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1

Background

**• Consider the reaction given below:
**

A

B (1)

**• Let kf and kb are the rate constants of the
**

forward and backward reactions

2

Reaction rates

• Rate of the forward reaction is given by:

Rf = kf * CA (2)

• Rate of the backward reaction is given by:

Rb = kb * CB (3)

3

kb * CB (4) 4 .Net reaction rate • The net rate of reaction is given by: Rnet = Rf – Rb • Thus. Rnet can be written as: Rnet = kf * CA .

and is called the equilibrium constant (K) 5 .Equilibrium Equilibrium is defined as the point at which the net reaction rate is zero • From equation 4. we obtain an equilibrium concentration ratio kf / kb = K = CB /CA (5) • K is a constant.

Requirement Every kinetic theory requires that the kinetic equations collapse to thermodynamic relations at equilibrium • Equation similar to (5) required of any kinetic theory 6 .

• Information about the reaction rates is provided by kinetic equations • For a kinetic expression to be valid. kinetics • Thermodynamics provides a description of the behaviour at equilibrium • Predicts whether a reaction is feasible (spontaneous). reduction to thermodynamic equations at equilibrium is essential 7 .Thermodynamics vs.

activation energy R .pre exponential factor 8 .gas constant. A .The Arrhenius theory • Rate constants vary with temperature (generally increase with T) • Most common relationship between rate constant (k) and temperature is of the form: k = A e -Ea/RT (6) Ea .

called Arrhenius relationship • Activation energy : Energy barrier that has to be surmounted by the reactants before they can be converted to product • Larger the activation energy .Activation energy • Above relationship .more energy needed by reactants to surmount barrier 9 .

also called the frequency factor 10 .represents the number of attempts made at surmounting the barrier . • Pre exponential factor (A) .Significance k = A e -Ea/RT (6) • Exponent term (e -Ea/RT ) .represents the probability that the energy barrier will be surmounted.a probabilistic feature .

Activation energy E a Energy 11 .

Requirements of kinetic theories • Consider the general reversible electrode reaction O + ne = R (7) with kf and kb as the forward and backward reaction rate constants • This is a typical redox reaction Note that O and R stand for Oxidized state and Reduced state respectively 12 .

RT / nF [ln (CR * / CO*)] (8) • Relates the equilibrium potential of the electrode (Eeq ) to the concentration of the reactants and products (O and R) 13 . the equilibrium state is governed by the Nernst equation .See section on thermo: Eeq = E° .• For this reaction.

1st requirement of an electrode kinetic theory 14 .Any electrode kinetics theory must reduce to the Nernst equation when equilibrium conditions are placed upon it .

must provide information about the dependence of current on electrode potential • When a current is passed. i • Electrode kinetic theory .E vs. some electrochemical change occurs at the electrode 15 .

Overvoltage • Due to irreversibility .E (9) Eeq .expected (equilibrium) electrode potential E .actual electrode potential 16 .sustaining a given current requires that a penalty be paid in terms of electrode potential – penalty called overvoltage η = Eeq .

Tafel equation • Experimental observation: At low currents. i is the current density • Called the Tafel equation • Any successful electrode kinetic theory must also explain Tafel behaviour – 2nd requirement of an electrode kinetic theory 17 . the current is exponentially related to the overpotential η= a + b log i (10) • a and b are constants .

Rate equations must reduce to the Nernst and Tafel equations when the appropriate conditions are introduced. 18 .Recap 1. Any electrode kinetics theory must reduce to the Nernst equation when equilibrium conditions are placed upon it 2. Any electrode kinetic theory must also explain Tafel behaviour 3.

Kinetics of Electrode Reactions 19 .

t) = ia /nF (12) Recall that reaction rate and current are interlinked – also recall that reduction occurs at the cathode and oxidation at the anode 20 . t) = ic /nF (11) Where CO (0.Rates of forward and backward reaction O + ne = R (7) • For the above reaction. t) is the surface concentration of O • Similarly the rate of the backward reaction is given by: Rb = kb CR (0. the rate of the forward reaction is given by: Rf = kf CO (0.

Net reaction rate • The net reaction rate (and hence the net current) is given by Rnet = Rf – Rb = i/ nF = [ic – ia]/ nF = [kf CO (0. t) . t)] (13) 21 .kb CR (0.

the rate increases as the electrode potential becomes more negative • This is because the electrode can give away electrons more easily 22 .Potential dependence of kf and kb • Both kf and kb are potential dependent functions • The forward reaction (a reduction) is an electron accepting process .

the rate increases as the electrode potential becomes more negative This potential dependence needs to be qualified to obtain a true picture of electrochemical kinetics 23 .• The opposite trend is seen for the backward (oxidation) reaction .

Potential dependence of kf and kb Value of k kf kb More positive E 24 .

At equilibrium • It is possible to adjust the electrode potential and O and R concentrations make net reaction rate zero. t) = kb CR (0. t) (15) 25 . At this point: ic = ia . Rf = Rb (14) In other words: kf CO (0.

t)] = F/RT (E – E°) (17) 26 . invoking the Nernst equation: ln (kb) – ln (kf) = ln [CO (0. t)/ CR (0.Relating the rate constants to potential • Rearranging equation 15. t)/ CR (0. and taking logarithms on both sides : ln (kb) – ln (kf) = ln [CO (0. t)] (16) • Equation 16 is stated under conditions of equilibrium (zero net current) • Therefore.

• Differentiation of eqn 17 with respect to E (first and last terms only) yields: RT/F [d/dE {ln (kb)} + d/dE {ln (1/kf)}] = 1 (18) 1-ά + ά =1 • The two terms on the left sum up to one are called symmetry factors in the case of an one electron transfer reaction 27 .

Symmetry factors ά as an indicator of the symmetry of the energy barrier – the dashed lines show the shift in the curve for O + e (reactants) as the potential is made more positive 28 .

associated with the forward reaction .α RT/F d/dE {ln (kb)} = 1.Reductive and oxidative symmetry factors • The reductive symmetry factor .represented by the Greek alphabet α RT/F d/dE {ln (1/ kf)} = α (19) • The oxidative symmetry factor therefore becomes 1.α (20) 29 .

α.Significance • The term α is a measure of the symmetry of the energy barrier • If the effect of changing the potential is identical on both sides of the barrier. then α = 0. 30 .5 = 1. • Any asymmetry results in other (fractional) values of α.

Influence on kinetics Will return to this picture after detailed understanding of kinetic expressions 31 .

[αF/RT] (E-E°)} (22 .a) Similarly: kb = kb° e{[(1-α)F/RT][(E-E°)} (22 -b) 32 .Standard rate constants • Equation 19 on integration gives: ln (1/ kf) = αFE/RT+ c (21) • If kf = kf° @ E = E° kf = kf° e{.

• kf° and kb° are termed the standard (or conditional) rate constants • If the concentrations of O and R are equal. kf° = kb° Can be replaced by a single symbol k°. . 33 . and the potential is maintained at E° to prevent current flow: from equation 15.

• Systems with small standard rate constants are typically sluggish 34 .Significance of ko • k° . • Measure of the “kinetic facility” of the redox couple – • The larger the value of k°.very important parameter in electrode kinetics. the faster equilibrium will be attained.

g. • The largest measured values of these constants are on the order of 1-10 cm/s. : reactions involving a single electron transfer – such as: H2 = 2 H+ + 2e in a PEM fuel cell. 35 .• The standard rate constant is large for simple redox couples • e.

and can be as lower as 10 –9 cm/s in certain cases.a 4 electron process . O2 + 4 H+ + 4e = H2O • The oxygen reduction reaction .• These values drop rapidly with increasing reaction complexity.has a lower value of k° than the hydrogen oxidation reaction – increased complexity 36 .

Sluggish cathode kinetics • k° for oxygen reduction << k° for hydrogen oxidation • Note however that forward and backward rate constants can still be large kf = k° e{. need a larger overpotential to maintain a given k • Larger overpotential – lower net cell voltage . for small k° s.less efficient fuel cell Urgent need to improve oxygen reduction kinetics – increase k° 37 .[αF/RT] (E-E°)} (22-a) kb = k° e{[(1-α)F/RT][(E-E°)} (22-b) • Thus.

The Butler – Volmer Theory 38 .

[αnF/RT] (E-E°)} . t) e{. of electrons transferred) This formulation is called the Butler – Volmer formulation of electrode kinetics • Note – two components (anodic and cathodic) of current • Note – exponential dependence on potential 39 .End Result i = nF k° [CO (0.CR (0. t) e{[(1-α)nF/RT](E-E°)}] (25) (n – stands for no.

Typical V.I relationship 40 .

kb CR (0. t) . t)] (23) • Thus: i = nF [kf CO (0.Derivation • Writing an expression for net reaction rate: Rnet = i/nF = [kf CO (0. t)] (24) 41 . t) .kb CR (0.

CR (0. of electrons transferred This formulation is called the Butler – Volmer formulation of electrode kinetics 42 . t) e{.[αnF/RT] (E-E°)} . t) e{[(1-α)nF/RT](E-E°)}] (25) • n – stands for no.• Substituting the values for kf and kb from 22 in 23: i = nF k° [CO (0.

B-V Theory • This formulation links four important parameters: .Concentration of reactant .Concentration of product.Faradaic current . 43 .Electrode potential .

rearranges to give the Nernst equation 44 .H.CR (0.At equilibrium Equation 25 can be rewritten (after some arithmetic) as: CO (0.S. i = 0 • Right hand side (R. t) . t) e{[nF/RT][(E-E°)} = [i/nF k°] [e{[αnF/RT] (E-E°)}] (26) • At equilibrium.S) = 0 • L.H.

of equation 25 goes to zero • Depending on whether the overpotential is positive or negative.E°).S.H. one or the other of the exponents on the R. either the cathodic or anodic component vanishes • B-V formulation reduces to the form: ή = a +b log i (27) 45 .Tafel kinetics • For very large overpotentials (ή = E .

Reduces t the Nernst equation at equilibrium .• Thus the B-V formulation satisfies the following requirements: .Explains Tafel behaviour Has the makings of a good electrode kinetics theory 46 .

at equilibrium -net current is zero • Also. t) e{. t) e{[(1-α)nF/RT](E-E°)}] (25) Now becomes: nFk°CO* e{.The exchange current Current that flows (equal magnitude in opposite directions) at equilibrium • Recall .[αnF/RT] (Eeq-E°)} = nFk°CR* e{[(1-α)nF/RT](Eeq-E°)} (28) 47 .surface concentrations of O and R = bulk concentrations i = nF k° [CO (0.CR (0.[αnF/RT] (E-E°)} .

faradaic activity is still in progress at the electrode surface An equal magnitude of anodic and cathodic current flows 48 . 28 reduces to: e (nF/RT)[Eeq-E°] = CO* /CR* (29) • Restatement of the Nernst equation (8) • Though the net current is zero.• Eqn.

**This current density is referred to as the
**

exchange current (io)

• Thus the exchange current may be written

as:

io = nFk°CO* e{- [αnF/RT] (Eeq-E°)} (30)

49

e (nF/RT)[Eeq-E°] = CO* /CR* (29)

• Raise both sides of equation 29 to the power –α,

substitute for the term e{- [αnF/RT] (Eeq-E°)} to yield:

io = nFk°CO*(1-α) CR*α (31)

• In the case where CO* = CR* = C:

io = nFk°C (32).

50

Significance of io

• io is directly proportional to the standard

rate constant k°

• Frequently used as an important kinetic

parameter in place of k°

Ideally, one would like to have as high an

exchange current density as possible for

fast kinetics

51

(b) io= 10 –6 A/cm2).5).Effect of exchange current density on kinetics Const. (c) ) io= 10 –9 A/cm2 52 . α (0. (a) io= 10 –3 A/cm2.

Eeq) • Unlike earlier formulation (B-V). where the relationship was between the current and the quantity (E – E° ) • Uses io instead of ko 53 .provides direct relationship between current and overpotential (E .Current – overpotential equation • Especially convenient .

t) / CO *]e{. t)/ CR*] e{[(1-α)nF/RT] ή }] (34) Where ή = E .Eeq 54 . t) / CO *]e{.[αnF/RT] ή} . t)/ CR*] e{[(1-α)nF/RT](E-E°)}[ CO * / CO *] -(1-α) (33) using equation 29 to substitute for [ CO * / CO *]α and [ CO * / CO *] -(1-α) : i/io = [CO (0.Current – Overpotential eqn.[αnF/RT] (E-E°)}[ CO * / CO *]α . 25) by the exchange current density (eqn. we have: i/io = [CO (0. 31).[CR (0. .Derivation • Dividing the current density (eqn.[CR (0.

Typical current – overpotential curve 55 .

Effect of exchange current density Const. α (0.5). (c) ) io= 10 –9 A/cm2 56 . (b) io= 10 –6 A/cm2). (a) io= 10 –3 A/cm2.

= 10 –6 A/cm2 57 .Effect of the transfer coefficient io = const.

e{[(1-α)nF/RT] ή }] (35) • Known as the Butler .Volmer equation Used as a good approximation to eqn.their ratio equals unity • The current – overpotential eqn.surface and bulk concentrations are identical . 34 i is smaller than 10% of the smaller of the anodic or cathodic limiting currents 58 .Limiting cases • No mass transport effects .[αnF/RT] ή} . (34) becomes: i = io[e{.

• For very small values of η the B-V equation can be written in a linear form as: i = . the exponent ex is approximately equal to 1+x.io F ή/RT (36) • Linear relation between current and overpotential • Ratio of the two . Rct = .ή / i = RT/ io F (37) 59 .called the charge transfer resistance (Rct).Limiting cases • For very small values of x.units of resistance .

Limiting cases • Very large values of ή: • One of the exponents in eqn 35 goes to 0 • For large positive ή: i = io[e{[(1-α)nF/RT] ή }] (38) which becomes: ln (i /io) = (1-α)nF ή /RT (39) 60 .

[RT/(1-α)nF] ln io and b = [RT/(1-α)nF] Such an approximation is only valid for a given oxidation or reduction component when the other component contributes 1% or less to the total current.• Eqn.[RT/(1-α)nF] ln io (40) • Fits the Tafel formulation (eqn. 61 . with a = . 39 reduces to: ή = [RT/(1-α)nF] ln i . 10).

3 RT and – αnF/2. ή is called a Tafel plot • Shown in Fig.α)nF/2. • Comprises an anodic branch and a cathodic branch • Slopes of (1.3 RT respectively Sharp deviation from linearity as ή approaches zero – due to breakdown of assumptions 62 .Tafel plots • A plot of log i vs.

Tafel plot 63 .

Mass transport effects • Equations (35 – 40) assumed no mass transport effects • Mass transport effects are frequently present in electrochemical systems • Need for corrections to account for mass transport effects 64 .

Recall from the electrochemistry notes (eqn. 40): C(x=0)/C* = [1 – (i/il)] Where il is the limiting current 65 .

c)] e{.i/io = [CO (0.[CR (0. t) / CO *]e{.[1 – (i/il.[αnF/RT] ή} .a)] e{[(1-α)nF/RT] ή }] (41) Current –overpotential equation corrected for mass transfer effects 66 .[αnF/RT] ή} . t)/ CR*] e{[(1-α)nF/RT] ή }] (34) • Incorporating limiting currents into eqn 34: i/io = [1 – (i/il.

this equation can be linearized • Need to apply Taylor's series expansion • This yields (derivation omitted): ή = [RTi/nF] (1/io +1/ il.c –1/ il. 67 .a) (42) • Transport corrected analog of linearized B-V eqn.Limiting cases • Very small overpotentials.

• Recall: RT/Fio represents the resistance to charge transfer (37) • Thus.c +Rmt.a) (43) • Rmt.i (Rct + Rmt.c +Rmt.a are mass transfer resistances at the cathode and anode 68 . eqn. 42 can be re written as: ή = .

The overpotential close to equilibrium is due to poor charge transfer.Kinetics of the reaction is very slow . 69 .a: .c and il.Kinetics of the system are very fast • If the reverse is true: . 43 • When io >> il.Overpotential occurs mainly due to mass transport effects even at very close to equilibrium .Interpretation of eqn.

Limiting cases • For very large overpotentials a Tafel like expression can be obtained • For insignificant anode overpotentials: i/io = [1 – (i/il.c)] e{.[αnF/RT] ή} (44) 70 .

44 on rearrangement gives: ή = [RT/αnF] ln (io/il.i)/i] (45) • Equation can be used to fit a mass transport corrected Tafel plot • Can be used to obtain kinetic parameters in systems having mass transport effects.c .• Eqn. 71 .c) + [RT/αnF] ln [(il.

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