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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This is the maximum voltage that can be withdrawn from this system.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

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

where i 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.

Chemical Nature

Ideal gas

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 N 2 in air.
Since air approximately contains 78 % N 2
(by volume), the activity of N 2 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

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the activity is doubled, i.e. 1.56.

Nonideal gas

Dilute solution

ai=i (pi/po); where i is an activity

coefficient, while p i and p 0 have the same
meanings as defined for the case of an ideal
gas.i is the measure of deviation from
ideal behavior (0 < i < 1). The theories
are available from thermodynamics to
quantify i. Please note that while
calculating the activity of N 2 above, we
assumed the ideal gas case. However,
nonideal behavior of N 2 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, the
activity of Na + ions in 0.1 M Na2 SO4
would be 0.2, since 1 mol of Na2 SO4 gives
2 moles of Na+ ions
(Na2 SO4 -------> 2Na+ + SO42-)

Nonideal solution

ai=i(ci/co); where i is an activity

coefficient, used to measure the deviation
from ideal behavior. As already discussed, 0
<i < 1 and therefore, the activity
calculated assuming a nonideal behavior of
a species is low compared to that of ideal
behavior.

Pure components

ai=1; i.e. the activity of the pure

components can be taken as unity. For
example the activity of pure aluminum in
an aluminum electrode is 1. Also, the
activity of liquid water is taken as unity.

Table 1. Activity of species depending on their chemical nature

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

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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 H 2, O2 and H2 O in the two
reactions. Therefore, it becomes necessary to work with molar Gibbs free energy change,g' 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 H 2 at
standard temperature and pressure. However, if 10 moles of O 2 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
conditions, i.e. 1 atm and 298 K.

; is the Gibbs free change for the reaction at standard

...............................................................................................(5)
The amount of Gibbs free energy change (g'rxn) can be related to the electrical work by

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

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where n is the number of moles of electron transferred, F is Faradays 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

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

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

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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 100C, the SOFCs are operated at very high temperatures ranging from
750-1000C. 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.

Partial
Pressure
of H 2
(atm)

Partial
Pressure
of O2
(atm)

Open
Circuit
Voltage
(V)

Difference
between
OCV and
E0 cell
(mV)

1.229

1.233

1.236

1.238

1.239

10

1.242

13

1.250

21

1.256

27

1.260

31

1.238

1.243

14

1.247

18

1.250

21

Table 2. OCV (at standard temperature condition, i.e. T = 298.15 K) vs. partial pressures of H 2 and O2
as calculated by Nernst Equation
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

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Fig.1. A schematic representation of a hydrogen concentration cell

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

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)

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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.

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