CHAPTER IV

MEASUREMENT OF THERMODYNAMIC PROPERTIES: PART II:

ELECTROMOTIVE FORCE (EMF)MEASUREMENTS
III-1: Introduction
It is well-known that structure and properties of a system are inter-related. The advances in
experimental techniques still have limitations in determination of the structure by direct
observation. The use of computational tools in estimating high temperature properties needs
further refining in order to get reliable results. On the other hand, experimental techniques are
available which can provide us with high temperature data and thereby, give an insight into
the structure. This is illustrated in Fig. IV-1.

Fig. IV-1: Illustration of Structure – Property correlation

Thus, high-temperature property measurements with respect to molten metal and slag systems
have a significant place in process metallurgy research.
As it can be seen in Fig. IV-1, the properties are generally divided into
a) Thermochemical properties which consists of partial molar Gibbs energies and enthalpies,
b) Thermophysical properties such as densities, viscosities, thermal diffusivities, interfacial
tensions etc.
Densities can even be considered as a thermodynamic property, termed “molar volume”; thus
be placed in either of the above categories. In this chapter, the measurement of the partial
molar Gibbs energies at high temperatures using a high temperature galvanic cell method,
which is an extremely useful method for high temperature systems is presented. While the
chapter discusses the galvanic cell method in general, a greater emphasis is laid on the solid
electrolyte method with zirconia-based oxygen conducting electrolytes and their applications
in thermodynamic measurements.
IV-2: Galvanic cells-Principles
Electrochemical cells are designed to harness the reaction that is relevant for monitoring the
chemical potential of a particular species in a phase, solid, liquid or gas.
In order to give a basic understanding, the basic principles of the method are presented in the
following sections.
IV-2-1: Electrochemical reactions:
The concept of first law of thermodynamics, which brings out the principle of conservation of
energy (started with mechanical and thermal energies) is extended to different forms of energy
like chemical energy, electrical energy, nuclear energy etc. The most relevant here is the
conversation between chemical and electrical energy, which forms the basis of electrochemical
cells. The chemical energy difference between two states (μ1 and μ2) where the μ-terms
represent the chemical potentials could be measured as an electrical potential in a typical
electrochemical cell. With a knowledge of the chemical potential of one of the states, we can
know the other if we are able to measure the corresponding electrical energy.
μ2 - μ1 = ∆μ = constant. ∆E (IV-1)

The term “Chemical potential” refers to the partial molar Gibbs energy of a species in solution.
∆μ is the chemical potential difference between the states 1 and 2, while ∆E is the EMF
generated by the conversion (described as a difference between the two states) and the constant
term, at constant temperature and pressure is the conversion factor.
III-2-2: Nernst equation
Let us take a typical galvanic cell we can think of:
O2 (gas, pressure P1) // O2- (pure O2-conductor) // O2(gas, pressure P2) (cell IV-1)
Let us assume that P2 > P1
The chemical potential of oxygen in the left-hand side electrode is μ1 and the corresponding
value for the right-hand side electrode is μ2. Let us try to understand these terms.
µ

μ2
Right-hand side electrode
∆μ = (μ2-μ1)

μ1
Left-hand side electrode
Figure IV-2: A schematic representation of the chemical potential difference between the two
electrodes of cell I.
As we see in Figure IV-2, in the case of cell I, the difference in the chemical potential of the
two electrodes is ∆μ. The oxygen gas at the right-hand side electrode at a higher pressure
(consequently has a higher chemical potential) will tend to flow to the left-hand side electrode
with oxygen at a lower level (which has a lower chemical potential). In other words, the term
∆μ represents the driving force for oxygen to move from the right-hand side to the left.
From basic thermodynamics, we can derive that
μi = oμi + RT ln pi (IV-2)
where oμi is the chemical potential of “I” in its standard state. In our case, oxygen gas in cell I
would be considered to be in its standard state in both the electrodes if it is 101 325 Pa (1 atm)
Thus,
∆μ = [(oμi +RT ln p2) – (oμi +RT ln p1)] (IV-3)
= - RT ln (p2 / p1) (IV-4)
Let us look at the way in which oxygen is getting transferred from one electrode to the other.
Oxygen from the right-hand side electrode at a higher pressure cannot pass through the
electrolyte as oxygen molecule. The electrolyte will only allow oxygen ions. Thus, oxygen
molecule on the right-hand will get transferred to oxygen ions according to the reaction
O2 (gas, pressure p2) + 4 e = 2 O2- (IV-5)
This will leave 4 positive charges at the right-hand side electrode. The first oxygen ion will
arrive at the left-hand side and gets transformed to an oxygen molecule according to the reaction
2 O2- = O2 (gas, pressure p1) + 4 e (IV-6)
Thus, the total cell reaction is the sum of (III-5) and (III-6) and can be written as
O2 (gas, pressure p2) = O2 (gas, pressure p1) (IV-7)
We should remember that the transfer of two oxygen ions leaves the right-hand electrode with
4 positive charges and the left-hand electrode with negative charges. Further transfer of oxygen,
driven by the chemical potential difference is opposed by the electrical potential difference.
Electrical potential due to charge separation: = nEF (IV-8)
Where n refers to the number of electrons involved in the reaction, E is the EMF in V generated
due to charge separation and F is the Faraday constant (96,485 J per volt gram equivalent).
Considering equations (IV-5) and (IV-6), n would be equal to 4.
Thus, the two opposing forces at equilibrium can be represented as
∆μ = - 4 EF = RT ln (p2/p1) (IV-9)
which is one of the forms of Nernst equation. Similar equations can be derived for
thermodynamic activities in solutions, which is basic thermodynamics.
The above equation illustrates the relationship between the Gibbs energy change of a chemical
reaction and the electromotive force when the chemical reaction is incorporated into a galvanic
cell. It is to be remembered that, in this book, the right-hand side electrode, which gets a positive
charge due to the electrochemical reaction occurring is the cathode (reduction reaction) and the
left-hand side electrode, where there is an oxidation reaction occurring is the anode. We will
try to restrict the use of the terms “anode” and “cathode” in this book and keep the arguments
to redox reactions in order to avoid confusion.
The application of Nernst equation presupposes
1. The chemical reaction is totally represented in the cell reaction and no side reaction occurs.
This could occur due to wall reactions, reactions with the electrode leads or parallel reactions.
2. The electrolyte is a pure ionic conductor and no electronic conduction under the measurement
conditions exist.
We will discuss later the consequences of these two conditions as we discuss the cell design.
IV-2-3 Reversibility of the galvanic cells
Nernst equation requires that the cell EMF, as represented by equation (III-9) or similar
equation incorporating thermodynamic activities instead of partial pressures, should be
reversible.
Since the basic equation is ∆μ = - 4 EF , if the chemical potential difference is manifested as
the cell EMF, the forward reaction, accompanied by a decrease in the chemical potential of the
species involved in the galvanic cell reaction, ∆μi, would produce a cell EMF, E.
Let us write the cell reaction as
∆μi = μ’i → μ’’i = -nEF (IV-10)
Please note that μ’ > μ’’
If a counter EMF, E+δE which is opposite to the cell EMF is applied to the cell, the electrical
potential, which is slightly higher than the chemical driving force of the cell will reverse the
cell reaction so that there will be an “uphill pumping of species i corresponding to
μ’’i → μ’i (IV-11)
under the condition that μ’ > μ’’ is still valid. This implies that the chemical potential
difference is matched by the electrical potential and that the chemical potential difference
actually corresponds to the species i involved in the chemical reaction. A typical test of the
reversibility is to change the direction of the galvanic cell and make sure that the cell EMF
comes back to the original value when the external EMF is removed.
Galvanic cells that do not respond to this reversibility condition are considered as irreversible.
The measured EMF of these cells cannot be related to Nernst equation. An in-depth analysis of
irreversible cells is out of the scope of the present book.
IV-2-4 Side reactions
Side reactions always pose problems in electrochemistry. In the case of electrochemical
measurements, side reactions, which can disturb the cell reaction or contribute positively or
negatively to the cell EMF would give rise to misleading results. Let us take the example of a
molten salt electrolyte containing iron chloride (both ferrous and ferric). Consider the galvanic
cell:
(-) Fe // NaCl + KCl + FeCl2// Fe (alloy) (+) (Cell IV-2)
The cell reaction would be
Fe (solid, pure) → Fe (solid, alloy) (IV-12)
∆μ(III-12) = μ(Fe, alloy) - μFe = RT ln aFe (IV-13)
Where the μ-terms represent the chemical potentials and aFe stands for the activity of Fe in the
alloy.
The cell EMF, E, should represent
E `= - ∆μ = - RT ln aFe (IV-14)

If Fe2+ is oxidized to Fe3+ due to oxygen leakage in the cell, the redox reaction between Fe2+
and Fe3+, viz.
Fe2+ = Fe3+ + e (IV-15)
would lead to transfer of electrons across the cell.
Other important side reactions with respect to high temperature galvanic cells are the chemical
reactions between the electrolyte and the electrodes as well as the container walls. The former
will alter the chemical nature of the electrode surface and thus contribute to “over potential”, a
term we will explain a little later. In the case of container reaction, the nature of the electrolyte
may be changed.
In the case of solid electrolyte like CaO-stabilized ZrO2 being used in contact with liquid slags,
the dissolution of the electrolyte is fast, especially if the slag contains FeO. A product layer can
adhere to the electrolyte. We will discuss the consequences in a later part of this chapter.
III-3: Ionic conduction
Application of Nernst equation (Equation III-9) presupposes that the electromotive force of the
cell is equal and opposite to the chemical potential difference between the electrodes. This
would mean that the redox reactions (III-5) and (III-6) together would constitute the total cell
reaction and the oxygen transfer is in ionic form. The above reasoning would hold not only for
galvanic cells with oxygen ion-conducting electrolytes; but also for electrolytes conducting
other types ionic species.
In case part of the electricity is conducted through the electrolyte in the form of electronic
conduction (imagine a metal wire of definite resistance is connecting the two electrodes), the
flow of oxygen ion after reaction (III-7) would be accompanied by a counter-current flow of
electrons neutralizing the charge separation between the two electrodes and would lead to
lowering of the EMF (short-circuiting effect) as well as a net oxygen flow between the
electrodes from right –hand electrode to the left. The latter would be affected, to some extent
by factors like fluid flow affecting the mass transfer of oxygen across the electrolyte.
III-3-1 Ionic conduction in ionic liquid electrolytes
While liquid electrolytes are relatively uncommon in designing electrochemical sensors due
probably to the difficulties in handling the liquid phase, which includes the choice of containers
and possible evaporation problems, there are a few cases as in the case of Mg sensor in which
liquid chloride was used. What are the factors we need to consider in these cases?
The chlorides of alkali and alkaline earth metals are ionic and are generally completely
dissociated into cationic and anionic species. On the other hand, when the chloride of a metal
that exhibits variable valency is involved, then redox reactions are likely within the electrolyte
phase if the conditions are favourable. Let us consider FeCl2 dissolved in NaCl-KCl molten salt
mixture. Under favourable oxidizing conditions, as for example, air leakage into the galvanic
cell, Fe2+ will be oxidized to Fe3+ according to reaction (III-15). The occurrence of redox
reactions will lead to an electronic contribution to conduction, which, in turn, will lead to
deviations from Nernst equation.
Reactions wherein refractory walls dissolve in the electrolytes can lead to electronic
contributution to conduction if there are possibilities of redox reactions occurring due to such
a dissolution.
III-3-2 Ionic conduction in solid electrolytes
In the case of solid electrolytes, the situation can be quite interesting. The ionic conduction is
mainly attributed to crystal defects, Frenkel or Schottky type of defects. The readers with more
interest are directed to the standard text books on ceramics, like the book by Professor Kingery.
The vacancy formation reaction associated with defects in the crystal is related to the reaction
with the gas phase. These reactions are different for p-type and n-type conductors. Let us
exemplify this by considering an oxygen-deficient oxide, The oxygen vacancy can be
considered to be created by the transfer of an oxygen “atom” (O2- can be considered as “O” and
2 e) to the gas phase.
The defect reaction in the case of an oxygen-deficient oxide may be written as :
OO = VÖ + ½ O2(g) + 2 e (IV-16)
where OO is oxygen in the normal lattice position, VÖ is a neutral oxygen vacancy and O2(g) is
oxygen gas.
The equilibrium constant for reaction (II-16), viz. K(II-16) is given by
K(III-16) = [VÖ] . pO2½ (IV-17)

The concentration of vacancies is inversely proportional to the oxygen partial pressure, pO2½.
Consequently, the electronic component of the electrical conductivity, which is directly
proportional to the oxygen vacancy will increase with the decrease of oxygen partial pressure,
the behavior of an n-type conductor.
Figure IV-3: Relationship between electrical conductivity and oxygen partial pressure
(expressed in atmin the case of ZrO2-15 mol % CaO at 1273 K reported in literature.
Thus, the electrical conductivity of ZrO2-15 mol % CaO is unaffected by the oxygen partial
pressure down to a value of 10-17 Pa (10-22 atm) according to Figure III-4. This value has been
improved slightly due to more accurate measurements later. Thus, ZrO2-based solid electrolyte
is a pure (>99 %) ionic conductor at 1273 K down to an oxygen partial pressure of 10-15 Pa (10-
22
atm).
It would be interesting to look at the opposite behavior, reaction with between oxygen on the
gas phase and a metal-deficient oxide.
The reaction similar to (IV-16) can be written as
½ O2 + 2 e = VM’’ + OO (IV-18).
Where VM’’ corresponds to a neutral cation vacancy and OO refers to a normal oxygen at its
lattice site. Reaction (III-18) corresponds to a p-type conductor. The corresponding equilibrium
constant can be written as
K(III-18) = [VM’’] / pO2½ (III-19)
The metal vacancy concentration is directly proportional to the square root of oxygen partial
pressure. Thus, the vacancy concentration and consequently, the electronic component of the
electrical conductivity will show an increase with increasing oxygen partial pressure.
A typical example is ThO2-Y2O3 as shown in Figure III-4.
Figure IV-4: The conductivity as a function of oxygen partial pressure for the
system 0.85 ThO2-0.15YO3 at 1273 K

Figure IV-4 shows that, in contrast to zirconia-based electrolytes, thoria-yttia electrolyte shows
a variation of the electrical conductivity with oxygen partial pressure at high oxygen partial
pressures (pO2 > ca 10-3). Thus, thoria-based electrolytes could be used as pure ionic conductors
at low oxygen pressures while, zirconia-based electrolytes are suitable as ionic conductors at
higher pO2 values.
The above treatment is a simplified description of the gas-ceramics interactions at high
temperatures in order to illustrate the impact of oxygen partial pressure on the electrical
conductivity. For example, this discussion does not consider the presence of uncharged
vacancies and the reactions involving them. For more detailed discussions, the reader is
suggested to consult standard text books on the subject. as for example, P. Kofstad; “Non-
stoichiometry, Diffusion and Electrical Conductivity in binary Metal Oxides”, John Wiley
&Sons, 1972, ISBN -471-49776-2).
It is to be noted that the defect concentration is a function of aliovalent imopurities, as for
example Zr4+ being replaced by Ca2+ in the oxygen ion matrix when CaO is added to ZrO2.It
has already been mentioned that temperature is another important factor. Thus, in the choice of
an electrolyte, the concentration of the “impurity” with a different valency, temperature and the
interaction with the gas atmosphere are very important considerations.
The ionic conductivity regions for various solid electrolytes as functions of temperature and log
(pX/po) is presented in Figure IV-5.

Figure IV-6: log (px/po) for a variety of solid electrolytes.

III-3-3 Impact of electrolyte contaminations in solid electrolytes
The above discussions pertain to solid electrolytes that have been carefully synthesized
avoiding contaminations. Commercially available electrolytes can be of varying qualities and
the impurities can affect the conduction mechanism. Similarly, chemical attack on the solid
electrolyte can affect the electrolytic conduction of the electrolyte. It has been shown by Iwase
and group that, despite the slag attack on the electrolyte, even a thin layer of the electrolyte
remaining would still keep the cell functioning. Thus, the basic condition of a solid electrolyte
is that there is a layer (albeit thin) of pure ionic conductor, the cell should be following Nernst
equation. This would imply that a cheaper, less pure electrolyte can be used with a layer of pure
electrolyte to get reliable results as the latter would effectively filter off all other types of
conduction except that by the ion. This has been further verified at Imperial college by Steele.
Steele has further developed the theory behind the relationship between cell EMF and the
reaction between the electrodes and the electrolyte. When the electrochemical potentials of the
ionic species vary across the electrolyte due to the formation of layers of products between the
electrodes and the solid electrolyte. irreversible diffusion of the ions at different chemical
potential levels might occur.
III-3-4: Electronic conduction
Electronic conduction in the electrolyte would lead to a short-circuiting of the galvanic cell and
lead to a lowering of the cell voltage.

∆μ = -nEF

Rμi
Internal
Short-
circuit
∆μ ∆μ’
Lμ circu
i
iting

Left-hand side electrode Right-hand side electrode

Figure IV-7. A presentation of the internal short-circuiting due to electronic conduction of the
electrolyte- ∆μ = Theoretical Chemical potential difference while ∆μ’ is the reduced potential
due to internal short-circuiting in the electrolyte due to the electronic component of conduction.
Schmalzried has presented equations for the correction of the EMF values for a galvanic cell
with partial electronic conduction.
III-4 Material transfer across the cell due to electronic conduction
In there is a short circuit between the electrodes, this will be followed by a net material transfer.
This is illustrated in this section taking an oxygen concentration cell as the example.
Let us construct the galvanic cell (Cell IV-3):

O2(gas, pressure P1) // O2- (oxygen ion conductor) // O2(gas, pressure P1) (Cell IV-3)
We have earlier mentioned that P1< P2. Let us assume that P1 is very low that the cell has to
operate in the electronic conduction zone of the electrolyte.
Due to the electronic conduction, the cell is short-circuited. This will lead to the electron transfer
from the one electrode to the other, with consequent release of oxygen at the electrode. This
can lead to an oxygen accumulation near the electrode if the electrode kinetics is not fast
enough. A similar zone of oxygen depletion can occur at the other electrode. This would lead
to the electrodes “recoding the pseudo potentials” instead of the actual potentials at the electrode
leading to the galvanic cell registering a lower value in addition to the short-circuit effect. In
the case of electrolytes with electrical conduction through other ionic species, cationic, anionic
or both, with an electronic component in conduction, there will be corresponding accumulation
of the various conducting species at the respective electrodes.
Fig. IV-8 illustrates the accumulation problem with respect to oxygen measurements in liquid
steel. The electrolyte, in this case, is working at an oxygen potential domain where the zirconia
electrolyte is not a 99 % ionic conductor. The values of oxygen obtained in the plant were higher
than those obtained by analysis.

Fig. III-8: Accumulation of oxygen in liquid steel

III-5: Potential gradient in an electrode
In the case of an electrode with varying potential within the electrode, the question arises as to
which potential the cell is actually responding to. If there is a chemical potential variation in
the bulk of the measuring electrode (assuming that the reference electrode is homogeneous),
the situation is represented in Figure III-9.
- +

μ’i

Reference
electrode μ’’i

Working
electrode
Figure IV-9 A galvanic cell with a working electrode where there is a gradient of the chemical
potential of the reversible species “i”. The gradient shading indicates μ’I > μ’’i.
It is axiomatic that the galvanic cell recognizes always the chemical potential at the interface
between the electrode and the electrolyte. If the material transport processes are fast within the
electrode, the gradient in the electrode will be reduced to the minimum. An important factor is
the time of response of the galvanic cell at the electrode/electrolyte interface. If the electrode
reactions are much faster than the mass transfer within the electrode, the galvanic cell will
register the instantaneous potential existing at the interface. This would be very important in
the case of dynamic measurements wherein the changes in the chemical potential occurring due
to chemical reactions or mass transfer within the electrode can be continuously monitored by
the galvanic cell. If the electrode reaction is sluggish, the cell would register an average
potential, which could be difficult to interpret.
A very interesting question arises as to the response of the cell if there is a chemical potential
gradient along the electrode/electrolyte interface. Let us assume that the electrode reactions are
equally fast at all the points along the electrode/electrolyte interface. Since the electrode is an
electronic conductor, there is likely to be an equalization of the electrical potential along the
interface in the vertical direction. But the question arises as to the equalization of the chemical
potential in the vertical, downward direction since the gradient high above and decreases in the
downward direction. If the migration of the species “i” along the interface downwards is fast
enough in comparison to the electrode reaction, the galvanic cell may register an average
potential.
III-6: Various ionic conductors
The aim of a galvanic cell sensor is to monitor the changes in the chemical potential of a
species of interest in a given system. The system may be solid, liquid or gas, metallic or
ceramic. We restrict ourselves to high temperature galvanic cells. Organic or bio sensors are
outside the scope of this book.
Towards this aim, it is necessary to design a galvanic cell the cell reaction of which represents
the changes in the chemical potential of the species of interest. In designing of these cells,
these galvanic cells can be divided into
1. Direct Reversible cells and
2. Indirect reversible cells.
It is emphasized that the choice of the electrolyte in the sensor depends, to a great extent, on
the cell design.

III-7: Direct and indirect reversible cells

In this type of galvanic cells, the galvanic cell is reversible to the ionic conducting species and
the cell EMF is directly related to the chemical potential difference of this species between the
two electrodes.
Let us take a typical example. We need to measure the standard Gibbs energy of formation of
the compound ABO4(s). This compound is formed by the reaction between the oxides AO(s)
and BO3(s). The reaction can be written as
AO(s) + BO3(s) = ABO4 (s) (IV-20)

Let us consider that the oxide AO is less stable than the oxide BO3, which implies that the
Gibbs energy change for the exchange reaction of the type
3A (s) + BO3(s) = 3AO(s) + B(s) (IV-21)
is highly positive.
Let us construct a galvanic cell with an oxygen ion conducting solid electrolyte as for
example ZrO2-15 % CaO.
The cell can be written as
(-) A(s), BO3(s) // ZrO2-CaO // AO(s), A(s) (+) (Cell IV-4)

(p’O2) (pO2)
where (p’O2) < (pO2)
The electrode reaction at the left hand side is written as
A (s) + ½ O2(pO2) = AO(s) (IV-22)
And the one on the right hand side would be
A (s) + BO3(s) + ½ O2 (p’O2) = ABO4(s) (IV-24)
Thus the total cell reaction would be (III-24) – (III-23), which is
AO(s) + BO3(s) `= ABO4(s) (IV-25)
It is seen that the cell is so designed that the migrating ionic species is directly involved in the
cell reaction. The cell is reversible to oxygen ions. This is an example of the direct reversible
cell.
Let us try to measure the Gibbs energy change of the same reaction (IV-25) by means of a
galvanic cell which is a total fluoride ion conductor.
The cell is written as follows:
(-) O2 (g), AO (s), AF2(s) // CaF2 (s) // AF2 (s), ABO4 (s), BO3 (s), O2 (g) (+) (Cell IV-5)
In this case, the cell has the same gas atmosphere, 101 325 Pa (1 atm), pure oxygen gas,
which takes part in the electrode reactions on both sides.
The reaction at the left hand side electrode would be
AO (s) + F- (μ’F2) = AF2 (s) + ½ O2 (g, 1 atm.) + 2 e- (IV-26)
and the reaction at the right hand side electrode would be
AF2 (s) + ½ O2 (g, 1 atm) + 2 e- = ABO4 (s) + 2 F- (μF2) (IV-27)
Once again, the cell reaction would be (IV-1). What is the basic difference between cells (IV-
4) and (IV-5) ?
Cell (IV-5) is reversible with respect to F- ions while cell (IV-4) is as stated earlier, reversible
to O2.- ions. Both ZrO2-CaO as well as CaF2 are nearly 100 % ionic conductors under defined
conditions as described earlier. Cell (IV-4) utilizes the oxygen potential difference between
the right hand side and left hand side electrodes, which is reflected in the electrode reactions.
On the other hand, in the case of cell (IV-5), the chemical potential difference across the
electrolyte is with respect to the fluorine. The electrolyte is a pure anti-Frenkel F- ion
conductor.
The differences are illustrated in Table (IV-1)

Table (IV-1): Reversible and irreversible electrodes

Cell (IV-4)
Electrolyte is O2+ conductor
The cell works on the difference in the
oxygen potentials between the two
electrodes
The electrode reactions are redox reactions
with respect to oxygen
Functions in inert atmosphere.
Directly reversible with respect to oxygen
No indirect reversibility
Cell (IV-5)
Electrolyte is F+ conductor
The cell works on the difference in the
fluorine potential between the two
electrodes.
The electrode reactions involve fluoride
exchange
Atmosphere is pure oxygen at 1 atm.pr.
Directly reversible with respect to fluorine
Indirectly reversible with respect to oxygen

IV-8: Choice of solid electrolyte materials

The choice of the solid electrolyte is obviously based on the species the chemical potential of
which has to be detected; thus, the electrically conducting species. There has been an
excellent compilation by Rapp and Shores (“Techniques in Metals Research, vol. 4, Part 2, ed.
R. A. Rapp, Interscience, N. Y. (1970), p. 123). We attempt to focus on solid electrolytes that
have applications or potential use in sensors in pyrometallurgical industries in Table IV-2.
 Table IV-2 Some electrolytes with applications in metallurgical industries

Conducting Chem. Potential to Electrolyte Reference Comments

species be measured
Anionic species
H+ Hydrogen dissolved CaF2, Doped ? Extremely
in metals SrCeO3, useful, gas phase
NaFION, analysis
CaZr0.9In0.1O1-x
(NOTORP)
C22+ Carbon in alloys BaF2-BaC2 Limitations in
applications
N3+ Nitrogen in alloys AlN ?
O2+ Oxygen in metallic, ZrO2-based and ? Choice of
ceramic, slag, gas ThO2-based electrolyte is
systems. electrolytes. based on
temperature and
oxygen partial
pressure
F- Fluoride potentials, CaF2, MgF2, SrF2, ? Slow response.
metal, oxide, BaF2, Used in lab.
nitride… potentials Na3AlF6(cryolite) Measurements,
in indirectly etc. not gone to
reversible cells industrial
applications.
Cationic species
Li+ Lithium in mostly LiH, LixSiyOz, ? Application area
solid compounds LiAlSixOy, (Li, has been limited
Ag/Na)2SO4 so far. Battery
industry can be
benefitted
Na+ Sodium in alloys Na-β alumina, ? Sensors are in
(for ex, Al) and Na- Moltensalts need for Al
compounds containing NaCl.. industry
K+ Potassium in alloys K-β alumina, ? Limited
like Al. molten salts applications
containing KCl.
Cu+ Cu potential in Copper halides or ? Limited
compounds chacogenides applications
 Ag+
Mg2+ Mg potential in MgCl2 (molten `? Very important
reactive metal melts salt), MgF2 applications in
(For example Al) Al industry
Al3+

IV-9 Oxygen ion conducting solid electrolytes

These electrolytes occupy an important position as they have a significant role in industrial
oxygen sensors. These can also be used, after suitable modifications with auxiliary
electrodes, to sense other elements like phosphorus in liquid copper or silicon in liquid iron.
Zirconia based ceramics as oxygen ion conducting solid electrolytes was first introduced by
Kiukkola and Wagner in 1957. These authors used ZrO2-15 mol % CaO as the solid
electrolyte for measuring the Gibbs energies of formation of a number of transition metal
oxides. Since then, a great number of research publications have come out regarding the
structure of these electrolytes and application of these in thermodynamic and kinetic
measurements at high temperatures. Parallelly, industrial applications of zirconia-based
electrolytes were are developed. Today, most of the metallurgical industries and others
including automobile industries incorporate the solid electrolyte based sensors as an integral
part of process measurement and control. Thus, it is imperative that the main attention of this
book is focused on zirconia-based electrolytes.
Pure zirconia has a monoclinic structure and transforms to tetragonal form above 1200oC.
The cubic fluorite phase of zirconia can be stabilized by adding stable oxides of different
valencies like CaO, MgO or Y2O3 (cation valency < 4) to ZrO2 lattice. This would produce
vacancies in the oxygen sublattice. The stabilization is accompanied by a lowering of the
eutectoid temperature. The phase diagram of the system ZrO2-CaO is shown in Figure III-10.
 Figure IV-10: Phase diagram of the system ZrO2-CaO

The stabilization of the cubic phase can also be enabled by other oxides like MgO, Y2O3 etc.
A discussion into the depths of the relative advantages of these electrolytes is out of the scope
of the present book. However, suitable literature can be consulted, as for example, “Solid
Electrolytes and their Applications”, Ed. E.C. Subba Rao, Plenum Press, N.Y.
Even thoria-based electrolytes could be used as oxygen-ion for thermodynamic measurements
(H. Peters and H. Möbius, Z. Phys. Chem. 209, 298 (1958); H. Peters and G. Mann, Z.
Electrochem. 63, 244 (1959)). Thoria-based electrolytes are p-type conductors at oxygen
pressures above 0.2 Pa. (B. C. H. Steele and C. B. Alcock, Trans. Metall. Soc. AIME, 233,
1359,(1965))
Figure (IV-11) illustrates the ionic conduction domains of zirconia- and thoria-based
electrolytes at 1273 K. This serves as an easy guide to the choice of the electrolyte at different
oxygen partial pressures and thus, is of help in designing oxygen concentration cells.
Fig. IV-11: Ionic transport number (tion > 0.99) as a function of composition and oxygen
pressure for zirconia- and thoria based solid electrolytes at 1273 K.
Zirconia- based electrolytes have electrical conductivities of the order of 10-4 Ohm-1.cm-1 at
about 973 K. Thus, their applications at lower temperatures is somewhat limited. Attempts
have been made to employ other oxygen-ion conducting oxides like CeO2-based (T. Kudo and
H. Obayashi, J. Electrochem. Soc., 122, 142, (1975)) and δ-Bi2O3-based (T. Takahasi, H.
Iwahara and Y. Nagai, J. Appl. Electrochem., 2, 97 (1972)). In view of the fact that these
electrolytes have not made serious inroads in the design of elexctrochemical sensors for
industrial applications, no extensive discussions are presented on the performance of these
electrolytes.
IV-10 Fluoride electrolytes
In 1957, Ure (R. W. Ure, Jr. J. Chem. Phys., 26, 1363, 1957) reported that CaF2, both pure as
well as doped as pure fluoride ion conductors. The transport number of fluoride ion, tF- was
reported to be close to unity in the temperature range 690 – 920oC. Since then, CaF2 has
widely been used as a solid electrolyte for measuring not only fluoride potentials; but also
through indirectly reversible cells for measuring oxide, carbide or nitride potentials. The
concept was widened to alkaline earth fluorides, BaF2, SrF2 and MgF2. The application
extended to PbF2 as a solid electrolyte as well. The advantage of fluoride electrolytes is that
they can be used in applications with strongly reactive metals like Th. A number of earlier
reviews are available with respect to fluoride solid electrolytes (T. L. Markin, “Electromotive
Force Measurements in High Temperature Systems”, Ed. C. B. Alcock, Inst. Min. Metall.
London (1968), p. 125.; J. M. Reau and J. Portier, “Solid Electrolytes”, Ed. P. Hagenmüller
and W. Van Goo, Academic Press, N. Y. 1978, p. 273, S. Seetharaman and K. P. Abraham, J.
Sci. Indust. Res. (India), 32, 641, 1973, T. Takahashi, “Superionic conductors”, Ed. G. D.
Mahan and W. L. Roth, Plenum Press, N. Y. 1978, p. 379, M. O’Keefe, “Superionic
conductors”, Ed. G. D. Mahan and W. L. Roth, Plenum Press, N. Y. 1978, p.101)It was
shown that doped-CaF2 exhibited anti-Frenkel type of defects.
While the upper limit for fluoride potential measurements using this electrolyte has not been
specified, fluoride potentials corresponding to Ni, NiF2 can be measured using CaF2
electrolytes. The lower limit for the measurement of fluoride potentials corresponds to that of
Ca/CaF2. PbF2 has high conductivity compared to CaF2. In the case of NaF and Na3AlF6
(Cryolite), both Na+ as well as F- contribute to the electrical conductivity. The electrical
conductivity of the latter isenhanced 50 times by doping cryolite with CaF2 (E. W. Dewing,
Trans. AIME, 245, 1829, 1969.)
The disadvantages of fluoride electrolytes are their upper temperature limit of about 1100oC,
reactivity with electrode components and sensitivity to moisture in the atmosphere.
IV-11: Metal ion conducting solid electrolytes

Direct metal cation conducting electrolytes can be very useful if they could be used at high
temperatures. An important class of compounds in this category is the β-alumina group with
different cations impregnated. The name itself is a misnomer; these are not polymorphous
forms of alumina. The composition of β-alumina is Na2O. 11 Al2O3; but varies up to Na2.O.9
Al2O3 due to the presence of excess Na2O. In β’’-alumina, part of Al3+ are replaced by Mg2+
(or even by Ni2+, Zn2+ or Cu2+) and the charge balance is achieved by extra Na + ions. The
Na+ in β-alumina can be partly or fully exchanged by Li+, Ag+, K+ or other cationic species.
β’’ alumina decomposes to β-alumina and sodium aluminate above 1773 K.. The application
of these electrolytes at lower temperatures is a great advantage. On the other hand, the use of
this electrolyte for molten metal processing has been very limited in view of the maximum
temperature limit of this electrolyte. Generally, the use of β-alumina compounds as solid
electrolytes have so far been limited to a maximum temperature of 1100oC
Na3Zr2Si2PO12 “Nasicon” is a Ne+ conductor with high ion mobility synthesized by Hong and
coworkers (H. Y.-P. Hong, Mat. Res. Bull. 11, 173, 1976; J. B. Goodenough, H. Y.-P. Hong
andJ. A. Kafala´s, Mat. Res. Bull. 11, 203, 1976). The Na+ conductivity for this electrolyte
was reported to exceed 0.3 ohm-1.cm-1 at 573 K and an activation energy, 0.24 eV. This
electrolyte offers the potential of being used as a solid electrolyte for Na-potential
measurements in liquid aluminium.
IV-12 Hydrogen conductors
Proton conductors are very useful in the application as electrolytes for sensors for the
measurements of hydrogen potentials. These electrolytes are intended to be used for
measurements of hydrogen levels in molten aluminium.
Gee and Fray (Metall. Trans. B9B, 427, 1995) had developed CaH2 as the solid electrolyte for
the measurement of hydriogen levels in molten aluminium. The current transporting ion is
believed to be H22- ion. The reliability of the electrolyte is still being examined. One of the
major problems is the reactivity of CaH2 in air, thus making it as a difficult material to handle
for industrial applications.
Iwahara et al ( H. Iwahara, T. Esaka, H. Uchida and N. Maeda (Solid state ionics, vol. ¾, p.
359, 1981) have reported that SrCeO3 doped with Y2O3, Yb2O3 or Sc2O3 exhibit high proton
conductivity. Dean and FrayF. W. H. Dean and D. J. Fray, Solid State Ionics, vol. 70-71, p.
595, 1994) developed a polymeric electrolyte that could be sensitive to hydrogen in gas
mixtures at low temperatures. Tomatsu (Y. Totatsu, Keiso, 36, 96, 1993; Keiso, 38, 44,
1995) have reported that the compound CaZr0.9In0.1O3-x , commercially named NOTORP
could be used asa proton conductor that could have strong industrial applications.
IV-13: Molten salts aselectrolytes
The use of molten salts as electrolytes has not been highly promoted in view of the
fabrication problems with molten chlorides at high temperatures. However, in some cases, this
could be an excellent alternative, especially in the case of reactive metals. An impressive
measurement of Mg potentials in molten Al-Mg alloys using molten chloride electrolyte
MgCl2-CaCl2 (B. L.Tiwari, Metall. Trans. , 18A, 1645, 1987). The potentials of this field
have not been fully utilized.
IV-14: Criterial for the choice of electrolytes for thermodynamic measurements
1. In order to avoid uncertainties with respect to electronic conduction and consequent
potential drop due to short circuiting as well as accumulation of species near the electrode, it
is safe to use electrolytes that are nearly pure ionic conductors (tion > 0.99) in the
measurement temperature and oxygen partial pressure ranges.
2. The activation energy for ionic transport should be less than that corresponding to electron
transport.
3. The electrolyte should be stable in the measurement environment. Reactions with the
electrodes and contact material should be minimum.
4. Variable valencies of the electrolyte components can lead to electronic contributions. This
should be avoided.

IV-15: Construction of oxygen concentration cells for Gibbs energy measurements

We shall now examine the design of sensors for monitoring the various species in solid, liquid
or gaseous systems. The discussion will be based on oxygen-conducting solid electrolytes.
IV-15-1:Choice of Electolytes
In designing an electrochemical sensor, primary attention should be paid to the choice of the
electrolyte suitable for the measurements. For this purpose, we should know the range of the
oxygen partial pressures to be measured. The measurement range should be within the ionic
conduction domain of the electrolyte. We have already discussed the ionic and electronic
conduction in solid electrolytes and their impact on the measurement accuracies. To reiterate
the point, it is always preferable to choose an electrolyte, the ionic conduction domain of
which covers the measurement region with respect to temperatures and oxygen partial
pressures.
In the case of oxygen sensors, the choice has been restricted to zirconia-based electrolytes.
Experience has shown that fully stabilized zirconia solid electrolyte is not quite suitable as a
sensor material as the thermo-mechanical properties are not very good to withstand the
thermal shocks and mechanical stress. In this respect, partially stabilized zirconia electrolytes
are found to be more robust. The fabrication process has improved significantly and thus,
quality improvement is substantial.
With respect to ionic conduction region of zirconia-based electrolytes, the electrolytic domain
diagram has already been presented. It should be remembered that the limits are based on
measurements carried out earlier; for example, the lower line is partly based on the
thermodynamic measurements in the case of the reference electrode Cr/Cr2O3. Later
measurements have shown (Seetharaman et al, unpublished work) that the measurements with
this electrode were below the electrolytic domain of the zirconia electrolyte and suitable
corrections have to be applied. Thus, it is always safer to have a margin. Further, it should be
remembered that the correction equation for electronic conduction does not account for the
net flow of material due to short-circuiting, which would lead to accumulation of the
conducting species in the vicinity of the electrode leading to further lowering. This factor
depends upon a number factors including convection and stirring and cannot be corrected.
The ionic condction domains presented in (IV-9) and (IV-11) were drawn on the basis of the
experimental information available at the time of the publication and needed to be updated
taking into account the latest information on the ionic conductivity of the electrolyte. For
example, the measurements with the system Cr/Cr2O3 shows definite electronic conduction
contribution (Seetharaman, unpublished work).
Other important aspects to be considered in the choice of the oxygen ion conducting solid
electrolyte are the mechanical strength and thermal shock resistance of the electrolyte. It is
generally known that partially stabilized zirconia has better mechanical and thermal properties
than fully stabilized zirconia without the transport properties getting seriously affected. It has
also been claimed that MgO-stabilized zirconia is superior to calcia-stabilized one in the
application as the solid electrolyte. Further, calcium zirconia-based materials have been found
to be superior to conventional zirconia solid electrolytes in view of their better chemical
stability, high density, good strength and tolerance against thermal shock..
In view of the n-type conduction exhibited by ZrO2-based electrolytes, thoria-based
electrolytes are suitable for low oxygen potential measurements. On the other hand ,in view of
their p-type conduction, these are not very suitable for high oxygen potentials. But, thoria-
based solid electrolytes have not found their way to commercial application due to a number
of reasons including the heavy restrictions due to possible radioactivity.
Thus, in the choice of the solid electrolyte for oxygen potential measurements, the following
criteria apply:
1. The oxygen potential of the measurement system must be in the ionic conduction domain
of the electrolyte
2. The electrolyte should withstand the chemical attack by the electrode components
3. The electrolyte should have good mechanical strength and thermal shock resistance.
Experiments in a smaller scale has shown in some cases that liquid electrolytes can be suitable
as sensor electrolyte. In the case of the design of a sensor for Mg in liquid Al, Tiwari (Ref.71)
have come up with the use of liquid MgCl2-CaCl2 electrolyte.
Jacob and Jeffes have reported that they could arrest the oxygen flux due to electronic
conduction by applying a small external voltage in the opposite direction. This idea has been
adopted by Li ei al in extending the life of oxygen sensors by applying a small recharging
current between EMF measurements. It is claimed that this method could extend the working
life of the sensor more than ten times.
IV-15-2: Choice of reference electrodes
The choice of a suitable reference electrode is an important aspect in the design of
electrochemical sensor. The important criteria are:
1. The ranges of the chemical potentials of the species should be within the ionic conduction
region of the electrolyte
2. The electrode should be reversible’
3. The electrode reaction at the electrode/electrolyte interface is fast and that the response
time is very short
4. The chemical reaction between the electrode and the electrolyte should be negligible.
With regard to the first criterion, we have already discussed this aspect elaborately. But, it
would be interesting to take a case study to discuss a special situation. Extensive work has
been carried out in the case of galvanic cells with oxygen ion conducting solid electrolytes. In
the case of other types of galvanic cells, the information is not as extensive. Hence, the
present discussions are mostly centered around oxygen concentration cells. Details regarding
the other types of galvanic cells will be taken up depending upon the extent of information
available.

IV-15-3: Oxygen concentration cells

Electrodes in the case of oxygen concentration cells
In the case of measurements, where the galvanic cell starts exhibiting the effects of electronic
conduction such as oxygen transport and consequent decrease in the cell EMF with time,
Jacob and Jeffes suggest that the choice of the reference electrode may be such that the cell
EMF is near zero. This would result in negligible oxygen flux across the electrolyte.
Reversibility of the electrodes
Steele (Ref. 12) reports that Fe-FeO electrode exhibits a high degree of reversibility while Nb-
NbO and Cr-Cr2O3 electrodes tend to be much less reversible. This, ofcourse depends also on
the temperature of the galvanic cell. Cu-Cu2O electrode also shows good reversibility. The
order of reversibility in the case of oxide electrodes can approximately be represented as
Fe-FeO > Cu-Cu2O > Co-CoO > Ni-NiO > Mo-.MoO2 > Cr-Cr2O3 > Nb-NbO
Worrell and Iskoe have demonstrated the polarizability of these electrodes experimentally.
Recently, Huang et al (Ref. 14) have measured the diffusivity of oxygen in these electrodes as
the rate-determining step in the continuous measurements of oxygen in liquid copper melts.
Chemical attack on the electrolyte
With respect to the chemical attack on the electrolyte, the reaction between the oxygen-
conducting solid electrolyte and the Fe-FeO electrode is generally severe. The useful life time
at about 1000oC is about 10 h. Mo-MoO3 is found to be very suitable for measurements with
steel melts. Formation of a liquid phase in the electrode, generally is undesirable as it leads to
accelated reaction with the electrolyte amonmg other things. In fact, , in the case of Cr-Cr2O3
electrode, the liquid phase formation limits the maximum temperature of application of this
electrode.
In the case of galvanic cells where a fluoride electrolyte ii involved, a metallic fluoride
intermediate phase is necessary to get the cell reversible to fluoride ions. A typical cell can be
illustrated as

(-) Pt, AO, AF2, CaF2 // CaF2 // CaF2, BF2, BO (Cell IV-5)

The fluorides, AF2 or BF2 can form solid solutions or eutectic melts with CaF2 and the cell
can be ruined.
In the case of other chemical sensor, the information available is very limited. We will take
up specific cases when we discuss the individual sensors for various species.
Choice of the Contact material
In the case of solid state measurements, it is convenient to use the metal of the electrode as the
contact wire with the electrode. This would avoid reactions between the electrode and the
contact lead. On the other hand, use of contact leads of different materials for the reference
and working electrodes can lead to thermal EMF which is added to the cell EMF. Extreme
care should be taken to measure this thermal EMF in the case of non-similar leads. One good
example is the measurements by Iwase and his group on Mo-Pt combination. These authors
measured the thermal EMF of this combination which they could successfully use in the case
of a number of galvanic cell measurements.
In the above figure, the conductors A to G are connected in a series. The connections B-C, C-
D, D-E anf E-F are in the constant temperature zone. The thermal EMF effect will be only due
to the contact between A and G.
As mentioned earlier, the development work with respect to oxygen ion conducting solid
electrolytes has been far ahead of work with other types of galvanic cells. Hence, our
discussions will be mainly focused on oxygen potential measurements. The contact material
choice is not a serious problem in the case of solid electrodes. Sometimes, it is more
convenient to use platinum as this could be a joint lead for both EMF as well as temperature
measurements. This is illustrated in the figure below.
In the case of gaseous electrodes, for oxygen potential measurements, platinum seems to be a
good choice as contact material. The adsorption/desorption reactions are observed to be fast
and reversible. There is no reaction with the electrolyte.
In the case of measurements in liquid systems, the reaction between the liquid electrode and
the contact material can be a serious problem. After a number of unsuccessful trials, Cr-
cermet was found to be useful as a contact lead material for liquid copper (Ref. ). The
observations of the present authors show that, with small quantities of Zn in liquid copper, Cr-
cermet showed signs of reaction. The use of tungsten lead was an alternative. This is very
suitable for very low oxygen potentials in the liquid phase. With slightly higher oxygen
levels, tungsten was observed to react with oxygen in the vicinity leading to local deoxidation
(Ref.), thereby changing the chemical potential of oxygen in the measurement system. Other
types of chromate leads, apart from Cr-cermet have also been tried as lead materials in liquid
copper.
In the case of liquid iron, Mo-cermet has been used with reasonable success. In the case of
slag systems, wires of refractory metals like Mo can be used. Care should be taken in the case
of slags containing FeO or MnO. The reaction of the type
FeO (slag) + Mo = Fe-Mo (alloy + ½ O2 (IV-28)
are likely to affect the results. If this type of reactions are local and if the size of the
measuring system is significant, the error involved may be negligible.
Gas atmosphere
The effect of the gas atmosphere is an important factor and has seldom been given much
attention. This aspect has been discussed earlier in Chapter II.
It is to be remembered that the galvanic cell responds to the oxygen potential prevailing at the
electrode/electrolyte interface, thus the local potential. This interfacial potential is affected by
the oxygen potential of the inert gas atmosphere. If the oxygen partial pressure of the inert gas
atmosphere is higher than the interfacial oxygen partial pressure, oxygen from the gas phase
can diffuse to the interface and increase the potential. On the contrary, where the inert gas has
extremely low, there is likely to be oxygen transfer from the electrode/electrolyte interface to
the gas phase.
Cell design:
Measurements of the Gibbs energies of formation of oxides:

(-) A(s), AO(s) // ZrO2-CaO // BO(s), B(s) (+) (Cell IV-6)

(p’O2) (pO2)
where (p’O2) < (pO2)
Cell (III-6) provides the means to determine the Gibbs energy of formation of BO if we have
a knowledge of the Gibbs energy of formation of AO since the cell reaction is:
AO + B = BO + A (IV-29)
(Cell III-3) which is quite similar to (Cell IV-6) above provides a method for measuring the
Gibbs energy of formation of the compound ABO4.
The construction of the cells has been simplified over the years since the inception of the
method by Kiukkola and wagner. Some of the later experimental designs are given in Fig. IV-
12.

Fig. IV.12: Some designs of the solid electrolyte galvanic cells for measurements in solid
state.
Measurements of the thermodynamic activities in alloys:
Cell (III-6) can be modified to measure the activity of a component in a solid alloy (can be
multicomponent). The cell configuration is given below:
(-) A(s), AO(s) // ZrO2-CaO // AO(s), A-B(s) (+) (Cell IV-7)
The net cell reaction would be
A(s) = A(s) (IV-30)
Measurements of the thermodynamic activities in oxide systems:
The same concept can be modified to measure the activities in oxide systems:
(-) A(s), AO-BO(s) // ZrO2-CaO // AO(s), A(s) (+) (Cell IV-8)
The corresponding cell reaction would be
AO(s) = AO(BO) (IV-31)
Measurements li liquid metals:
These measurements had helped a great deal in understanding the thermodynamics of dilute
metallic solutions.
The galvanic cell in the case of measurements with liquid copper may be represented as

(-) O (Cu) // ZrO2-CaO//FeO-Fe (Cell IV-9)

A diagram of the apparatus used is given in Fig. IV-13.
Fig. IV-13: The experimental arrangement for the measurement of oxygen activities in liquid
copper (Ref.)
1. Kanthal shields, 2. Mullite tube, 3. Alumina tube, 4. Pt-10 % Rh-Pt thermocouple. 5.
Alumina outer crucible, 6. Pt foil, 7. Fe-FeO electrode, 8. Copper melt, 9. Cr-cermet
electrode, ZrO2-CaO crucible, 11. ZrO2-CaO lid, 12. Alumina tubes, 13. Pt-leads for the cell,
14. Pt-10 % Rh-Pt thermocouple, Arrows indicate the direction of gas flow.
 In these experiments, the reference electrode was in the path of argon flow which was purified
to the level 0f ca 10-18 atm. before entering the cell compartment. Oxygen from the Fe-FeO
electrode got transferred to the gas so that the oxygen partial pressure in the gas corresponded
to 10-13 atm. The initial oxygen level in the copper melt was varied by means of coulometric
titration and, after the titration was over, the change of EMF was followed as a function of
time. A schematic diagram of the variation of cell EMF with time is shown below:
EMF

0 Time

II

Fig. IV-14 The variation of cell EMF with time

I : Molten Cu has higher oxygen level than Ar.
II. Molten Cu has lower oxygen level than Ar

Diffusion calculations show in this case that the diffusion of oxygen from the bulk to the
interface was the rate-controlling mechanism . The EMF changes could be well-reproduced
by assuming the diffusivity of oxygen in liquid copper at the experimental temperature,
available in literature.

These experiments shows the negative effects of ultra-cleaning of argon gas which will drain
out oxygen from the system altering the composition. The EMF will start drifting
continuously. In order to avoid these effects, it is preferable to have the gas atmosphere
buffered suitably with oxygen levels somewhat close to the measuring system.

Measurements of oxygen in gas phase

In the case of measurements of oxygen in a gas phase, the design of the EMF probe has to be
designed so that the contact between the gas phase and the electrode as well as the electrode
and electrolyte are proper. Normally, a CaO- or MgO stabilized ZrO2, vacuum-tested and
confirmed vacuum-tight is used. The bottom of the tube is coated with platinum paint up to a
height of about 1 cm using a long pipette. The coating should be thin and uniform. The
outside is also coated with platinum paint to about the same height as the inside. The tube is
 them placed in a furnace and heated slowly at the rate of about 5 K/ min. to about 773 K. The
organic part of the paint starts burning evolving fumes. After the fumes subside, the furnace is
cooled slowly (about 5 k/ min.) without disturbing the tube in the furnace. The tube is taken
out after the furnace had reached the room temperature. A platinum boll with a Pt-10 % Rh
/Pt, attached to it is positioned inside the tube so that the Pt boll is in good contact with the
bottom. One of the arms of the thermocouple is insulated by a long alumina tube which
extends outside the zirconia tube. Air or oxygen is passed through this inner alumina tube
which serves as the reference electrode. The A thin Pt-foil is wrapped around the outside at
bottom of the and a Pt wire is attached to it. The cell EMF is measured between the Pt-wires
inside and outside, while the temperature is measure using the thermocouple inside the
zirconia tube.

Pt

Cell EMF
Pt paint
Pt

Pt/Rh

Fig.IV-15: Illustration of a common lead for EMF measurements as well as temperature

An oxygen probe constructed along these lines is presented in Fig. below. It is important that
every gas cleaning system has this probe in order to monitor the oxygen partial pressure in the
gas continuously. The temperature of the probe can be kept at about 973 K.

In the case of gas mixtures, care should be taken so that there is no thermal segregation of
gases during the passage and the gas mixture is delivered very close to the zirconia tube
bottom.
Fig. IV-16: An oxygen probe for the measurement of oxygen partial pressures in the gas
phase.

Auxilliary Electrodes

The concept of auxiliary electrodes was introduced into the world of electrochemical sensors
by Iwase and coworkers.(Ref. 48, 49). He has introduced three component electyrode
mixtures which would enable the measurement of phosphorus in liquid copper or silicon in
liquid iron. The example of the electrode in the case of P in liquid Cu is presented below:

Mo, MoO2 // ZrO2-MgO // MgO, Mg3P2O8, Cu-P (Cell IV-10)

The reaction atnthe right-hsnd side electrode would be

3MgO (s) + 2 P (Cu, liq.) + 5/2 O2 = 3 MgO.P2O5 (s) (IV-32)

The cell was demonstrated to be sensitive to phosphorus levels in liquid Cu and could be used
in a reliable P –sensor for Cu. Similar idea for As was tried by the collaboration between
KTH and CODELCO, Chile. Preliminary experiments indicated that the cell functioning
could be improved to design an arsenic electrode. Iwase and coworkers have designed theSi
electrode for molten iron in a similar fashion and have shown the reliability of this cess as
well (REF).

The design of auxiliary electrodes require contact between three phases and hencde, one
should be careful in the preparation of the electrodes.

Summary

This chapter presents some of the fundamental aspects that have to be considered in designing
a galvanic cell sensor. The choice of the various components for the cell are discussed. The
electrolyte, reference electrodes, contact materials and gas phase interactions are discussed.
Finally, the design of auxilliary electrodes for the measurement of P in liquid Cu and Si in
liquid Fe are taken up to show the potentialities of galvanic cell measurements.