FUEL CELLS ANA BATTERIES Dr.

HASSAN ABDUL‐ZEHRA

Reaction Rate Expressions

1. Charge transfer controlled reaction

If the reaction rate is under the electron (charge) transfer control, (i.e. the electrode
process is occurring at a low rate compared to the rate at which reactant
is supplied to the surface or product is removed), for a first order reaction (1):

(13)

(14)

where the concentrations of the reactant and product species at the electrode surface
are related to the rate constants for the cathodic and anodic reactions, respectively.
They are related to the electrode potential, E by:

(15)

(16)

Where kc,0 and ka,0 are the rate constants for the reduction and oxidation processes
at E=0, respectively. αc and αa are the cathodic and anodic transfer coefficients. For a
simple electrode reaction i.e. αc + αa=1; they are kinetic parameters indicating the
direction of electrochemical reaction due to the applied potential and signify the fraction
of overpotential that affects the current density by lowering the free activation energy for
the reaction at an electrode-electrolyte interface.

2. Mass transport controlled reaction

If the reaction rate is only restricted by the rate of mass transport of species
(i.e. electron transport is very fast), then equations (13) and (14) become:

(17)

(18)

Where cO and cR are the bulk concentrations of the reactant and product species,
respectively and km is the mass transport coefficient given in equation (8).

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FUEL CELLS ANA BATTERIES Dr.HASSAN ABDUL‐ZEHRA

By the conservation of mass at the electrode surface, the reactant loss flux is
proportional to the electron transfer flux, which is proportional to the product
formation flux.
For pure diffusion transport:

(19)
Where DO and DR are the diffusion coefficients of the reactant and product
species, respectively. The current density is:

(20)
where δ is the distance travelled from the bulk to the electrode surface (Nernst
diffusion layer).

3. Mixed controlled reaction

With the contribution from both electron transfer and mass transport to the
overall conversion of O to R in reaction (1), equations (13) and (14) become:

(21)

(22)
Solving equations (13) and (21) to get:

(23)
Similarly, solving equations (14) and (22) to get:

(24)
Substitute equations (23) and (24) into equations (21) and (22), respectively to
get:

(25)

(26)
Equations (25) and (26) can be used to recognise the determining step in the
reaction process, i.e. if kc or ka <<km, then the slow step is the charge transfer
and the overall rate is electron transfer controlled and therefore, equations (25)
and (26) reduced to equations (13) and (14), respectively. On the other hand,

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FUEL CELLS ANA BATTERIES Dr.HASSAN ABDUL‐ZEHRA

if kc or ka >>km, then the reactant supply or the removal of the reaction products is the
rate determining step and the overall rate is mass transport controlled and thereby,
equations (25) and (26) reduced to equations (17) and (18), respectively.

Butler-Volmer Equation
Substitute equations (15) and (16) into equations (13) and (14), respectively, to get:

(27)

(28)

The surface concentration of species will be very close to that in bulk solution, since
the surface reaction occurs at a low rate. Therefore, the net (observed) current
density, j can be obtained from equations (27) and (28):

(29)
eq
At some value of E , the rate of the cathodic reaction equals the rate of anodic
reaction and the net rate of reaction, j is zero, therefore:

(30)
and therefore, equation (29) becomes:

(31)
Noting that αa + αc=1, rearrange equation (31) to get:

(32)
Substituting equations (9) and (32) into (29) leads to Butler-Volmer equation which
relates the current density to overpotential:

(33)
where the exchange current density, j0 depends on the concentrations of reactants
and products, temperature, the nature of the electrode-electrolyte interface and
impurities that may contaminate the surface:

(34)

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FUEL CELLS ANA BATTERIES Dr.HASSAN ABDUL‐ZEHRA

Four cases of electron transfer control may be distinguished according to the magnitude
and sign of the overpotential as shown in Figure 2:
• By taking decadic logarithms of equation (35), manipulation leads to the cathodic
Tafel slop=−2.3RT/(αcnF) which has the value of −118 mV at 298 K
for one electron change and αc=0.5.
At a very negative value of η (region 1), j≈jc, E << Eeq and η < −118/n mV.
Equation (33) reduces to:

(35)

• At a very positive value of η (region 2), j≈ja, E>>Eeq and η >118/n mV.
Equation (33) reduces to:

(36)

Figure 2: Current density vs overpotential curve for a charge transfer controlled

reaction.

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FUEL CELLS ANA BATTERIES Dr.HASSAN ABDUL‐ZEHRA

and the anodic Tafel slope=2.3RT/(αanF) which has the value of 118 mV at
298 K for one electron change and αa=0.5.
• At equilibrium (region 3), η=0, j=0, j0 = jc = −ja and E=Eeq from equation (9).
• At very small value of η, |η|<10 mV (region 4), equation (33) reduces to:

(37)

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