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The Ellingham Diagram: How to Use it in Heat-Treat-Process

Atmosphere Troubleshooting



Harold Johann Thomas Ellingham (1897-1975) was a British physical chemist and is best
known for the diagrams named after him that plot the change in standard free energy with
respect to temperature for reactions like the formation of oxides, sulfides and chlorine of
various elements, such as:
2x/
y
M + O
2
2 x/
y
M
x
O
y

The oxide plot tends to be the most common and will be highlighted here as its applicability
to heat-treating processes is the most relevant. This phenomenon was known before
Ellinghams time, but Ellingham demonstrated it more clearly and made it more accessible to
industry as a tool. His diagram and its variants help to select the best reducing agent for
various ores in the extractive-metal process.

Ellingham discovered that by normalizing the thermodynamic functions to a given reaction
with one mole of oxygen he was able to compare the temperature stability of many different
oxides on the same diagram. In particular, and this reaction is critical to metal reduction
systems that use carbon dioxide, he could show graphically that carbon becomes a stronger
reducing agent as the temperature increases. The reduction of metal oxides with carbon (or
carbon monoxide) to form the free, reduced metals is of immense industrial importance (blast
furnace reduction of iron ores), and Ellingham diagrams show the lowest temperature at
which the reaction will occur for each metal.

Lets restate and go stepwise through the Ellingham diagram to set up and make clearer how
metal heat treaters can use it. We can adapt the diagram from its original use as a higher-
temperature extractive-metallurgy tool to one where we can predict the effects of protective
atmospheres and common atmosphere impurities and their impact on heat-treated product.
See Fig. 1 for the classic Ellingham diagram that would typically be used for heat-treating
atmosphere processes.


Background

An Ellingham diagram is a plot of DG (change in Gibbs free energy) versus temperature,
which, for our purposes, would be a temperature in a continuous furnace by zone or in a
batch furnace by time in the cycle. The Ellingham diagram shown is for metals reacting to
form oxides.

Since any explanation of how to calculate and plot an Ellingham diagram is more about the
mechanics of the derivation process and less about how to use the tool, which is the intent of
this article, the concept is covered very briefly here.

Enthalpy (DH) and entropy (DS) are essentially constant with temperature. Unless a phase
change occurs, the free energy (DG) versus temperature plot can be drawn as a series of
straight lines, where DS is the slope and DH is the y-intercept.

DG = DH T DS

The slopes of those plotted lines change when any of the materials involved melt (M) or
vaporize/boil (B). In a heat-treat system this is (for the most part) irrelevant, except in the
brazing and sintering processes where those phase changes (melting) can indeed occur.

The free energy of formation is negative for most metal oxides, which means the reaction can
proceed without further influence. Therefore, the diagram is drawn with DG=0 at the top of
the diagram, and the values of DG shown are all negative numbers. Temperatures where
either the metal or oxide melt (M) or vaporize (B) are marked on the diagram.

Note that the majority of the plots for metals slope upward because both the metal and the
oxide exist as condensed solid or liquid phases. The oxygen partial pressure is taken as 1
atmosphere, and all of the reactions are normalized then plotted to represent consumption of
one mole of O
2
.

Interestingly, there are two plots that do not look like all of the others.

C + O
2
=> CO
2


Carbon, a solid, reacts with one mole of oxygen and produces one mole of carbon dioxide
(CO
2
), which results in little change of entropy an almost horizontal plot. The other has a
distinct negative slope:

2C + O
2
=> 2CO

In this reaction, a solid once more reacts with one mole of gas but produces two moles of gas
carbon monoxide (CO). This causes a substantial increase in entropy, and the plot has a
distinct negative slope.

The severe negative slope of this carbon reaction results in an increasingly more powerful
reducing agent as temperature increases. For example, at 1500C (2732F), the carbon
reaction crosses under that for silicon dioxide (SiO
2
), resulting in the potential ability to
reduce the highly stable compound of SiO
2
to silicon under oxygen-starved conditions.

Note on the diagram there is a scale on the right and along the bottom of the graph illustrating
P
O2
(atm). P
O2
is plotted showing partial-pressure values from 1 to 10
-100
. It will be shown
how to use this scale in the next section, along with the scales immediately to the right of this
one showing the relationship of P
H2/H2O
and P
CO.CO2
to the various metals and their oxides as a
function of temperature. These partial-pressure values and their associated ratios can be
plotted on the Ellingham diagram and can be obtained by sampling the process atmosphere at
various temperatures, or at specific times (temperatures) in a cycle, using familiar and readily
available atmosphere analytical tools (oxygen, hydrogen, dewpoint/moisture, CO and CO
2
).


Ellingham Diagram for Metals Processing

When plotting whether a given metal system will oxidize, reduce or remain as an oxide or
pure metal, the Ellingham diagram does not indicate the quantitative rate of the reaction, only
the probability of it occurring based on a given set of conditions. One can make the
assumption that the reaction will qualitatively occur more rapidly as temperature increases or
as the conditions for reducing or oxidation deviate farther from neutral-atmosphere
conditions.

We can use the diagram to determine the relative ease by which a metal can be oxidized or an
oxide can be reduced. Metals plotted high up on the diagram are easier to reduce (noble
metals) than those plotted lower on the diagram, which naturally tend to exist in very stable
oxide forms. For example, Ag, or silver, is very hard to oxidize, while Ca, or calcium, does
not naturally exist in its elemental form, indicating a very stable oxide form. The metal/metal
oxide plots also interrelate to each other. A metal plotted below another metal can reduce the
oxide of the one plotted higher up the diagram. Hence titanium, not the oxide, can reduce the
oxide of chromium, which is plotted higher on the diagram.

We can also use the diagram to determine the following at a given temperature:
The ratio of hydrogen to water/dewpoint (P
H2/H2O
) that can reduce a metal oxide to
metal or prevent a metal from oxidizing
The ratio of CO to CO
2
(P
CO/CO2
) that can reduce a metal oxide to metal or prevent a
metal from oxidizing
The partial pressure of oxygen that will be in equilibrium with a metal oxide
Determining the Equilibrium Partial Pressure of Oxygen

For a P
O2
higher than the equilibrium value at a given temperature, the metal will be oxidized.
Conversely, for an oxygen partial pressure that is lower than the equilibrium value at a given
temperature, that metal will be reduced.

Use the scale or nomograph to determine the equilibrium P
O2
by the following method. Using
a straightedge and knowing the temperature or series of temperatures you wish to use (and
the metal/metal-oxide system), put the one side of the straightedge on the upper left-hand
corner of the diagram that is labeled O (near the Ag to silver-oxide plot). Next, position the
straightedge from that anchor point to the temperature point where the metal in question
intersects that temperature value. Now, continue across the straightedge plot to the value on
the P
O2
scale. This is the equilibrium partial pressure of oxygen. For this diagram, it is
expressed in atmospheres. Once again, any oxygen partial pressure that is lower than the one
derived will cause metallic reduction. Any partial pressure above will cause oxidation.

For a real-life example, find the equilibrium partial pressure of oxygen for chromium at a
temperature of 1300C (2372F). Put the straightedge on the O dot in the upper left hand
corner of the diagram. Find the chromium plot and where it intersects the temperature of
1300C. While anchoring the one end of the straightedge on the O dot, move the other end
of the straightedge so that it runs through that intersection point and continue down the
straightedge to the P
O2
scale. Read off the value, which should be 10
-16
expressed in
atmospheres. This is an extremely small amount of oxygen than can be present in this high-
temperature system before the deleterious effects of oxygen will adversely oxidize the
metallic chromium.

The effect of chromium oxidation by even the smallest amounts of oxygen can be countered
by using a strong atmosphere reducing agent such as hydrogen. Lets go next to determining
the equilibrium ratio (P
H2/H2O
) or the hydrogen-to-water (dewpoint) ratio.

Determining the Equilibrium P
H2/H2O
Ratio

For a P
H2/H2O
, or hydrogen-to-water ratio, that is higher than the equilibrium value relatively
more hydrogen to water at a given temperature, the metal will be reduced. For a P
H2/H2O
that
is lower than the equilibrium value (relatively less hydrogen to water) at a given temperature,
the metal will be oxidized.

Using essentially the same straightedge method that we used above to plot the equilibrium
partial pressure of oxygen, we now plot from the H dot on the left side of the diagram
through our desired metal and desired temperature and now read from the P
H2/H2O
plot on the
right side of the diagram.

A real-life example would be to find the equilibrium hydrogen-to-water ratio for chromium at
a temperature of 1300C. Locate the straightedge left side on the H dot, pass through the
chromium equation where it intersects at 1300C and read off the equilibrium hydrogen-to-
water ratio value on the P
H2/H2O
scale. The value should be between 10
2
and 10
3
. This
represents a value of between 100 and 1,000 to 1 ratio of hydrogen needed to water or
dewpoint level. For this exercise, we can estimate the hydrogen-to-water ratio to be 400 to 1.

This is a high level of hydrogen that is necessary to counter the oxidizing effects of water or
dewpoint on chromium, hence the reason why most stainless steel (chromium present as an
alloy) high-temperature processing is usually done in very high levels of hydrogen often
100%. At the processing temperature of 1300F, in the presence of hydrogen, oxygen species
will convert to water and become a part of whatever background moisture or dewpoint that
might be in the process-atmosphere system. Enough hydrogen must be present in the
atmosphere system to counter oxidation of chromium. With too low of a hydrogen ratio to a
given moisture level, chromium oxidation will occur. With no hydrogen in such an
atmosphere system (vacuum-furnace processes excluded), it is literally impossible to exclude
enough oxygen from the system to prevent chromium oxidation.

Determining the Equilibrium P
CO/CO2
Ratio

The P
CO/CO2
, or CO/CO
2
ratio, is used with more frequency in extractive-metallurgy systems
for all metals to determine whether this reaction will reduce or oxidize a given metal system
at a given temperature. In heat-treated metals, the ratio is usually used for carbon-bearing iron
alloys to determine whether the metal will decarburize or carburize. It is the backbone of
carburizing and hardening and all of its derivative processes.

The topic of carburization and its derivative processes is reserved for articles far beyond the
space allotted and the scope of this article on the Ellingham diagram. There is far more to
consider than merely plotting the equilibrium value for the CO/CO
2
ratio. In these systems,
we are often interested in depth of the carbon in the iron, activities, diffusion rates, time at
temperature, degree of surface oxidation and its removal, carbon concentration profiles,
avoiding intergranular oxidation (IGO), etc. to name but a few variables. However, we can
get a rough idea of what the equilibrium ratio should be so that conditions can be set to
promote deliberate decarburization in the case of electrical steels. In the case of carburization
of steel, we can at least see what equilibrium ratio we must roughly exceed to cause the
carburization process to occur.


Summary

Harold Ellinghams work made clearer and more accessible, in an easy-to-understand
graphical format, the well-known concepts of standard free energy with respect to
temperature for reactions like the formation of oxides, sulfides and chlorides. In the case of
his metal and metal-oxide diagram, by normalizing the thermodynamic functions to reaction
with one mole of oxygen, Ellingham was able to compare the temperature stability of many
different oxides on the same diagram. The result was his relatively easy-to-use Ellingham
Diagram to determine reduction and oxidation conditions without resorting to painstaking
efforts to interrelate all metal systems free-energy-based calculations from scratch. The
addition of the original nomograph tool that plots, in a continuous scale, the values of P
O2
for
ease of calculation by the user is the work of F. D. Richardson and Jeffes.

Since CO/CO
2
and H
2
/H
2
O ratios are often used in conjunction with determining equilibrium
partial pressure of oxygen, L.S. Darken and R.W. Gurry added their calculations as
nomograph scales for these additional ratios. These diagrams have subsequently been referred
to as Ellingham, Ellingham-Richardson, Darken and Gurry, or modified Ellingham diagrams.

http://www.industrialheating.com/Articles/Feature_Article/BNP_GUID_9-5-
2006_A_10000000000001026454


















Diagram Kellog

Secara termodinamika pemanggangan oksidasi terhadap logam sulfide dapat diatur sehingga
didapat : logam oksida, logam sulfat, logam, dll.
Untuk menentukan kondisi yang tepat bagi pembentuk produk, perlu ditinjau hubungan
kesetimbangan system : logam, belerang, oksigen.
Reaksi pemanggangan oksidasi dibagi menjadi 3 (tiga) kelompok :
Reaksi utama :
2 MS + 3O
2
= = = = 2 MO + 2SO
2
(1)
MS + 2O
2
= = = = = MSO
4
(2)
MS + O
2
= = = = = = M + SO
2
(3)
Reaksi Samping, Fase Gas
2 S + 2O
2
= = = = = = 2 SO
2
. (4)
2SO
2
+ O
2
= = = = = = 2SO
3
. (5)
Reaksi Samping, Fase Padat
4MSO
4
= = = = = = 2MO.MSO
4
+ 2SO
2
+ O
2
. (6)
2MO.MSO
4
= = = = 4MO + 2SO
2
+ O
2
(7)
2MO = = = = = 2 M + O
2
... (8)
Catatan :
a. Tidak semua senyawa padat dapat terbentuk, missal oksida basa (mo.mso
4
). Ada
beberapa logam yang sangat tidak stabil. Hal ini diabaikan.
b. Beberapa logam mungkin dapat membentuk lebih dari satu jenis oksida basa
(mo
x
.mso
4
), x disini bervariasi.
c. Bila logam mempunyai lebih dari satu macam valensi, dapat terbentuk lebih banyak
lagi jenis senyawa padat.




Masing-masing reaksi kesetimbangan dapat diperoleh suatu persamaan termodinamika

Misal reaksi (1) pada kesetimbangan :

K1 =

Bila semua fasa terkondensasi (padat) berada dalam keadaan standard, maka harga activity
(a) = 1


K1 =

jika harga ini dilogaritmakan, maka didapat persamaan :

log k1 = 2 log p. so
2
3 log p . o
2

pada temperatur tertentu harga k dapat diperoleh dari persamaan :

g
0
= - 4. 575 t log k
g
0
= harga energi bebas standart (lihat
table)
t = temperatur


log k1 = , jadi log k dapat dihitung







A
2
MO.P
2
SO
2

A
2
MS.P
3
O
2

P
3
O
2

P
2
SO
2

4.575 T
G
0

maka dari reaksi (1) (8) dapat ditulis persamaan :

2 ms + 3 o
2
= = = 2 mo + 2 so
2
(1)
ms + 2 o
2
= = = mso
4
.. (2)
ms + o
2
= = = m + so
2
.. (3)
2 s + 2o
2
= = = 2 so
2
. (4)
2 so
2
+ o
2
= = = 2 so
3
(5)
4 mso
4
= = = 2 mo.mso
4
+ 2 so
2
+ o
2
(6)
2 mo.mso
4
= = = 4 mo + 2 so
2
+ o
2
.. (7)
2 mo = = = 2 m + o
2
. (8)

(1) log k1 = 2 log p.so
2
3 log p.o
2

(2) log k2 = - 2 log p. o
2

(3) log k3 = log p. so
2
lo p. o
2

(4) log k4 = 2 log p. so
2
2 log p.s
2
log p. o
2

(5) log k5 = 2 log p. so
3
2 log p. so
2
log p.o
2

(6) log k6 = 2 log p. so
2
+ log p. o
2

(7) log k7 = 2 log p. so
2
+ log p. o
2

(8) log k8 = log p. o
2


dari reaksi :

a. terlihat bahwa komposis gas campuran ditentukan oleh tekanan parsial, dua
diantaranya adalah komponen gas-gas dalam system.

b. untuk komposisi gas tertentu, maka komposisi fasa padat yang stabil akan tertentu
pula, oki daerah masing-masing komposisi padat yang stabil dapat digambarkan
diagramnya dengan tekanan parsial dua komponen gas sebagai koordinat (log p. so
2

dan log p. o
2
).

c. pada diagram kellog persamaan kesetimbangan (1) (3) dan (6) (8) merupakan
garis lurus, sebagai pembatas stabilitas komponen padat sesuai reaksi yang
bersangkutan.
untuk persamaan (4) dan (5) masing-masing mewakili reaksi pembentukan so
2
, so
3

untuk temperature tertentu, hubungan antara log p. so
2
dan p. o
2
juga tergantung harga
p. s
2
atau p. so
3
.bila p. so
2
dan p. o
2
membesar, maka p. so
3
juga akan membesar.
harga p.s
2
akan membesar bila p.so
2
besar & p.o
2
kecil.

d. bila titik a berada pada daerah ms merupakan keadaan awal dengan p.so
2
dan p.o
2

tertentu, sedangkan p.o
2
diperbesar p.so
2
tetap. maka akan didapat komposis mo. jika
p.o
2
diperbesar lagi akan didapatkan mo.mso
4











catatan : p.s
2
= 1 atm (pers.4)
p.so
3
= 1 atm (pers.5)











(5)
(6)
(2)
(4)
(1)
(3)
(8)
MO
M
MO.SO
4

MSO
4

MS
+
0
-
0 + -
Pyrometallurgy

Pirometalurgi adalah Suatu proses ekstraksi metal dengan memakai energi panas. Suhu yang
dicapai ada yang hanya 50o 250o C (proses Mond untuk pemurnian nikel), tetapi ada yang
mencapai 2.000o C (proses pembuatan paduan baja). Umum dipakai hanya berkisar 500o
1.600o C ; pada suhu tersebut kebanyakan metal atau paduan metal sudah dalam fase cair
bahkan kadang-kadang dalam fase gas.

Umpan yang baik adalah konsentrat dengan kadar metal yang tinggi agar dapat mengurangi
pemakaian energi panas. Penghematan energi panas dapat juga dilakukan dengan memilih
dan memanfaatkan reaksi kimia eksotermik (exothermic).

Sumber energi panas dapat berasal dari :
1. Energi kimia (chemical energy = reaksi kimia eksotermik).
2. Bahan bakar (hydrocarbon fuels) : kokas, gas dan minyak bumi.
3. Energi listrik.
4. Energi terselubung/tersembunyi (conserved energy = sensible heat), panas buangan
dipakai untuk pemanasan awal (preheating process).

Peralatan yang umumnya dipakai adalah :

Tanur tiup (blast furnace)

Blast Furnace
Reverberatory furnace.


Sedangkan untuk pemurnian Pirometalurgi dipakai :
Pierce-Smith converter.

-
Bessemer converter.

-
Kaldo cenverter.
-
Open hearth furnace.


http://www.anakunhas.com/2011/11/penjelasan-pirometalurgi-pyrometallurgy.html

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