Nernst Equation Analysis

In a hydrogen-oxygen fuel cell system, water is produced as the final product. With pure hydrogen
and oxygen at standard conditions, i.e. 1 atm and 298 K, the reversible cell potential obtained is
1.229 V. This is the maximum voltage that can be withdrawn from this system.

However, in reality the feed streams, i.e. hydrogen and oxygen are often diluted for several reasons.
For example, air can be used as a source of oxygen, which also contains nitrogen. Similarly, the
products from water gas shift reaction (CO2 + H2) can be used as a source for hydrogen. Additionally,
pure hydrogen and oxygen can be used at different pressures and temperatures. Therefore, there is a
need to understand the dependency of the reversible cell potential on the concentration of various
species.

In order to build a relationship between the cell potential and concentration of different species, we
first recollect the concept of chemical potential learnt in thermodynamics. Chemical potential
measures the change in the Gibbs free energy of a system with change in chemistry of the system. It
is defined for each species in the system. Chemical potential for a species i in phase a can be related
to the Gibbs free energy change as follows
Nernst Equation Analysis

...................................................(1)

where μiα is the chemical potential of species i in phase a and measures the
change in the Gibbs free energy of the system with infinitesimal change in the number
of moles of species i, while temperature, pressure and the moles of other species are
held constant.

Also, from thermodynamics the chemical potential of a species i, can be related to its
concentration through activity, a –
...........................................................(2)

where is the chemical potential of species i at standard conditions, i.e. 1 atm and 298 K; ai
denotes the activity of species i.

The activity of species is a function of its chemical nature. In other words the activity of a
chemical species depends on the chemical nature of the species. The following table lists the
activity of species depending on their chemical nature.
Table 1. Activity of species depending on their chemical nature
Chemical Nature Activity
ai=pi/po; where pi and p0 are respectively the partial pressure of species i and the standard state pressure,
i.e. 1 atm. For example, activity of nitrogen (N2) in air at 1 atm would be partial pressure of N2 in air.
Ideal gas Since air approximately contains 78 % N2 (by volume), the activity of N2 would be 0.78 for 1 atm air
pressure. However, if the air pressure is increased to 2 atm, the N2 pressure increases proportionally and
hence the activity is doubled, i.e. 1.56.

ai=γi (pi/po); where γi is an activity coefficient, while pi and p0 have the same meanings as defined for
the case of an ideal gas.γi is the measure of deviation from ideal behavior (0 < γi < 1). The theories are
Nonideal gas
available from thermodynamics to quantify γi. Please note that while calculating the activity of N2 above,
we assumed the ideal gas case. However, nonideal behavior of N2 and air would decrease the activity.

ai=ci/co; where ci and c0 are respectively the molar concentration of species i and the standard state
concentration, i.e. 1 M (1 mol/L). For example, the acitivity of Na + ions in 0.1 M NaCl is 0.1. However,
Dilute solution the activity of Na + ions in 0.1 M Na2 SO4 would be 0.2, since 1 mol of Na2SO4 gives 2 moles of Na+
ions
(Na2SO4 -------> 2Na+ + SO42-)
ai=γi(ci/co); where γi is an activity coefficient, used to measure the deviation from ideal behavior. As
Nonideal solution already discussed, 0 <γi < 1 and therefore, the activity calculated assuming a nonideal behavior of a
species is low compared to that of ideal behavior.
ai=1; i.e. the activity of the pure components can be taken as unity. For example the activity of pure
Pure components
aluminum in an aluminum electrode is 1. Also, the activity of liquid water is taken as unity.
Cont.
Therefore, in order to calculate the Gibbs free energy change of the total system, the
contributions from all species are added –
(Using Equation 1)

(Using Equation 2)
...............................................................(3)
For hydrogen-oxygen fuel cell system, we have the following overall reaction –

It should be noted that the above reaction can be written in the following manner
too –

However, the total Gibbs free energy change calculated for this system would be different for the
above two reactions. This is due to the difference in stoichiometric coefficients of H2, O2 and H2O in
the two reactions.
Cont.
Therefore, it becomes necessary to work with molar Gibbs free energy change,Δg' which is defined
on a per mole basis and is therefore intrinsic, i.e. independent of the quantity of the system. For our
case, the molar Gibbs free energy change for the formation of water is -237 kJ/mol H2 at standard
temperature and pressure. However, if 10 moles of O2 reacted then the total Gibbs free energy
change is given by

Hence, on a molar basis for species H2, the molar Gibbs free energy change for this reaction can be
calculated from the chemical potentials of various species participating in the reaction –
.........................................(4)

Using Equations 2 and 4, we have –

Where ; is the Gibbs free change for the reaction at standard conditions, i.e. 1 atm and 298 K.
Cont.

..............................................................................................(5)

The amount of Gibbs free energy change (Δg'rxn) can be related to the electrical work by –

.........................................................(6)

where n is the number of moles of electron transferred, F is Faraday’s constant and Ecell is the
potential difference across the cell. It should be noted that the value of n is 2 in our case, since for
every one mole of water formed, 2 moles of electrons are transferred.
Using Equations 5 and 6, we get –
Cont.
As we discussed previously, the activities of H2 and O2 can be replaced by their respective partial
pressure assuming ideal behavior. This assumption leads to

...............................................(7)

The above relation clearly shows the dependency of reversible cell potential on the partial pressures
of H2 and O2 and is known as the Nernst Equation.

In general for any arbitrary number of products and reactants, we have –

.....................(8)

where vi denotes the stoichiometric coefficient of ith species involved in the chemical reaction. For
example, in our case the stoichiometric coefficient of O2 is 1/2.

The Nernst equation relates the reversible cell potential to the effective concentrations of various
species and is therefore, a very significant result.

In case of a hydrogen-oxygen fuel cell system, we have n = 2 and hence –

Cont.
This expression gives the maximum theoretical voltage across the cell at a particular temperature and pressure. This theoretical
voltage is also known as the open circuit voltage (OCV), i.e. the voltage observed when no current is drawn from the cell. When
the activities if H2 and O2 are both unity, i.e. the partial pressure of both H2 and O2 is 1 atm, it can be easily seen that the
expression reduces to –

Both the proton exchange membrane fuel cell (PEMFC) and the solid oxide fuel cell (SOFC) use hydrogen and oxygen as the feed
streams, however, the OCV observed is different for the two. This is due to the difference in operating temperatures of PEMFC
and SOFC. While the operating temperature range for a PEMFC is 40 to 100°C, the SOFCs are operated at very high temperatures
ranging from 750-1000°C. It should be noted that the temperature dependency of the OCV is not that straightforward as
indicated by the Nernst equation and one needs to be careful in analyzing those results. This is because the E0 cell value is also a
function of temperature, i.e. changes with change in temperature. The E0 cell decreases with increase in temperature. Therefore,
at standard pressure conditions, pH2 = pO2=1 atm, the OCV of a SOFC is lower than that of a PEMFC.
Table 2. OCV (at standard temperature condition, i.e. T = 298.15 K) vs. partial pressures of H2 and
O2 as calculated by Nernst Equation

Partial Partial Difference

Open Circuit
Pressure of Pressure of between OCV
Voltage (V)
H 2 (atm) O2 (atm) and E0 cell (mV)
1 1 1.229 0
1 2 1.233 4
1 3 1.236 7
1 4 1.238 9
1 5 1.239 10
2 2 1.242 13
3 3 1.250 21
4 4 1.256 27
5 5 1.260 31
2 1 1.238 9
3 1 1.243 14
4 1 1.247 18
5 1 1.250 21

As seen from the values in the table, the OCV increases slightly with increase in pressure of hydrogen
and/or oxygen. However, it can be seen that the OCV difference is not very significant even after
reaching higher pressures, i.e. 5 atm H2 and O2, only 31 mV voltage difference is observed.
Nernst equation also shows that potential difference can be generated with the same redox couple
by having different concentrations of species at the anode and the cathode side. This type of
arrangement is known as a concentration cell. For example, voltage can be obtained from a
hydrogen concentration cell where the anode and the cathode are maintained at different partial
pressures of hydrogen. For a hydrogen concentration cell, the following reactions take place –

1.At anode : H2 ------> 2H+ + 2e- ; E0a = 0.0 V vs. NHE

2.At cathode :2H+ + 2e- --- --> H2 ; E0c = 0.0 V vs. NHE
3.Overal : H2 ----------> H2 ; E0cell = E0c - E0a = 0 V

Fig.1. A schematic representation of a hydrogen

concentration cell
Cont.

We can write the following Nernst equation for this hydrogen concentration cell –

where (aH2)cathode and (aH2)anode are the activities of H2 at the cathode and anode side
respectively.

Assuming ideal gas behavior, and replacing the activities of H2 by its partial pressure, we get –

where (PH2)cathode and (PH2)anode are the partial pressures of H2 at the cathode and anode
side respectively.
Replacing the values of E0cell (= 0 V), n (= 2), R (= 8.314 J/(mol-K)), T (= 298.15 K), F (= 96500
C/mol) and (say), in the above equation we get –
Cont.
Therefore, for Ecell (or OCV) to be positive, Q should be less than unity. In other
words, (PH2)cathode < (PH2)anode

The variation in values of OCV with different values of Q has been listed in Table 3. This clearly shows that
OCV increases with decrease in the value of Q.

OCV (V) Q
0 1
0.059 10-2
0.118 10-4
0.177 10-6
0.236 10-8
0.295 10-10
0.354 10-12

Table 3. Variation in OCV with Q

This hydrogen concentration cell can produce decent voltage without oxygen and therefore can be
used in outer space where oxygen unavailable.