temperature

(a) Oxidation of Si by dissolved oxygen in the metal:

[Si] + 2[O] = (SiO2); DG° = – 542,165 + 202.83T;

(b) Oxidation of Si by oxygen in the gaseous phase:

[Si] + (O2) = (SiO2); DG° = – 775,851 + 198.04T;

(c) Oxidation of Si by iron oxides in the slag:

[Si] + 2(FeO) = 2[Fe] + (SiO2); DG° = – 29,991 + 98.04T

 All these reactions occur with evolution of much heat.

 Oxidation of Si occurs intensively in the presence of an oxidant
in the whole range of steelmaking temperatures

9/21

Effect of Slag Composition

In basic slags,
• silica formed reacts with basic oxides
• activity of SiO2 in basic slags is negligibly low
• the reaction of silicon oxidation occurs practically to the end

In acid slags
• slags are saturated with silica,
• activity of silica in acid slags is close to unity, 𝑎𝑆𝑖𝑂2 = 1.

10/21
 Reduction of silica
If there is no intensive supply of oxidants (oxygen, air, iron ore) to a melt under an acid
slag, Si reduction takes place:
(SiO2) + 2[Mn] = 2(MnO) + [Si]; DG° = 32,200 – 132.80T
(SiO2) + 2[C] = 2{CO} + [Si]; DG° = 611,302 – 336.47T
• These reactions occur with heat absorption.
• Si reduction is favoured by a high temperature.
The process of Si reduction is influenced by
the compositions of the metal and slag.
(SiO2) + 2[Fe] = 2(FeO) + [Si]
2
𝑎𝐹𝑒𝑂 x 𝑎𝑆𝑖 • SiO2 reduction increases for slags with low aFeO.
𝐾=
𝑎𝑆𝑖𝑂2 • C, Mn lower [O] (thus lower aFeO) in slag and
favours SiO2 reduction
𝐾 (For SiO2
𝑎𝑆𝑖 = 2 saturated • In basic slag, CaO breaks iron silicates, frees
Equilibrium curves of reaction 𝑎𝐹𝑒𝑂 slag) FeO, and favours SiO2 reduction
SiO2 + 2C = Si + 2CO in iron-carbon melts
11/21

Silicon as a Deoxidising Agent

Silicon has a very high affinity for oxygen

 silicon can be used as a deoxidizing agent

𝑎𝑆𝑖𝑂2
[Si]1wt% + 2[O]1wt% = (SiO2) 𝑂 =
𝐾 x 𝑆𝑖

 addition of Si reduces [O] content

@ 1500 °C, K = 3.24×105, 0.308 x105 of steel
and using 𝑎𝑆𝑖𝑂2 = 1 𝑂 =
𝑆𝑖  Compared to Mn, deoxidation with
Si is one order magnitude better

In practice, better deoxidation Silicon, wt% Manganese, wt% Oxygen, wt%

resulted when both Si and Mn 0.1 0.00 0.019
are used 0.1 0.50 0.015
0.1 0.77 0.011
0.1 1.33 0.006
12/21
 Oxidation and Reduction of Manganese

• Blast furnace iron usually contains between 0.5 and 2.5 wt% Mn.
• Manganese is soluble in iron in any proportions,
[Mn] = [Mn]1wt%
and forms almost ideal solutions in iron.
DG° = – 9.11T
• In pure Fe-Mn alloys, the activity of Mn varies
almost precisely by Raoult's law.

• In practice, Mn present as a ternary solution

Fe-C-Mn.
 Carbon lowers the activity of Mn and gives
a negative deviation from Raoult's law

Variation of the activity coefficient of Mn with

C content in liquid Fe-C-Mn alloys at 1540 °C 13/21

• Manganese oxide has extensive solubility in slags.

In pure Fe-Mn system,

• simple deoxidation by manganese results FeO-MnO inclusions.

In acid steelmaking,
• the slag is basically a FeO-MnO-SiO2 ternary system.
• In these liquid slags, the maximum solubility of silica is ~ 50 wt% at 1600 °C
and the activity coefficient of MnO has a constant value of 0.22 - 30 mol%.

In basic steelmaking slags,

• MnO is present only as a minor constituent (<10 wt% of the slag)
during the refining period.
14/21
 • Mn oxidizes readily to form the following
(FeO) + [Mn]1wt% = (MnO) + [Fe]
oxides: MnO2, Mn2O3, Mn3O4, and MnO.
• Only MnO is stable at high temperatures
𝑎𝑀𝑛𝑂 x 𝑎𝐹𝑒 𝛾𝑀𝑛𝑂 x 𝑁𝑀𝑛𝑂
𝐾 = ≅
𝑎𝐹𝑒𝑂 x ℎ𝑀𝑛 𝛾𝐹𝑒𝑂 x 𝑁𝐹𝑒𝑂 x 𝑓𝑀𝑛 𝑀𝑛

𝛾𝐹𝑒𝑂 x 𝑓𝑀𝑛 (𝑀𝑛)

𝐾 = = 𝐾∗ Using (NMnO) = (NMn) ≈ (Mn)
𝛾𝑀𝑛𝑂 𝑁𝐹𝑒𝑂 [𝑀𝑛]
K* is an equilibrium quotient and it depends on composition of the slag

Distribution of Mn between slag and metal can then be written as

(𝑀𝑛) 7940
= 𝐾 ∗ 𝑁𝐹𝑒𝑂 log 𝐾 ∗ = − 3.17
[𝑀𝑛] 𝑇

Factors favouring oxidation of manganese:

 a high activity of FeO in slag (which means an oxidizing slag)
 a high K* value (which is obtained at low temperatures)
15/21

Variation of manganese, silicon and oxygen contents of iron

in equilibrium with silica saturated FeO-MnO-SiO2 slags
16/21
 Effect of Temperature

Oxidation with the oxygen dissolved in metal:

[Mn] + [O] = (MnO); DG° = – 244,521 + 108.78T

by direct interaction with the oxygen in the gaseous phase:

[Mn] + 1/2{O2} = (MnO); DG° = – 361,464 + 106.39T

or by reaction with iron oxides in slag:

[Mn] + (FeO) = (MnO) + [Fe]; DG° = – 123,516 + 56.40T

• all reactions of manganese oxidation occur with heat evolution

• manganese oxidation is favoured by a decrease in temperature

17/21

Reduction of MnO in slag

• transfers Mn from slag to metal and increases the concentration of Mn.

• Under favourable conditions, MgO of the slag can be reduced by Fe, C or Si.
𝑎𝑀𝑛𝑂
(FeO) + [Mn] = (MnO) + [Fe] ; 𝐾=
𝑎𝐹𝑒𝑂 x 𝑎𝑀𝑛
𝑎𝑀𝑛𝑂
𝐾= (as Mn forms an almost an ideal solution in iron)
𝑎𝐹𝑒𝑂 x 𝑀𝑛

Conditions for the reduction of MnO in slag:

 Low activity of FeO in slag (which means a reducing slag)

 High temperature (which decreases K*)

18/21
Effect of slag composition

𝑎𝑀𝑛𝑂 1 𝑎𝑀𝑛𝑂
𝐾= 𝑀𝑛 = x
𝑎𝐹𝑒𝑂 x 𝑀𝑛 𝐾 𝑎𝐹𝑒𝑂

 [Mn] in metal is determined by the ratio of the activities

of MnO and FeO in the slag

In acid slag
• aMnO decreases due to silicate slag formation and, thus,
Mn oxidation proceeds more deeply
• in a Bessemer converter, for instance, manganese is
oxidized practically to its traces in the metal

Effect of Mn content of metal

on (MnO)/(FeO) ratio
19/21

In basic slags containing MnO,

• the content of Mn in the metal is determined by the temperature and (aFeO).
• Addition of iron ore to the bath causes an increase of (aFeO), which results in a
decrease of manganese content in the metal
• on the contrary, a vigorous course of the reaction (FeO) + [C] = {CO} + [Fe] causes
a slight decrease of (aFeO), and therefore, increases [Mn].

Addition of strong deoxidants

• decreases oxygen content of the slag, which decreases (aFeO), and raises [Mn].

Addition of manganese ores (containing higher manganese oxides e.g., MnO2)

• Releases [O] as it reduced to more stable (MnO), raises (aFeO) and decreases [Mn].

Addition of metallic manganese (in the form of ferro-manganese)

• partially oxidized and the remaining part is left as [Mn]
20/21
 Example 3.1
The activity coefficient of MnO in slag having a slag of basicity 1.8 is 1.6.
The mole fraction of FeO and MnO in slag is 0.25 and 0.05 respectively.
Determine the equilibrium content of Mn and O in steel at 1873 K.
Given that, at 1873 K, [O]sat = 0.233%, and
[Mn] + (FeO) = (MnO) + [Fe]; ΔG° = −27800 + 11.8T J/mol
aFeO = 0.514 (NFeO)0.2665

𝑎𝑀𝑛𝑂 𝛾𝑀𝑛𝑂 x 𝑁𝑀𝑛𝑂 −∆𝐺 0 𝛾𝑀𝑛𝑂 x 𝑁𝑀𝑛𝑂

𝐾= ≅ ln 𝐾 = = ln
ℎ𝑀𝑛 x 𝑎𝐹𝑒𝑂 𝑀𝑛 x 𝑎𝐹𝑒𝑂 𝑅𝑇 𝑀𝑛 x 𝑎𝐹𝑒𝑂

∆𝐺 0 𝛾𝑀𝑛𝑂 x 𝑁𝑀𝑛𝑂 @1873K, ΔG° = 6880 J/mol

ln[𝑀𝑛] = + ln For (NFeO) = 0.25, (aFeO) = 0.36
𝑅𝑇 𝑎𝐹𝑒𝑂
[Mn] = 0.048%.

[O] = [O]sat × aFeO = 0.233 × 0.36 = 0.084%

21/21