FEATURE | Industrial

Gases/Combustion

The Ellingham Diagram:

How to Use it in Heat-Treat-Process
Atmosphere Troubleshooting
Michael J. Stempo Air Liquide International U.S. LP; Houston, Texas
The Ellingham diagram is not always thought of as a heat-treaters tool. This article
demonstrates its usefulness.

a
arold
Johann Thomas Ellingham
(1897-1975) was a Brith
ish physical chemist and is
best
b 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, suldes and chlorine of various
elements, such as:
2x

y M + O2 2 y MxOy

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 extractivemetallurgy 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 6G
(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 briey here.
Enthalpy (6H) and entropy (6S) are
essentially constant with temperature.
Unless a phase change occurs, the free energy (6G) versus temperature plot can be
drawn as a series of straight lines, where
6S is the slope and 6H is the y-intercept.
6G = 6H T 6S
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
inuence. Therefore, the diagram is drawn
with 6G=0 at the top of the diagram, and
the values of 6G 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 O2.
Interestingly, there are two plots that
do not look like all of the others.
C + O2 => CO2
Carbon, a solid, reacts with one mole of
oxygen and produces one mole of carbon dioxide (CO2), which results in little
change of entropy an almost horizontal
plot. The other has a distinct negative
slope:
2C + O2 => 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
IndustrialHeating.com - April 2011 55

FEATURE | Industrial
Gases/Combustion

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
56 April 2011 - IndustrialHeating.com

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 (PH2/H2O) that can reduce a
metal oxide to metal or prevent a metal
from oxidizing
The ratio of CO to CO2 (PCO/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 PO2 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 PO2 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

PH 2 /PH2O
O

10-8 10-7

PCO/PCO2

10-14 10-12 10-1010-910-8 10-7 10-6

-100
-200
-300

10-6

Cu 2O
O =2
4Cu + 2
2C +
O2 =
2CO

-400

10-5

10-5
10-4

-500

C
-600

r + O2
4/3C

-700

-900

-1100

nO
= 2M

M 10-14
M

l + O2
4/3A

Al 2O 3
= 2/3

gO
= 2M
+ O 2 2CaO
g
M
2
=
+ O2
2Ca
0
200
PO2,(atm)

400
10-100

800

10

10-1
1
10

102
103

102

1000
10-60

1200
10-50

104

105

10-20

107

106

10-22

108

107

10-30
1400

109
1010

PCO/PCO2

1011

10-34

1010
1011

1013
1300 C

109

1013

1014

PH2/PH2O

108

1012

1600
10-38

104

106

10-28

10-42

103

10-18

10-24

M
M Melting point of metal
B Boiling Point of metal
M Melting point of oxide

10-80

105

600

10-2

10-1

10-16

10-26

Temp. C

-1200

O Kelvin

SiO 2
O =
Si + 2 TiO 2
=
O
Ti + 2

-800

-1000

+ O2
2Mn

Cr 2O 3
= 2/3

10-3
10-2

10-12

3/2Fe + O2 = 1/3Fe3O4

10-4

10-3 1
10-1
10-2
M
10-3
O4
-4
2Fe 3 10
M
=
M
O2
+
e
iO
oO 6F
10-5
M
= 2N
= 2C
+ O2
2H 2O
+ O2
=
2Ni
o
O
O
C
+
2
2
2
2H 2
= 2C
M
+ O2
10-8
2Co
M
C + O2 = CO2 10-10
M

4Ag + O2 = 2Ag2O

6G = RTInpO 2,k j

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 (SiO2), resulting in the potential ability to reduce the
highly stable compound of SiO2 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 PO2 (atm). PO2 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 PH2/H2O and
PCO/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 specic times (temperatures)
in a cycle, using familiar and readily available atmosphere analytical tools (oxygen,
hydrogen, dewpoint/moisture, CO and
CO2).

1012

the straightedge plot to the value on the

PO2 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, nd 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 PO2 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
(PH2/H2O) or the hydrogen-to-water (dewpoint) ratio.
Determining the Equilibrium
PH2/H2O Ratio
For a PH2/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 PH2/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 PH2/H2O plot on the right side of
the diagram.
A real-life example would be to nd 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 PH2/H2O scale. The value
should be between 102 and 103. 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,

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FEATURE | Industrial
Gases/Combustion

hence the reason why most stainless steel

(chromium present as an alloy) hightemperature 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 (vacuumfurnace processes excluded), it is literally impossible to exclude enough oxygen
from the system to prevent chromium
oxidation.
Determining the Equilibrium
PCO/CO2 Ratio
The PCO/CO2, or CO/CO2 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/CO2 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 proles, 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
58 April 2011 - IndustrialHeating.com

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-tounderstand graphical format, the wellknown concepts of standard free energy
with respect to temperature for reactions
like the formation of oxides, suldes 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 PO2 for ease of calculation by the
user is the work of F. D. Richardson and
Jeffes.
Since CO/CO2 and H2/H2O 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 modied Ellingham diagrams. IH
For more information: Contact Michael J.
Stempo, P.E., business development/applications engineering, Air Liquid Industrial U.S. LP,
2700 Post Oak Blvd., Suite 1800, Houston, TX
77056; tel: 610-997-0936; fax: 713-803-7344;
e-mail: mike.stempo@airliquide.com; web:
www.us.airliquide.com

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