Introduction to Electrochemistry

(電化學概論)

Electrode Potential
2023/3/17
 Electrode Potential
• A galvanic cell is a combination of two electrodes
• Each electrode can be considered to make a
characteristic contribution to the overall cell potential
• A compelling and widely used way to report standard
cell potentials is to ascribe a potential to each electrode
• Electrode potentials are widely used in chemistry to
assess the oxidizing and reducing the power of redox
couples and to infer thermodynamic properties,
including equilibrium constants
• Redox couple with lower electrode potentials tends to
reduce those with higher potentials
• (Topic 6C Electrochemical Cells -> Topic 5F Activities ->
Topic 6D Electrode Potential)
 Standard Potentials
• Standard hydrogen electrode (SHE):
⚬ 2H ! aq + 2e" ⇌ H# g
𝑃 /𝑃 $
𝑅𝑇 %
𝐸 = 𝐸$ − 𝑙𝑛 ! #
2𝐹 𝑎% "
⚬ Pt(s)|H2(g)|H+ (aq) E0 = 0
⚬ Activities of the H+ must be 1
⚬ Hydrogen gas is 1 bar

Other electrode
⚬ Pt(s)|H2(g)| H+ (aq) |X
$
⚬ 𝐸 $ 𝑋 = 𝐸&'((
$
⚬ 𝐿∥𝑅 𝐸&'(( = 𝐸 $ R − 𝐸 $(L)
 Reference Electrode
• To measure the relative amount of Fe#! and Fe)! in a
solution

⚬ Right electrode: Fe)! + e" ↔ Fe#! 𝐸!$ = 0.771 𝑉

⚬ Left electrode: AgCl(+) + e" ↔ Ag (+) + Cl" 𝐸!$ = 0.222 𝑉
 Standard Reduction Potentials
• The electrode potentials are:
Fe#!
𝐸! = 0.771 − 0.5916log
Fe)!
𝐸" = 0.222 − 0.5916log Cl"

• And the cell potential is:

𝐸 = 𝐸! − 𝐸"
Fe#! "
= 0.771 − 0.5916log − 0.222 − 0.5916log Cl
Fe)!
• The [Cl-] is fixed by the solubility of KCl (saturated), therefore
the cell potential only changes when the quotient [Fe2+]/[Fe3+]
change
 Ag/AgCl Reference Electrode
• Ag|AgCl electrode: 𝐸 $ = +0.222 𝑉
• AgCl(+) + e" ↔ Ag (+) + Cl" 𝐸(saturated KCl) = +0.197 𝑉
⚬ AgCl s + e" ⇌ Ag s + Cl"
$
𝑅𝑇
𝐸=𝐸 − 𝑙𝑛𝑎-(#
𝐹

Ag(s)|AgCl(s)|Cl- (aq)
 Calomel Electrode (氯化亞汞, 甘汞)
• Calomel electrode:
1
Hg #Cl#(+) + e" ↔ Hg (.) + Cl"
2
• 𝐸 $ = +0.268 𝑉
• 𝐸(saturated KCl) = +0.241 𝑉

• A calomel electrode saturated

with KCl is called a saturated
calomel electrode (S.C.E.)
 Voltage Conversions Between Different
Reference Scales

• What is the potential with respect to a Ag/AgCl electrode

and to the S.H.E. if an electrode has a potential of -0.461
V versus a calomel electrode?
 R.E. in Non-Aqueous Systems
• Even in non-aqueous solvents, the most frequently used
reference electrode is the aqueous saturated calomel
electrode (SCE) connected to the measurement
solutions by a salt-bridge
• Aqueous reference electrodes, e.g., calomel and
Ag/AgCl, have several drawbacks
• These include liquid junction potentials, contamination
of the solvent solution by water, and precipitates at the
reference electrode frit, which cause noise and even
failure of the reference electrode
• A suitable non-aqueous electrolyte must be contained
 Ag/Ag+ Reference Electrode
• Ag ! + e" ⇌ Ag s
𝑅𝑇 1
𝐸= 𝐸$ − 𝑙𝑛
𝐹 𝑎/0"
• The Ag/Ag+ reference electrode is commonly employed in
non-aqueous electrochemical studies
⚬ The Ag/Ag+ reference electrode is made by placing a
silver wire into an electrolyte containing silver ions by by
dissolving 0.001 to 0.01 M AgNO3, AgClO4
⚬ Often the electrolyte in the reference compartment is the
same as the solution electrolyte: Tetrabutylammonium
perchlorate (TBAP) at approximately 0.1 M concentration
 Properties of the Ideal Reference
Electrode
• It should be reversible and obey the Nernst equation
concerning some species in the electrolyte
• Its potential should be stable with time
• Its potential should return to its initial value after small
currents are passed through the electrode (no hysteresis)
• If it is an electrode of the second kind (e.g., Ag/AgCl),
the solid phase must not be appreciably soluble in the
electrolyte
• It should show low hysteresis with temperature
 Types of Metallic R.E.
• Electrode of the first kind -- A pure metal electrode that is
in direct equilibrium with its cation in the solution, e.g.,
Ag/Ag+, Hg/Hg2+

• Electrode of the second kind – a metallic phase in

equilibrium with its sparingly soluble metal salt, e.g.,
Ag/AgCl, Hg2Cl2/Hg, Hg2SO4/Hg, HgO/Hg

• Inert redox electrodes, e.g., H+/H2(Pt)

Potential Values of Common Secondary
Reference Electrodes (at 25 oC)

x
 Harned Cell

Pt(s)|H2(g)| HCl (aq, b)|AgCl(s)|Ag(s)

1
H! g + AgCl s → H " aq + Cl# aq + Ag s
2
'
𝐸$%&& = 𝐸 ' AgCl/Ag, C𝑙 # − 𝐸 ' 𝑆𝐻𝐸
= 𝐸 ' AgCl/Ag, C𝑙 # , υ = 1

• The Nernst equation:

$ 𝑅𝑇 𝑎%" 𝑎-(#
𝐸&'(( = 𝐸&'(( − 𝑙𝑛 1/#
𝐹 𝑎 %!
For simplicity,
1/# $ 𝑅𝑇
𝑎%! = 1, 𝐸&'(( = 𝐸&'(( − 𝑙𝑛𝑎%" 𝑎-(#
𝐹
 The Harned Cell Potential
• Molality b of HCl(aq): 𝑎%" = 𝛾±𝑏/(𝑏 $), 𝑎-(# = 𝛾±𝑏/(𝑏 $)
$ 𝑅𝑇 $ 𝑅𝑇 𝑅𝑇
𝐸&'(( = 𝐸&'(( − 𝑙𝑛𝑎%" 𝑎-(# = 𝐸&'(( − #
𝑙𝑛𝑏 − 𝑙𝑛𝛾±#
𝐹 𝐹 𝐹
$ 2𝑅𝑇 2𝑅𝑇
= 𝐸&'(( − 𝑙𝑛𝑏 − 𝑙𝑛𝛾±
𝐹 𝐹
2𝑅𝑇 $ 2𝑅𝑇
𝐸&'(( + 𝑙𝑛𝑏 = 𝐸&'(( − 𝑙𝑛𝛾±
𝐹 𝐹
By applying Debye-Hückel Limiting Law
𝑙𝑜𝑔𝛾± = −𝐴 𝑧!𝑧" 𝐼 = −𝐴 𝑏
𝑙𝑛𝛾± = 𝑙𝑛10𝑙𝑜𝑔𝛾± = −𝐴𝑙𝑛10 𝑏
2𝑅𝑇 $ 2𝐴𝑅𝑇𝑙𝑛10 1/#
𝐸&'(( + 𝑙𝑛𝑏 = 𝐸&'(( + 𝑏
𝐹 𝐹
y intercept slope × x
 Example 6D.1
• The potential of the Harned cell at 25 oC has the following
values
𝑏/(10")𝑏 5 ) 3.215 5.619 9.138 25.63
𝐸&'(( /𝑉 0.52053 0.49257 0.46860 0.41824

• Determine the standard potential of the silver-silver chloride

electrode
2𝑅𝑇 $ 2𝐴𝑅𝑇𝑙𝑛10 1/#
𝐸&'(( + 𝑙𝑛𝑏 = 𝐸&'(( + 𝑏
𝐹 𝐹
𝑏/(10")𝑏 5 ) 1/# 1.793 2.370 3.023 5.063
𝑦 0.2256 0.2264 0.2273 0.2299
 Example 6D.1

$
• The data extrapolate to 𝐸!"## = 0.2323 𝑉
 The Electrochemical Series
• For two redox couples,
OxL/RedL and OxR/RedR
$
• 𝐿∥𝑅 𝐸&'(( = 𝐸 $ R − 𝐸 $(L)
𝑅𝑒𝑑6 + 𝑂𝑥7 → 𝑂𝑥6 + 𝑅𝑒𝑑7
• Electrochemical series: the
metallic elements (and
hydrogen) arranged in the order
of their reducing power as
measured by their standard
potentials in aqueous solution
• A metal low in the series (with a
lower standard potential) can
reduce the ions of metals with
higher standard potentials
 Quiz!
• 1. –1.47 V vs. SCE = ? V vs. SHE
• 2. –1.47 V vs. SCE = ? V vs. Ag/AgCl
• 3. –1.01 V vs. SHE = ? V vs. SCE
 Electromotive Force (EMF)
• Electromotive force, also called emf, is the voltage
developed by any source of electrical energy
• The voltage of an electrochemical cell, denoted by E,
is the potential difference between the two
terminals of the cell; it is expressed in volts (V)
• The word potential should be understood as an
abbreviation of electric potential vs. a reference
Applications of EMF
• The determination of activity coefficient
• Determination of equilibrium constant and solubility
product constant
• Determination of equilibrium constant of chemical
reactions
 Activity
Phase a
Solid 1
Gas p/po, where po is the standard pressure (1 atm =
101,325 pa or 1 bar = 100,000 Pa)
Solute γc/co, where co is the standard concentration for
that species (1 mol kg-1 or 1 mol L-1)
A pressure of 1 atm can also be stated as:
≡1.01325 bar
≡ 101325 pascal (Pa) or 101.325 kilopascal (kPa)
≡ 760 torr
 Calculating Cell EMF
A cell with the following cell notation is constructed at 25 oC:
Cr(s)|CrCl2(aq)(1 mol L-1)||HCl(aq)(pH=3.0)|O3(g)(0.01 bar),
O2(g)(0.2bar)|Pt
!
𝑂)(0) + 2𝐻(89) + 2𝑒 " → 𝑂#(0) + 𝐻#𝑂(() 𝐸 $ = +2.07 𝑉
#!
𝐶𝑟(89) + 2𝑒 " → 𝐶𝑟(:) 𝐸 $ = −0.91 𝑉
! #!
𝑂)(0) + 2𝐻(89) + 𝐶𝑟(:) → 𝑂#(0) + 𝐻#𝑂(() + 𝐶𝑟(89) 𝐸 $ = +2.98 𝑉
$
𝑅𝑇
𝐸=𝐸 − 𝑙𝑛𝑄
𝑛𝐹
(8.314 JK "1 mol"1 )(298.15 K) 𝑎;! 𝑎-<!"
= 𝐸 $ − 2.303 "1 log #
𝑛 f 96,485 C mol 𝑎;$ 𝑎% "
0.05916 𝑉 0.2 1
= 2.98 𝑉 − log ") # = 2.76 𝑉
2 (0.01)(10 )
The Determination of Activity Coefficient
• Once the standard potential of an electrode in a cell is
known, it can be used to determine the mean activity
coefficients by measuring the cell potential with the
ions at the concentration of interest
• For example, Harned cell potential
2𝑅𝑇 $ $ 2𝑅𝑇
𝐸!"## + 𝑙𝑛𝑏/(𝑏 ) = 𝐸!"## − 𝑙𝑛𝛾±
𝐹 𝐹
$
𝐸!"## − 𝐸!"##
𝑙𝑛𝛾± = − 𝑙𝑛𝑏/(𝑏 $ )
2𝑅𝑇/𝐹
Brief Illustration 6D.3
• The data in Example 6D.1 include 𝐸!"## = 0.46860 𝑉 when 𝑏 =
9.138×10&' 𝑏 $ . (2𝑅𝑇/𝐹 =0.05139 V in 25 oC)
• The mean activity coefficient at this molality is
0.2232 − 0.46860
𝑙𝑛𝛾± = − ln 9.138×10&' = −0.0799
0.05139
𝛾± = 0.9232
 𝐸 ! and the Equilibrium Constant, 𝐾
• A galvanic cell produces electricity because the cell
reaction is not at equilibrium
• The potentiometer allows negligible current to flow
through it, so concentrations in the cell remain
unchanged
• If we replaced the potentiometer with a wire, there would
be much more current, and concentrations would change
until the cell reached equilibrium
• At this point, nothing would drive the reaction, and 𝐄
would be 0
• When a battery runs down to 0 V, the chemicals inside
have reached equilibrium, and the battery is “dead”
 𝐸 ! and the Equilibrium Constant, 𝐾
• For the two half-reactions
Right electrode: 𝑎𝐴 + 𝑛𝑒 " ⇌ 𝑐𝐶 𝐸!$
Left electrode: 𝑑𝐷 + 𝑛𝑒 " ⇌ 𝑏𝐵 𝐸"$
Net reaction: 𝑎𝐴 + 𝑏𝐵 ⇌ 𝑐𝐶 + 𝑑𝐷 𝐸$

𝐸 = 𝐸! − 𝐸"
& >
$
0.05916 𝑉 Α - $
0.05916 𝑉 Α =
= 𝐸! − log 8 − 𝐸" − log @
𝑛 Α/ 𝑛 Α?
& @
$ $
0.05916 𝑉 Α - Α? $
0.05916 𝑉
𝐸 = 𝐸! − 𝐸" − log 8 > = 𝐸 − log𝑄
𝑛 Α/ Α= 𝑛
• When the cell is at equilibrium, 𝐸 = 0 and 𝑄 = 𝐾
 𝐸 ! and the Equilibrium Constant, 𝐾
• Finding 𝐸 $ from 𝐾
0.05916 𝑉
𝐸$ = log𝐾
𝑛
• Finding 𝐾 from 𝐸 $
AB % /$.$DE1F
𝐾= 10
Example
• Find the equilibrium constant for the reaction
Cu + + 2Fe)! ⇌ 2Fe#! + Cu#!
• Solution: Divide the reaction into two half-reactions
2Fe)! + 2e" ⇌ 2Fe#!(+) 𝐸!$ = 0.771 𝑉
− Cu#! + 2e" ⇌ Cu + 𝐸"$ = 0.339 𝑉
𝐸 $ = 𝐸!$ − 𝐸"$ = 0.771 − 0.339 = 0.432 V
𝐾 = 10(#)($.G)#)/$.$DE1F = 4×101G
 Finding 𝐾 for Net Non-Redox Reaction
• Consider the following half-reaction whose difference is
the solubility reaction for FeCO)(+)
FeCO)(+) + 2e" ⇌ Fe(+) + CO#"
) 𝐸!$ = −0.756 𝑉
Fe#! + 2e" ⇌ Fe + 𝐸"$ = −0.44 𝑉
FeCO)(+) ⇌ Fe#! + CO#")
𝐸 $ = 𝐸!$ − 𝐸"$ = −0.756 − −0.44 = −0. 316V
𝐾 = 𝐾:H = 10(#)("$.)1F)/$.$DE1F = 10"11
• From 𝐸 $ for the net reaction, we can compute 𝑲𝒔𝒑 for
FeCO)(+) (𝐾:H : Solubility Product Constant)
• Potentiometric measurements allow us to find
equilibrium constants that are too small or too large to
measure by determining concentrations of reactions and
products directly
 Relating 𝐸 ! and 𝐾
• If you know 𝐸!$ and 𝐸"$, you can find 𝐸 $ and 𝐾 for the net
cell reaction
• Alternatively, if you know 𝐸 $ (or 𝐾) and either 𝐸!$ or 𝐸"$, you
can find the missing standard potential

Example
• From the formation constant of Ni(glycine)2 plus 𝐸 $ for the
Ni2+ | Ni(s) couple,
Ni#! + 2glycine" ⇌ Ni(glycine)# 𝐾 = 1.2×1011
Ni#! + 2e" ⇌ Ni 𝐸 $ = −0.236 V
• Deduce the value of 𝐸 $ for the reaction
Ni(glycine)#+2e" ⇌ Ni + 2glycine"
 Relating 𝐸 ! and 𝐾
Solution
Ni#! + 2e" ⇌ Ni 𝐸!$ = −0.236 V
Ni(glycine)#+2e" ⇌ Ni + 2glycine" 𝐸"$ =? V
Ni#! + 2glycine" ⇌ Ni(glycine)# 𝐸 $ =? 𝐾 = 1.2×1011

0.05916 𝑉 0.05916 𝑉
𝐸$ = log𝐾 = log 1.2×1011 = 0.328 𝑉
𝑛 2
𝐸"$ = 𝐸 $ − 𝐸!$ = −0.236 − 0.328 = −0.564 𝑉
!
 Different Description of the Same Reaction
• The right half-reaction can be written
1. AgCl()) + e& ⇌ Ag ()) + Cl& 𝐸+$ = 0.222 𝑉
𝐸+ = 𝐸+$ − 0.05916× log Cl&
= 0.222 − 0.05916 ×log 0.0334 = 0.3093 𝑉
2. Ag + + e& ⇌ Ag ()) 𝐸+$ = 0.799 𝑉
In both cases, Ag(I) is reduced to Ag(0)
Therefore, both descriptions are correct
1
𝐸+ = 0.799 − 0.05916 ×log
Ag +
For AgCl, 𝑲𝒔𝒑 = Ag + Cl& = 𝟏. 𝟖×𝟏𝟎&𝟏𝟎
1.8×10 &0$
Ag + = = 5.4×10&1 𝑀
0.0334
1
𝐸+ = 0.799 − 0.05916 ×log
5.4×10&1 𝐾!" : Solubility Product Constant
= 𝟎. 𝟑𝟎𝟗𝟗 𝑽
EMF from Thermodynamic Data
 EMF from Thermodynamic Data
! "
e.g. 𝐻# + 𝐶𝑙# ↔ 2𝐻(89) + 2𝐶𝑙(89)

∆< 𝐻 $ = x(𝜈M ∆N 𝐻M$ − 𝜈7 ∆N 𝐻7$)

7,M

∆< 𝑆 $ = x(𝜈M 𝑆M$ − 𝜈7 𝑆7$)

7,M
∆< 𝐻 $ = 2∆N 𝐻%$ " + 2∆N 𝐻-(
$# $
− ∆N 𝐻%$! − ∆N 𝐻-(!
= −335.08 kJmol "1

∆< 𝑆 $ = 2𝑆%$ " + 2𝑆-(

$ $ $
# − 𝑆% − 𝑆-( = −243.57 JK
! !
"1 mol"1

∆< 𝐺 $ = ∆< 𝐻 $ − 𝑇∆< 𝑆 $ = −262.27 kJmol"1

$
∆𝐺 −262.270
𝐸 =− =− = 1.36 𝑉
𝑛𝐹 2×96.485
Electrochemical Series in Non-Aqueous
Solvents
 Survival Tips
• Some problems are brain-teasers designed to bring together your
knowledge of electrochemistry, chemical equilibrium, solubility, complex
formation, and acid-base chemistry
• They require you to find the equilibrium constant for a reaction that
occurs in only one half-cell
• The reaction of interest is not the net cell reaction and is not a redox
reaction
Here is a good approach
• Step 1. Write the two half-reactions and their standard potentials. If you
choose a half-reaction for which you cannot find 𝐸 ' , then find another
way to write the reaction
• Step 2. Write a Nernst equation for the net reaction and put in all the
known quantities. If all is well, there will be only one unknown in the
equation
• Step 3. Solve for the unknown concentration and use that concentration
to solve the chemical equilibrium problem that was originally posed
 Quiz!
• Calculate the equilibrium constant at 25 oC for the
reaction
2Cu+ → Cu2+ + Cu
Given:
Cu+ + e- → Cu E0 = 0.52 V
Cu2+ + e- →Cu+ E0 = 0.16 V
• What will be produced if Cu2O is dissolved in dilute
H2SO4?
 Thermodynamics
The chemical potential for the ith In a reaction
component of a mixture: 𝜈1𝑆1 + ⋯ + 𝜈O 𝑆O
𝜇O = 𝜇O$ + 𝑅𝑇𝑙𝑛𝑎O ⇌ 𝜈R 𝑆R + ⋯ + 𝜈S 𝑆S
𝜕𝐺
𝜇O = Δ< 𝐺 = x 𝜈O 𝜇O
𝜕𝑛O A PA ,H,Q O
& '
At chemical equilibrium:
𝐺 = x 𝑛O 𝜇O
O x 𝜈O 𝜇O = 0
O
• When two phases are in contact, chemical equilibrium is
(T) (TT)
established between the phases: 𝜇O = 𝜇O
• If this condition is not fulfilled, the reaction will take place
spontaneously until it is
• Before it is satisfied, the free energy can be lowered by the
transfer of i from one to the other phase
Thermodynamics
#!
𝐶𝑢 ⇌ 𝐶𝑢(8) + 2𝑒 "
 Inner Potential and Surface Potential
Electrode (M)
e-

c b outer potential ΨM a
inner potential 𝜑M = ΨM + cM
(Galvani potential)
surface potential cM
• 𝑊 1 = −𝐹ΨU ; 𝑊 2 = 𝜇'U − 𝐹𝜒 U
• 𝜇'U : chemical potential (except electrostatic force)
• 𝜇‡'U : electrochemical potential
• 𝜇‡'U = 𝜇'U − F ΨU + 𝜒 U = 𝜇'U − F𝜑 U
• 𝜑 U : inner potential or Galvani potential
 Electrochemical Potential of An Ion
HV8:' HV8:'
• 𝜇‡O = 𝜇O + 𝑧O F𝜑 HV8:'
• i: ion with charge number z
e.g. In a solution phase L
• 𝜇‡O6 = 𝜇O6 + 𝑧O F𝜑 6 𝜇‡O6 = 𝜇O$,6 + 𝑅𝑇𝑙𝑛𝑎O + 𝑧O F𝜑 6
Vacuum
Volta Potential Difference
surface
surface potential surface potential

Phase 1 Galvani potential difference Phase 2

 Galvani Potential Difference
• The difference in inner potentials between two phases is
referred to as the Galvani potential difference
• If one mole of z-valent ions, the conditions for equilibrium
for component i partitioned between two phases (M, L) with
potentials 𝜑 U , 𝜑 6
• It can be calculated for the equilibrium case when no net
current flows
𝜇OU + 𝑧O 𝐹𝜑 U = 𝜇O6 + 𝑧O 𝐹𝜑 6
Example:
#!
𝐶𝑢(89) + 2𝑒 " ⇌ 𝐶𝑢(:)
6 U
𝜇‡-W ‡'U# = 𝜇‡-W
!" + 2𝜇
0
$,6
𝜇-W !" + 𝑅𝑇𝑙𝑛𝑎-W!" + 2F𝜑 6 + 2𝜇'$,U
# + 2𝑅𝑇𝑙𝑛𝑎' # − 2F𝜑 U =
$,U 0
𝜇-W + 𝑅𝑇𝑙𝑛𝑎-W
 Standard Galvani Potential Difference
• The Galvani potential difference between electrode and
solution:
$,6 $,U $,U
U 6
𝜇 -W !" + 2𝜇 ' # − 𝜇 -W 𝑅𝑇
Δ𝜑 ≡ 𝜑 − 𝜑 = + 𝑙𝑛𝑎-W!"
2𝐹 2𝐹
• When 𝑎-W!" = 1: the standard Galvani potential
difference
$,6 $,U $,U
𝜇-W !" + 2𝜇 ' # − 𝜇-W
⇒ Δ𝜑 ≡ = Δ𝜑 $
2𝐹
$
𝑅𝑇
⇒ Δ𝜑 ≡ Δ𝜑 + 𝑙𝑛𝑎-W!"
2𝐹
 Electrode Potential
• A reference electrode can be introduced into the
solution, whose Galvani potential difference, Δϕ’, is
constant, then the potential of our working electrode with
respect to this second electrode E, is measurable: E =
Δϕ - Δϕ’
• If a reference electrode is set up, for the potential of a
metal electrode, M, in contact with a solution of its ions,
Mz+:
$
𝑅𝑇
𝐸≡𝐸 + 𝑙𝑛𝑎U("
𝑧𝐹
• 𝐸: electrode potential
• 𝐸 $: standard electrode potential
• 𝐸 ≡ 𝜑U − 𝜑6
 Redox Reaction
• 𝑂 X! + 𝑛𝑒 " ⇌ 𝑅 X"A ! (e.g. 𝐹𝑒 )! + 𝑒 " ⇌ 𝐹𝑒 #!)
𝜇‡; = 𝜇;$ + 𝑅𝑇𝑙𝑛𝑎; + 𝑧𝐹𝜑 6
𝜇‡7 = 𝜇7$ + 𝑅𝑇𝑙𝑛𝑎7 + (𝑧 − 𝑛)𝐹𝜑 6
• At equilibrium
𝜇‡; + 𝑛𝜇‡'U = 𝜇‡7
⟹ 𝜇;$ + 𝑅𝑇𝑙𝑛𝑎; + 𝑧𝐹𝜑 6 + 𝑛(𝜇'U −𝐹𝜑 U )
= 𝜇7$ + 𝑅𝑇𝑙𝑛𝑎7 + 𝑧 − 𝑛 𝐹𝜑 6
$ $ U
U 6
𝜇7 − 𝜇 ; − 𝑛𝜇 ' 𝑅𝑇 𝑎;
𝐸 ≡𝜑 −𝜑 =− + 𝑙𝑛
𝑛𝐹 𝑛𝐹 𝑎7
$ $ U $
𝜇 7 − 𝜇 ; − 𝑛𝜇 ' ∆𝐺
𝐸$ = − =−
𝑛𝐹 𝑛𝐹
U 6 $
𝑅𝑇 𝑎; $
𝑅𝑇 𝑎;
𝐸 ≡𝜑 −𝜑 =𝐸 + 𝑙𝑛 = 𝐸 + 2.303 𝑙𝑜𝑔
𝑛𝐹 𝑎7 𝑛𝐹 𝑎7
$
𝑅𝑇 𝑎7 $
𝑅𝑇 𝑎7
𝐸=𝐸 − 𝑙𝑛 = 𝐸 − 2.303 𝑙𝑜𝑔
𝑛𝐹 𝑎 𝑛𝐹 𝑎
 Short Summary
• Electrochemical potential
𝜇‡O = 𝜇O + 𝑧O 𝐹𝜑 = 𝜇O$ + 𝑅𝑇𝑙𝑛𝑎O + 𝑧O 𝐹𝜑
• At equilibrium
x 𝜈O 𝜇‡O = 0
O
• Electrode potential
𝐸 ≡ 𝜑 U − 𝜑 6 , ∆𝐺 $ = −𝑛𝐹𝐸 $
• It is clear that we must incorporate the effects of this
potential difference into our thermodynamic equations
• If one mole of z-valent ions is brought from a remote
position to the interior of the solution, in which there exists
a potential, 𝜑, then the work done will be zF𝜑
• This work term must be added to or subtracted from the
free energy μ depending on the sign of z
 Volta Potential Difference
• The Volta potential (also called Volta potential
difference, contact potential difference, or outer
potential difference) in electrochemistry is the
electrostatic potential difference between two
metals (or one metal and one electrolyte) that are in
contact and are in thermodynamic equilibrium
• Specifically, it is the potential difference between a
point close to the surface of the first metal, and a
point close to the surface of the second metal
 Example
• Please calculate the half-cell electrode potential of Cu
immersed in 0.1 M CuSO4 solution at (1) 298 K; (2) 50 oC
• (Assuming ideal solution, then aCu+2 = xCu+2 = 0.1;
$
𝐸-W!" /-W = +0.340 𝑉)

𝑅𝑇 𝑎-W!"
$
𝐸-W!" /-W = 𝐸-W!" /-W + 2.303 𝑙𝑜𝑔
𝑛𝐹 𝑎-W
• Assuming ideal solution, then aCu+2 = xCu+2 = 0.1
• => ECu2+/Cu = +0.340 V + 0.02955 log (0.1) = 0.310 V
• At 50 oC (323 K), 2.303 RT/F = 0.0641
• => ECu2+/Cu = +0.340 V + 0.0641/2 log (0.1) = +0.308 V
 Nernst Equation (half reaction)
𝑅𝑇 Y'
𝐸= 𝐸$ − 𝑙𝑛 Œ 𝑎O
𝑛𝐹
O
• 𝐸: the potential of the electrode vs. reference electrode
• 𝐸 $: the standard potential of the relevant redox couple
vs. reference electrode
• 𝑅𝑇: ideal gas constant and temperature
• 𝑛: stoichiometric number of the electron
• 𝑎O : activity of species i
• 𝑣O : the stoichiometric number of species I
• F: Faraday constant
 Harned Cell

Cu | Pt(s)|H2(g)| HCl (aq, b)|AgCl(s)|Ag(s) | Cu

I II III IV V VI I’
1
H! g + AgCl s → H " aq + Cl# aq + Ag s
2
anode: 2H ! aq + 2e" ⇌ H# g
)* )))
2𝜇6( 6%) = 𝜇(
# + 2𝜇
$

cathode: AgCl(+) + e" ↔ Ag (+) + Cl"

* ) % *) )*
𝜇+,-& + 𝜇6% = 𝜇+, + 𝜇6-& &

) ZT TZ# TZ Z 1 TTT
𝜇‡'T − 𝜇‡'T = 𝜇/0 + 𝜇‡-( + 𝜇‡% " − 𝜇/0-( − 𝜇%!
2
ZT TZ# TZ Z 1 TTT
= 𝜇/0 + 𝜇-( + 𝜇% " − 𝜇/0-( − 𝜇%! = ∆𝐺
2
 Harned Cell

∵ 𝜇‡O = 𝜇O$ + 𝑅𝑇𝑙𝑛𝑎O + 𝑧O 𝐹𝜑

) ) )
𝜇‡' − 𝜇‡' = 𝜇' − 𝐹𝜑 − 𝜇'T − 𝐹𝜑 T
T T T T
)
= −𝐹(𝜑 − 𝜑 T )
T
)
𝐸 ≡ 𝜑 − 𝜑T
T
)
𝜇‡' − 𝜇‡'T = ∆𝐺
T
∆𝐺
𝐸=−
𝐹

The Nernst equation:

1
H# g + AgCl s → H ! aq + Cl" aq + Ag s
2
$ 𝑅𝑇 𝑎%" 𝑎-(#
𝐸&'(( = 𝐸&'(( − 𝑙𝑛 1/#
𝐹 𝑎 %!
 Quiz Again!
• If Zn electrode was replaced by Cu, how to make this cell
work?

Cu

CuSO4(aq)