Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

References:
1. Bard, A.J. and Faulkner, L.R. 2001. Electrochemical Fundamentals: Fundamentals
and Applications. Ed-2. John Wiley and Sons: New York.
2. Goodridge, F. and Scott, K. 1995. Electrochemical Process Engineering: A Guide to
the Design of Electrolytic Plant. Springer Science and Business Media New York.
3. Brett, C. and Brett, A.M.O. 1993. Electrochemistry: principles, methods, and
applications. Oxford University Press:London.

1. Introduction:

We are all familiar with electrochemical cells as used in our daily life. To understand
the principles governing these processes, let us be familiar with some of the terms and
processes.

If we immerse two dissimilar metals in an electrolytic solution, we observe that a

current flow between the electrodes if connected through a conductor e.g. such as copper
wire. This process is called as Galvanic process. Understanding of galvanic process is
essential to understand corrosion as there are several parts of equipment made of different
materials. The principle is also useful in development of electrochemical sensors.

If potential is applied across the electrodes then the process is known as electrolytic
process. Understanding the behaviour of these processes help in the study of electrochemical
synthesis, fuel cells etc.

Galvanic Cell: Transforms energy obtained in a chemical reaction into electron

movement i.e. into electrical energy.

Electrolytic cell: Transforms electrical energy into chemical energy by applying

potential. Used industrially in brine electrolysis, in the extraction and refining of metals, in
electrosynthesis, etc.

Electrochemical reaction is a reaction in which electrons are involved. Either the

electron is consumed or is released. When electron is consumed an ion in oxidised state is
converted to a more stable reduced state. When electron is released in the electrochemical
reaction, ion in reduced state is converted to a more stable oxidised state. One may consider
the electrochemical reaction as a reaction in which electron takes part as a reactant or product
for the purpose of analysis.
 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

Note:

Unit of charge is Coulomb and is denoted by C.

1 C = Charge of 6.24x1018 electrons.

1 A = 1 C/s (Current is the rate of flow of charge)

2. Faraday's Law

It relates the amount of chemical reaction caused by the flow of

current to the amount of electricity passed. Faraday's laws states that the quantities of
substances involved in the chemical change are proportional to the quantity of electricity
which passes through the electrolyte (First law). The masses of different substances dissolved
by a given amount of electricity are proportional to their chemical equivalents (second law).
Combination of the two laws provides the following equation.

Let us write cathodic and anodic reactions as

aA + bB + ne- cC + dD (at cathode)

aA + bB - ne- cC + dD (at anode)

Amount of A, mA formed is proportional to current, I, and time, t.

aIt
mA  (1.1)
nF

Rate of formation of A per unit area, rA, may be written as

mA I ai
rA    (1.2)
t nFS nF

where I = current [A], i = current per unit area, also called as current density [A/m2], n =
stoichiometric number of electrons involved in an electrode reaction , S = surface area of the
electrode [m2], F = Faraday's constant [=96 485 C/mol e-].

3. Electrochemical processes

The reactions in which charges (i.e. electrons) are transferred across the metal-
solution interface may be called as charge-transfer reactions. Electron transfer causes
oxidation or reduction to occur. Such reactions are governed by Faraday's law and the process
is called as faradaic processes. Electrodes at which faradaic processes occur are sometimes
called charge-transfer electrodes. Processes such as adsorption and desorption in which no
 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

chemical reaction takes place are known as nonfaradaic processes. When an electrode
reaction takes place both faradaic and nonfaradaic processes takes place and hence are to be
considered to understand performance of the electrochemical systems.

An electrode reaction is a heterogeneous reaction since it occurs only at the electrode-

electrolyte interface and not in the entire solution. The reaction rate depends on mass transfer
processes between the electrode-surface, other processes at the electrode-surface and kinetics.
Due to heterogeneous nature of the reaction, its rate is described in units of mol/s per unit
area.

4. Nernst Equation

In an electrochemical cell it is possible to measure voltage across the two electrodes

under no-current state. It is called open-circuit potential, zero-current potential or rest
potential.

Let us study the potential developed in a Galvanic process.

Gibbs free energy change in a chemical reaction is given by

G  nFE (4.1)

where E is electrode potential.

Under standard conditions (1M, 25 oC, 1 atm), Equation (1) can be written as

Go  nFE o (4.2)

Where Go and Eo are the values of Gibbs free energy change in a chemical process and
electrode potential at standard state respectively. When Eo is positive, the reaction is
spontaneous and when Eo is negative the reaction is non-spontaneous.

G  Go  RT ln Q (4.3)

Here Q is reaction quotient for a reaction. It is defined as ratio of concentrations of products

to reactants. From Equations (1), (2) and (3) we get

nFE  nFE o  RT ln Q (4.4)

where T = Temperature [K] and

R = Universal gas constant [= 8.314 JK-1mol-1 = 8.314 VCK-1mol-1]

Dividing by –nF we get Nernst equation

 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

RT
E  E0  ln Q (4.5)
nF

It may be noted that Nernst equation relates the cell potential, E, to cell potential at
standard state, E0, and temperature and concentration of chemical species involved at the
electrode surface. The current does not flow. To make the current flow one must apply higher
potential.

5. Examples:

Q1. Find the standard cell potential for an electrochemical cell with following cell
reaction. At standard state (1M, 25 oC, 1 atm).

Zn(s)+Cu2+(aq)→Zn2+(aq)+Cu(s)

A1. Write the half-reactions for each process.

Zn(s)→Zn2+(aq)+2e-
Cu2+(aq)+2e-→Cu(s)

Standard potential for the reduction half-reaction.

Cu2+(aq)+2e-→Cu(s) ; E⁰red=+0.339V

Standard reduction potential for the reverse of the oxidation reaction (change the sign)

Zn2+(aq)+2e-→Zn(s) ; E⁰red=-0.762 V

Zn(s)→Zn2+(aq)+2e- ; E⁰ox=+0.762 V

Add the cell potentials to get the overall standard cell potential.

Cu2+(aq)+2e-→Cu(s) ;mE⁰red=+0.339 V

Zn(s)→Zn2+(aq)+2e- ;mE⁰ox=l+0.762 V

Cu2+(aq)+Zn(s)→Cu(s)+Zn2+(aq) ; E⁰cell=+1.101 V

Q2. Calculate the cell potential for the following reaction when the pressure of the oxygen
gas is 2.50 atm, the hydrogen ion concentration is 0.10 mol/L, and the bromide ion
concentration is 0.25 mol/L.

O2(g)+4H+(aq)+4Br-(aq)→2H2O(l)+2Br2(l)

A2. Write the half-reactions for each process.

 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

O2(g)+4H+(aq)+4e-→2H2O(l)
mmmmmmml2Br-(aq)→Br2(l)+2e-

Standard potential for the reduction half-reaction

O2(g)+4H+(aq)+4e-→2H2O(l); E⁰red=+1.229 V

Standard reduction potential for reverse of the oxidation reaction (change the sign)

2Br-(aq)→Br2(l)+2e-;E⁰ox=-1.077 V

Add the cell potentials together to get the overall standard cell potential.

mmll O2(g)+4H+(aq)+4e-→2H2O(l) ; E⁰red=+1.229 V

mmmmmmml2[2Br-(aq)→Br2(l)+2e-] ; E⁰ox=-1.077 V

O2(g)+4Br-(aq)+4H+(aq)→2Br2(l)+2H2O(l);E⁰cell=+0.152 V

Determine the new cell potential at the nonstandard conditions using Nernst equation.

RT
E  E0  ln Q
nF

Note: For a reaction aA + bB ⇌ cC + dD the reaction quotient is given by

[C ]c [ D]d
Q
[ A]a [ B]b

If K is equilibrium constant then

Q = K, at equilibrium

K > Q, reaction will proceed in forward direction

K < Q, reaction will proceed in the reverse direction

1 1
Q  4  4
 4 4
 1.0 x106
PO2 [ H ] [ Br ] (2.5)(0.1) (0.25)

Number of moles of electrons transferred in the balanced equation, n = 4

From Nernst equation

RT
Ecell  Ecell
o
 ln Q
nF
8.314 x 298
 0.152  ln(1.0 x106 )
4 x96845
 0.152  0.089  0.063 V
 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

6. Reaction kinetics:

Let us consider a simple reaction at an electrode

A+ ne- B

At steady state rate of transfer of A to the electrode, NA (Moles/time)

N A  kL S  CA  CA,S   rA (6.1)

Here kL = mass-transfer coefficient, CA and CA,S are concentration of A in bulk and at the
electrode surface respectively. The equation is applicable in the presence of convection also.
Correlations for kL are available in literature. It depends upon the hydrodynamics of the
reactor. The reaction rate is represented by rA and is a function of concentration at the
surface, electrode potential, temperature etc. Since the electrode reaction takes place at the
electrode surface, rA depends upon CA,S and not CA.

rA  Sf  CA,S , E s , T  (6.2)

Unfortunately CA,S cannot be measured while CA is easily measured. It may be noted that the
potential difference is the driving force for the transfer of ions.

Let E1 and E2 are activation energies of reactants and products respectively.

E1  E2  H (6.3)

From thermodynamics we know that

ln K H  E1  E2 
  (6.4)
dT RT 2 RT 2

For an elementary equation, equilibrium constant K=k/k’. Here k and k’ are forward
and backwards reaction rate constants.

d  ln k  E
 12 (6.5a)
dT RT

d  ln k ' E
 22 (6.5b)
dT RT

Upon integration we get

 E 
k  A0 exp   (6.6)
 RT 
 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

Equation (6.6) is Arrhenius law.

7. Charge Transfer, Activation and Nernst Equation.

Let us consider the reaction

O+ ne- R

Forward and backward rate of reaction is given by

  G*  
rO   AO exp   O   CO (7.1a)
  RT  

  GR*  
rR   AR exp     CR (7.2b)
  RT  

In an electrochemical reaction G* is influenced by applied potential, E’. Note that

G  nFE . Let the effect is proportional to nFE’.

 

rO   AO exp 
 GO*   nFE ' 
   nFE ' 
 CO  kOCO exp   (7.3a)
 

RT

  RT 


   GR  1    nFE ' 

    1    nFE ' 
*


rR  AR exp   CR  kRCR exp  
 

RT 
  RT 


(7.4b)

i
But rA  , Hence
nF

  nFE ' 
iO  kOCO nF exp   (7.5)
 RT 

  1    nFE ' 
iR  kRCR nF exp   (7.6)
 RT 

Net current is i  iO  iR . At equilibrium iO  iR and E=E’

  nFE    1    nFE 
kOCO exp    kRCR exp    iO  iR (7.7)
 RT   RT 
 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

 RT   kO   RT   CO   RT   CO 
E   ln      ln    E 
0
 ln   (7.8)
 nF   kR   nF   CR   nF   CR 

Equation (7.8) is Nernst equation. At equilibrium iO and iR are called exchange

current density.

When there is overpotential i  iO  iR . Let us define over-potential, =E’-E. Here E’

is applied potential.

  nFq 
iO  iO exp   (7.9a)
 RT 

  1    nF 
iR  iR exp   (7.9b)
 RT 

   nFq    1    nF  
Hence i  iO  iR  iO exp    exp   (7.10)
  RT   RT  

Equation (7.10) is Butler-Volmer equation in absence of concentration gradient i.e.

no mass transfer effects are considered. This equation describes the current vs. overpotential
relationship.

For iO  iR

   nFq  
iO  iO exp   (7.11)
  RT  

RT RT
Hence   ln iO  ln i (7.12)
 nF  nF O

Equation (7.12) is called as Tafel equation.

8. Electrodes

Electrode reactions are heterogeneous and take place in the interfacial region between
electrode and solution, the region where charge distribution differs from that of the bulk
phases. The electrode process is affected by the structure of this region. At each electrode,
charge separation can be represented by a capacitance and the difficulty of charge transfer by
a resistance.
 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

The electrode can act as only a source (for reduction) or a sink (for oxidation) of
electrons transferred to or from species in solution, as in where О and R are the oxidized and
reduced species, respectively.

O  ne  R

Alternatively, it can take part in the electrode reaction, as in dissolution of a metal M.

M  M n  ne

In order for electron transfer to occur, there must be a correspondence between the
energies of the electron orbitals where transfer takes place in the donor and acceptor. In the
electrode this level is the highest filled orbital, which in a metal is the Fermi energy level, EF.
In soluble species it is simply the orbital of the valence electron to be given or received.
Thus:

For a reduction, there is a minimum energy that the transferable electrons from the
electrode must have before transfer can occur, which corresponds to a sufficiently negative
potential (in volts).

For an oxidation, there is a maximum energy that the lowest unoccupied level in the
electrode can have in order to receive electrons from species in solution, corresponding to a
sufficiently positive potential (in volts).

The values of the potentials can be controlled externally. In this way we can control
which way an electrode reaction occurs and to what extent.

Electrode classification: Based on Electrode-materials, and solutions the electrodes can be

classified into following categories.

1. An electrode in contact with a solution of its ions.

(a) A metal is in contact with its cations, e.g. Cu Cu 2 where half reaction is

of the form

M n  ne  M

and cell potential is given as (in terms of activity)

RT
E  E0  ln aM n (8.1)
F
 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

(b) A non-metal is in contact with its ions, e.g. H 2 H  or Cl2 Cl  on the

surface of an inert conducting substance such as platinum. For H 2 H  ,

cell potential is given in terms of partial pressure of hydrogen.

1/2
RT pH 2
E  E0  ln (8.2)
F aH 

The potential is due to electron transfer between the neutral species and the
ion.

2. A metallic electrode in contact with a solution containing anions that form a

sparingly soluble salt with the metal's ions, e.g. Hg Hg 2 Cl2 Cl  (calomel

electrode). The salt activity, being almost entirely in the solid phase, can be
regarded as unity. Thus the potential is a function only of the anion activity. Cell
potential can be written as:

RT
E  E0  ln aCl  (8.3)
F

These systems are much used as reference electrodes since, because of the low
solubility product of the salt, the potential is very stable. Other examples are
Ag Ag Cl Cl  and, for alkaline solution, Hg Hg O OH  .

3. Redox or inert electrodes: The electrode work as a source or sink of electrons. It

however does not take part in the reaction. The surface of an electrode has to exert
an influence on the electrode reaction (perhaps small) and can form bonds with
species in solution (formation of oxides, adsorption, etc.). Such processes give rise
to non-faradaic currents. Examples of this kind of electrodes are Pt, Au, Hg, glassy
carbon, different types of graphite, and semiconductor oxides.

4. Modified electrodes: All such electrodes that cannot be grouped into the above
categories.

9. Mass transfer Effects

Let us consider the case when mass transfer takes place due to diffusion only. The
conductivity of a solution is a result of the movement of all ions in solution under the
 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

influence of an electric field. Let us consider an isolated ion. The force due to the electric
field, E, is

F  neE (9.1)

Viscous force given by Stokes' equation

F  6 rv (9.2)

Neglecting other forces and balancing these two forces we get an expression for
maximum velocity of ions, v

neE
v  uE (9.3)
6 r

Here u is ion mobility and is the proportionality coefficient between the velocity and
electric field strength.

Flux of charge, j, is given by

j  nevcN A (9.4)

Here cNA is ion density.

One mole of electron F is equal to eNA. Substituting this value in the above equation
we get electric current density (Am-2)

j  nvcF  ncuFE (9.5)

The current, I, that passes between two parallel electrodes of area S can be related to
the flux of charge j, and to the potential difference between them,  , by

 S
I  jA  k (9.6)
l

where k is the conductivity and l the distance between the electrodes, applied electric field of
strength E   / l . Hence, for each ion

ki  nci ui F (9.7)

A solution contains various ions. The measured conductivity, k is summation of all values.

ki  F  ni ciui (9.8)

The molar conductivity of an ion, i is given by

 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

ki
i   ni ui F (9.9)
ci

Electrolyte molar conductivity, , is summation of all values for all ions i.e.

ki
   i   (9.10)
ci

Diffusive force is written as

  
F   i  (9.11)
 x 

Potential for a dilute solution is given as

i  i0  RT ln ci (9.12)

Upon differentiation we get

 i  RT  ci 
     (9.13)
 x  P ,T ci  x  P ,T

RT  ci 
Therefore, F    (9.14)
ci  x  P ,T

Volume flux of ions i, Ji, can be written as

ji cu F u RT  ci 
Ji   ci ui E  i i   i   (9.15)
ni e ni e ni F  x  P ,T

Diffusivity is given by Einstein Relation

ui RT
D (9.16)
ni F

Nernst-Einstein relation relates conductivity and diffusion coefficient.

ni2 F 2 Di
i  (9.17)
RT

Equation (9.17) is used to estimate of diffusion coefficients from conductivity measurements.

Substitution of values of ui into Einstein Relation we get Stokes-Einstein relation.

k BT
D (9.18)
6 r
 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

Equation (9.18) can be used for estimation of Diffusion coefficients from viscosity
measurement.

10. Consideration of Mass Transfer and Charge Transfer Reaction

Till now we have considered the potential developed in an otherwise still fluid i.e.
there is no movement of fluid not even due to natural convection. Under such conditions
there is no mass transfer. All the potential developed is due to charge transfer reaction only.
The current flows only when there is an overpotential. Once there is a movement of ions
mass transfer also takes place. It also results in development of concentration profile (Figure
10.1). The concentration profile may be due to diffusion only or even in the presence of
convection. Both can be covered by consideration of mass transfer coefficient. It is a
proportionality constant based on the assumption that mass transfer rate is proportional to
surface area (in the present case it is also electrode area) and concentration difference
between the bulk and the surface. All the equations developed above consider the
concentration of reactant (e.g. chemical species/ion A) at the electrode surface, CA,s, where
charge transfer reaction takes place. But CA,s cannot be measured. The concentration in the
bulk solution, CA, is known. The relationship between CA,s and CA is governed by the mass-
transfer process.

Fig. 10.1 Mass Transfer and surface reaction

Three situations may be observed.

(i) If the surface reaction is slow then it is called reaction controlled. The mass
transfer need not to be considered. Potential is described by Nernst equation. The
surface concentration is approximately equal to the bulk concentration.
(ii) The surface reaction is fast but the mass transfer is slow, the condition is mass-
transfer controlled. The behaviour is described purely by mass transfer principles.
The potential is described by Nernst equation but the concentration at the
electrode surface has to be used. For the following reaction
Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

O  ne  R

The potential at equilibrium is estimated at the concentration in the bulk i.e.

RT  CO 
E  E0  ln   (10.1)
nF  CR 

Due to mass transfer controlling situation the applied potential is given by

RT  CO , s 
E '  E0  ln   (10.2)
nF  CR , s 

Overpotential, therefore, can be written as

RT  CO , s CR 
  E ' E  ln   (10.3)
nF  CR , s CO 

Current density, i, is given by

i  nFNO (10.4)

Here, NO , is flux of ion O from the bulk to the electrode surface due to mass
transfer and also due to migration of ion under the influence of the electric field.
The diffusional flux (per unit area), ND, is given as

N D  kL  CO  CO,s  (10.5)

Migration of ions due to influence of the electric field is written as

t i
NE  (10.5)
nF

Here t+ is transport number.

From Equation (10.4) and (10.5) we get

t i
NO  N D  N E  kL  CO  CO ,s   (10.6)
nF

Thus from Equation (10.4) and (10.6) we get

 t i 
i  nF  k L  CO  CO , s  
nF 
(10.7)


Hence
Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

nFk L  CO  CO , s 
i (10.8)
1 t

Equation (10.8) suggests that maximum current is observed when the

concentration of O at the surface is zero i.e. as soon as O reaches at the surface it
reacts immediately. This current is called limiting current, ilim.

nFk LCO
ilim  (10.9)
1 t

Equation (10.9) is the basis of measurement of mass transfer

coefficient under the conditions of limiting current. The equation can also be
written as

ilim 1  t  
CO  (10.10)
nFk L

Eliminating CO from Equations (10.8) and (10.10) we get

i 1  t    ilim  i  1  t  
CO , s  CO   (10.11)
nFkL nFkL

From Equations (10.10) and (10.11)

CO , s

 ilim  i 
(10.12)
CO ilim

Substitution of this value in Equation (10.3) results in

RT  ilim  i  CR 
 ln    (10.13)
nF  ilim  CR , s 

In electrolytic process with metal deposition or gas evolution the product do not
go to the bulk solution i.e. it has no role to play. The ratio of concentration of R in
the bulk to the value at the electrode surface is 1. Hence Equation (10.13) reduces
to the following equation.

RT  ilim  i 
 ln   (10.14)
nF  ilim 

Hence, the current density can be written as

 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

   nF  
i  ilim 1  exp   (10.15)
  RT  

(iii) Neither the process is mass transfer controlled nor it is charge transfer controlled.
Both have to be considered. Equation (7.9a) is written as
C    nFq 
iC  iO  O , s  exp   (10.16)
 CO   RT 

Net cathodic current can also be written as (with t+=0)

iC  nFkL  CO  CO,s  (10.17)

The ratio of concentrations of O in bulk to that at the electrode surface can be

written as

CO , s iC
 1 (10.18)
CO nFk LCO

Substitution of Equation (10.18) into Equation (10.16) gives

 iC    nFq 
iC  iO 1   exp   (10.19)
 nFkLCO   RT 

Equation (10.19) can be arranged to give

1
iC  (10.20)
1 1

nFk LCO   nFq 
iO exp  
 RT 

Equation (10.20) is analogous to expression for two resistances in series.

11. Electrochemical Reactors

An electrochemical reaction can be carried out in batch mode or continuous mode. A

high reaction rate results in reduction of the reactor volume. Therefore, design is aimed to
reduce mass transfer resistance so that the charge transfer reaction can take place at high
rates. The continuous reactors are tubular type or parallel plate type where flow rate can be
kept high enough to produce good turbulence so that mass-transfer coefficient is high. Let us
examine some of the reactor types and their study their performance equations.

11.1 Batch Reactors

 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

In a batch reactor the concentration of the reactants and product changes with time as all the
chemical species (ions) remain in the reactor. Let us consider the following cathodic reaction.

A+ ne- B

A charge balance provides the following

dC A
iA S  nFV (11.1)
dt

where V is the volume of the reactor.

Tafel type equation with mass transfer is given as

CA
i  iA  (11.2)
1 1

nFk L k A exp  bA E '

Eliminating iA from Equation (11.1) and (11.2) we get

SC A dC A
 nFV (11.3)
1 1 dt

nFk L k A exp  bA E '

Integration of Equation (11.3) provides the following equation

nFV CA, f  1 1  dC A
S     (11.4)
tB  nFk L k A exp  bA E '   C A
C A ,0

Here, tB, is batch time and CA,0 and CA,f are initial and final concentrations of A. The
integration has to be carried out numerically. Equation (11.2) gives the variation of current as
the concentration of A changes with time.

11.2 Recirculation Through a Plug-flow reactor

In this configuration the electrolytes are circulated using a large reservoir. The
reaction takes place in a continuous reactor. It is a tubular reactor with large flow rate so that
it behaves as plug flow reactor i.e. there is no radial concentration profile i.e. the
concentration of A is a function of axial position only. Note that we are using cylindrical co-
ordinates. Let Q be the flow rate in the reactor. Writing material balance in an elemental
volume
 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

i A, z S
QdC A. z  dz (11.5)
nFL

Here, CA,z is the concentration of reactant A at a position z measured from the entrance. L is
the total length of the reactor. If u is the fluid velocity let us define a time, , which a fluid
element takes to reach at a distance z from the entrance. Therefore,   z / u and u=Q/A. Here
A is the cross-sectional area of the reactor. Realising V=LA we can write Equation (11.5) as

dC A. z
iA, z S  nFV (11.6)
dt

The expression for local current has to be substituted. The expression for current will
depend upon the contribution of mass transfer and charge transfer reaction. For example if we
consider that the process is mass-transfer controlling then Equation (11.6) can be written as
CA 2 
dC S
C CAA, z.z  0 V kL d (11.7)
A1

Upon Integration we get

C 
ln  A2   ak L (11.8)
 C A1 

Note that a is electrode surface area per unit volume of the reactor i.e. a=S/V.
Equation (11.8) is valid when there is no recirculation. It describes the performance of the
plug flow continuous reactor. Now let us introduce the recirculation reservoir, which converts
the process as a batch process. The reservoir volume is very large as compared to the volume
of the reactor we can write variation of CA1 with time by the following equation.

dC A1
QC A2  QC A1  Vr (11.9)
dt

Elimination of CA2 gives the following equation

dCA1
Vr  QC A1  QC A1 exp  akL  (11.10)
dt

Let the residence time in the reservoir be r=Vr/Q. Integration of Equation (11.10)
gives

 t 
C Af1  C 0A1 exp   1  exp  ak L  (11.11)
 r 
 Lecture Notes: Electrochemical Engineering: Prof. A. K. Verma, deptt. of Chemical Engg. & Technol.

Here C Af1 and C 0A1 are initial and final concentrations of A in the reservoir (same as inlet to the

reactor).