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Equilibrium Electrode Potential: Nernst Equation

1) The document discusses various types of electrodes used in electrochemistry including electrodes of the first kind, second kind, gas electrodes, amalgam electrodes, redox electrodes, and glass electrodes. 2) It provides examples of each type of electrode along with the general electrode reaction and Nernst equation. Key examples include Ag+|Ag, Cl-|Hg2Cl2, and H+|H2 electrodes. 3) Additional topics covered include reference electrodes, factors that influence gas electrode reactions, and the use of potential mediators for complex redox systems. Glass electrodes are described as involving the exchange of hydrogen ions between solutions and glass.

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Smruthi Suvarna
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436 views10 pages

Equilibrium Electrode Potential: Nernst Equation

1) The document discusses various types of electrodes used in electrochemistry including electrodes of the first kind, second kind, gas electrodes, amalgam electrodes, redox electrodes, and glass electrodes. 2) It provides examples of each type of electrode along with the general electrode reaction and Nernst equation. Key examples include Ag+|Ag, Cl-|Hg2Cl2, and H+|H2 electrodes. 3) Additional topics covered include reference electrodes, factors that influence gas electrode reactions, and the use of potential mediators for complex redox systems. Glass electrodes are described as involving the exchange of hydrogen ions between solutions and glass.

Uploaded by

Smruthi Suvarna
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Equilibrium Electrode Potential

Nernst Equation
ze
νA A + νB B + νC C + …….. = νM M + νN N + νO O + ……..
At constant pressure the change in free energy of the above reaction is given by:
Δ G = - z F ET,P
ET,P = - Δ G/ z F but Δ G = Σ μi ν i
Again, we know μi = μo + RT ln a
Hence, νA μA = νA μAo + RT ln aAνA μB = μBo + RT ln aB μC = μCo + RT ln aC
μM = μMo + RT ln aM μL = μLo + RT ln aL μO = μOo + RT ln aO

Δ G = Σμiν i = (Σμpoν p - Σμroν r) + RT Σ ln (aLνL aMνM……….)/ (aAνA aBνB……….)

If the activities of all the reactants and products are unity, then
Δ G = Δ Go = Σμioν i = RT ln K
Δ G = RT ln K + RT ln Π (apνp ×1/ arνr)
E = - (RT / zF) ln K - (RT/ zF) ln (aLνL aMνM……….)/ (aAνA aBνB……….)

E = E0 + (0.059/z) log (aAνA aBνB ……….)/ (aLνL aMνM ……….)


Reference Electrode Potential

E = E0 + (0.059/z) log (aAνA aBνB ……….) / (aLνL aMνM ……….)

 Where, E = ER - EL and E0 = E0R - E0L

 Experimentally, we can determine E or E0 only for cell or a combination of electrodes. Individual


values of ER , EL E0R and E0L cannot be determined straightway.

 To solve this problem, a electrode is selected as a reference electrode, whose potential is assumed to
be zero and the potential of all other electrodes are represented with respect to this reference
electrode. Following are some of the examples of reference electrodes proposed over the years:

1) Hydrogen Scale: Proposed by Nernst, this electrode consists of a hydrogen electrode in which the
H+ ion concentration is unity and the pressure of H2 gas is 1 atm. The potential of this electrode was
assumed to be zero.

2) Absolute Potential Scale: Proposed by Ostwald, this electrode consists of a mercury electrode in
which its charge with respect to the solution is zero. The potential of this electrode was assumed to
be zero.

3) Standard Hydrogen Electrode (SHE): It is most widely used reference scale till now. It’s potential
is assumed to be zero at all temperatures. It differs from the hydrogen scale in the facts that, in SHE
the H+ ion activity is unity and the fugacity of H2 gas is also unity.
Types of Electrodes
1) Electrodes of First Kind: Can be defined as half-cell where a metal or a non-metal has been dipped
into a solution containing the ions of the same metal or non-metal. For example: Ag|Ag+ and Se2-|Se

2) Electrodes of Second Kind: Can be defined as half-cell where a metal is covered by one of its
sparingly soluble compound (salt, oxide, or hydroxide) and then it is immersed into a solution
containing the same anion as the sparingly soluble compound. For example: Hg, Hg2Cl2 | Cl - and
Ag, AgCl | Cl –

3) Gas Electrodes: Can be defined as half-cell where a metallic conductor is in simultaenous contact
with the corresponding gas and the solution containing its ions. Example: Cl - |Cl2, Pt & H2, Pt | H+

4) Amalgam Elctrodes: Can be defined as half-cell where amalgam of some metal is in contact with a
solution containing ions of this metal. Example: Cd 2+ | Cd, Hg

5) Redox Electrodes:

6) Glass Electrodes:
Electrodes of First Kind

Half-cells where a metal or a non-metal has been dipped into a solution containing the ions
of the same metal or non-metal. For example: Ag+|Ag and Se2-|Se

Generally these kind of electrodes are represented by: Mz+ | M


General reaction is: Mz+ + ze = M
General Nernst equation will be: E = E0 + (0.059/z) log (aMz+ /aM )

Example 1): Ag+|Ag : Ag+ + 1e = Ag: : E = E0 + (0.059) log (aAg+ /aAg )

E = E0 + (0.059) log (aAg+ )

Example 2) Cu2+|Cu: Cu2+ + 2e = Cu: : E = E0 + (0.059/2) log (aCu2+ /aCu )

E = E0 + (0.059/2) log (aCu2+ )

Example 3) Se2-|Se: Se + 2e = Se2- : : E = E0 + (0.059/2) log (aSe /aSe2- )

E = E0 - (0.059/2) log (aSe2- )


Electrodes of Second Kind
Half-cells where a metal is covered by one of its sparingly soluble compound (salt, oxide, or hydroxide)
and thin it is immersed into a solution containing the same anion as the sparingly soluble compound.
For example: Cl - |Hg2Cl2, Hg and Cl – | AgCl , Ag
Generally these kind of electrodes are represented by: Az- | MA, M
General reaction is: MA + ze = M + Az-
General Nernst equation will be: E = E0 + (0.059/z) log (aMA /aM aAz- )

Example 1): Cl - |Hg2Cl2, Hg : Hg2Cl2 + 2e = 2Hg + 2 Cl -


E = E0 + (0.059/2) log (aHg2Cl2 /a 2 Hg a 2 Cl- )
E = E0 - (0.059) log ( a Cl- )
SO42-|Hg2SO4, Hg : Hg2SO4 + 2e = 2Hg + SO42-
E = E0 - (0.059/2) log ( a SO42- )
Example 2) Cl – | AgCl , Ag

Example 3) Metal- Metal-oxide Electrode: OH- | HgO, Hg and OH- | Sb2O3, Sb

HgO + H2O + 2e = Hg + 2OH-


E = E0 + (0.059/2) log (aHgO aH2O /aHg a2OH- )
E = E0 - (0.059) log ( aOH- )

Sb2O3 + 3H2O + 6e = 2Sb + 6OH-


E = E0 + (0.059/6) log (asb2O3 a3H2O /a2sb a6OH- )
E = E0 - (0.059/) log (aOH- )
Gas Electrodes(used in fuel cells)
Can be defined as half-cells where a metallic conductor is in simultaneous contact with the
corresponding gas and the solution containing its ions. Example: Cl - |Cl2, Pt & H+ | H2, Pt
Use of Metallic Conductor: It creates electrical contact between the gas and the ions in the
solution and it also acts as a catalyst for the electrode reaction.
Characteristics of the Metallic Conductor:
1) Should have high catalytic activity with respect to the gas and the ions in the solution.
2) Must be independent of activity of other ions and its own ions.
3) Inert to other reactions.
4) Must provide large interfacial area.
Example 1): Cl - |Cl2, Pt side reaction includes formation of hypochlorites and chlorites.
Cl2 + 2e = 2Cl - or (½ )Cl2 + e = Cl -
E = E0 + (0.059/2) log (fCl2 /a 2 Cl- ) or E = E0 + (0.059) log (f Cl2 1/2 /a Cl- )
E = E0 + (0.059) log (f 1/2 Cl2 /a Cl- )
Example 2) H+ | H2, Pt
2H+ + 2e = H2 or H+ + e = (½ ) H2
E = E0 + (0.059/2) log (a 2 H+ / fH2) or E = E0 + (0.059) log (a H+ /f H2 1/2 )
E = E0 - (0.059) [-log (a H+ )] - (0.059) log (f H2 1/2 ) = E0 - 0.059 pH - (0.059) log (f H2 1/2 )
Example 3) OH- | O2, Pt
O2 + 2H2O + 4e = 4OH - or (½ )O2 + H2O + 2e = 2OH –
E = E0 + (0.059/4) log (fO2 a 2 H2O / a4OH-)
E = E0 + (0.059/4) log ( fO2) - (0.059)log (a OH-) = E0 + (0.059/4) log ( fO2) + 0.059pOH
side reaction : O2 + H2O + 2e = HO2- + OH -
Amalgam Electrodes (used for production of chlorine and alkali)

Can be defined as half-cell where amalgam of some metal is in contact with a


solution containing ions of this metal. Example: Cd 2+ | Cd, Hg

Generally these kind of electrodes are represented by: Mz+ | Mm, Hg


General reaction is: mMz+ + mze = Mm(Hg)
General Nernst equation will be: E = E0 + (0.059/mz) log (amMz+ /aMm(Hg) )

Example 1): Cd 2+ | Cd, Hg


Cd 2+ + 2e = Cd(Hg) E = E0 + (0.059/2) log (aCd2+ /aCd(Hg) )

Cadmium Amalgam electrodes containing 12.5 % Cd are used to prepare standard, or


normal Weston cell, whose emf remains almost constant over a long time period.

side reaction : xMz+ + xze + yHg = MxHgy(Hg)


E = E0 + (0.059/xz) log (axMz+ / aMxHgy(Hg))
Oxidation-Reduction Electrodes or Redox Electrodes

Can be defined as half-cell where the same metal is present simultaneously in two different
oxidation states along with a metallic conductor.
Generally these kind of electrodes are represented by: Red , Oxz+ | Pt
General reaction is: Oxz+ + ze = Red
General Nernst equation will be: E = E0 + (0.059/z) log (aOxz+ /aRed )

Examples: Fe3+|Fe2+, Tl3+| Tl+, MnO4-| MnO4 2- , [Fe (CN)6]3-|[Fe (CN)6]4-

Example 1): MnO4 - , Mn2+ | Pt


MnO4 2- + 8H+ + 5e = Mn2+ + 4H2O
E = E0 + (0.059/5) log (aMnO4- a8H+ /aMn2+ )
E = E0 + (0.059/5) log (aMnO4- /aMn2+ ) - (0.059*8/5) pH

Example 2): C6H4O2 , C6H4(OH)2 | Pt (known as quinone-hydroquinone)


C6H4O2 + 2H+ + 2e = C6H4(OH)2
Q HQ or QH2
E = E0 + (0.059/2) log (aQ a2H+ /aHQ )
E = E0 + (0.059/2) log (aQ /aHQ ) - 0.059 pH
Potential Mediators
 When the reactants in a redox reaction are complex organic substances (proteins),
the metallic conductor in contact with them loses its ability to assume equilibrium
potential value correspoding to this system.

 In such cases, some other ions are used as potential mediators for measuring the
redox potential.

 These mediators are generally used in very low concentrations and are made up of
simple redox systems, such as Ce3+ and Ce4+.
Ox+ Ce3+ = Red + Ce4+

 The metallic conductor assumes the steady potential of the mediator and the
identical potential of the multiple redox system.

 Since the concentration the mediator is taken very less, hence its effect on the
potential of the original redox reaction is negligible.
Glass Electrodes
 There is no involvement of electron.
 The electrode reaction here is merely an exchange of hydrogen ions between two
phases- Solution and Glass.

H+ = HG+

 The charge on hydrogen ion corresponds to elementary positive quantity of


electricity, which means the transfer of hydrogen from one phase to another is
equivalent to transport of unit charge.
 The value of z in case of glass electrode should be taken as unity.

E = E0 + (0.059) log (aH+ /a HG+ )


E = E0 + (0.059) log (aH+ + K aM+ ) - (0.059) log a
E = E’0 + (0.059) log (aH+ + K aM+ )
E = E’’0 + (0.059) log aOH-
H+ + MG+ = HG+ + M+
K = aH+ (a - aHG+ )/(a HG+ aM+ )
a = a HG+ + aMG+ or aMG+ = a - aHG+

aH+/ a HG+ = (aH+ + K aM+ )/a

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