Electrode potentials

Relative electrode potentials

§ Impossible to measure absolute electrode potential

§ Instead measure relative electrode potential wrt a second reference

interface

§ electrode potential vs. standard reference electrode

§ Hydrogen electrode : universal primary standard : 𝐸 ! = 0.00 𝑉

2𝐻" 𝑎𝑞, 𝑎 = 1 + 2𝑒 # ⇌ 𝐻$ (𝑔, 𝑃 = 1 𝑎𝑡𝑚)

§ Measure electrode potential wrt standard hydrogen electrode

𝐸 ! 𝑆𝐻𝐸 = 0.00 𝑉
50
Electromotive force series

§ list of standard half-cell electrode potential at 25 °C

§ most positive potential (Au3+ + 3e- à Au: 𝐸 ) = 1.498V),

forward (reduction) reaction favoured – noble – more
readily reduce – always cathode

§ most negative potential (K+ + e- à K : 𝐸 ) = - 2.931V,

forward (reduction) reaction not favoured – active –
always corrode – always anode

§ metals near top more stable and less prone to

corrosion

51
Electromotive force series

§ limitations –

§ pure metals in their own ions at unit activity

§ relative ranking not same in other media like

seawater

§ not applicable to alloys

§ gives corrosion tendency but not corrosion

rate

52
 Reference electrode for laboratory and field

§ standard hydrogen electrode inconvenient – uses H2

gas

§ saturated calomel reference electrode (SCE) useful in

chloride solution

§ Hg2Cl2(s) + 2e- à 2Hg(s) + 2Cl- (aq., saturated)

§ Electrode potential at 25 °C, 𝐸 ) = 0.242 V vs SHE

saturated calomel reference electrode

53
 Reference electrode for laboratory and field

§ silver-silver chloride reference electrode useful in

chloride solution

§ AgCl(s) + e- à Ag(s) + Cl- (aq.)

§ solid AgCl coating on a silver wire immersed in a

4M KCl solution with saturated AgCl

§ Electrode potential at 25 °C, 𝐸 ) = 0.222 V vs SHE

silver-silver chloride reference electrode

54
 Reference electrode for laboratory and field

silver-silver chloride reference in

copper-copper sulphate reference electrode, measurement on field
seawater

§ common features of reference electrodes

§ Half cell potential

§ doesn’t change with passage of small current thro’
reference electrode
§ must be constant
§ mustn’t drift with time 55
 Thermodynamics of corrosion - Basics

Free energy and chemical potential

§ Total energy of the system can be changed by adding or removing 𝑛% moles of various chemical
species 𝑖 to the system
𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 + ∑% 𝜇% 𝑑𝑛%

&'
chemical potential 𝜇% = &(" ),+,(
= 𝐺@%
#
For a chemical reaction
𝑣,𝐴, + 𝑣$𝐴$ + ⋯ → 𝑣,-𝐵, + 𝑣$-𝐵$ + …

∆𝐺 ! = 𝑣,-𝜇!(𝐵,) + 𝑣$-𝜇!(𝐵$) + … - {𝑣, 𝜇!(𝐴,) + 𝑣$ 𝜇!(𝐴$) +…}

∆𝐺 ! = ∑% 𝑣% 𝜇%! 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∑% 𝑣% 𝜇%! 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

56
 Thermodynamics of corrosion - Basics

Free energy and chemical potential

We know,
𝐺 = 𝐺 ! + 𝑅𝑇 𝑙𝑛𝑃

𝜇% = 𝜇%! + 𝑅𝑇 𝑙𝑛𝑃%

For solids and liquids,

𝜇% = 𝜇%! + 𝑅𝑇 𝑙𝑛𝑎%

𝑎% = 1, for solids
𝑎% = 1, for water
𝑎% = 𝐶% for other liquids and ions, valid for dilute solutions
𝑎% = 𝑃% for gases

57
 Thermodynamics of corrosion - Basics

The Nernst equation - Why is it important ?

consider general 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑐ℎ𝑒𝑚𝑖𝑐𝑎𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

−
𝑎𝐴 + 𝑏𝐵 + 𝑛𝑒 ⇌ 𝑐𝐶 + 𝑑𝐷

∆𝐺 ! = ∑% 𝑣% 𝜇%! 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∑% 𝑣% 𝜇%! 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

And in non-standard conditions,

∆G = ∑% 𝑣% 𝜇% 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∑% 𝑣% 𝜇% 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

∆G = 𝑐𝜇. + 𝑑𝜇/ − 𝑎𝜇0 − 𝑏𝜇1

𝜇0 = 𝜇0! + 𝑅𝑇 𝑙𝑛𝑎0

𝜇1 = 𝜇1! + 𝑅𝑇 𝑙𝑛𝑎1 58
 Thermodynamics of corrosion - Basics
The Nernst equation
𝜇. = 𝜇.! + 𝑅𝑇 𝑙𝑛𝑎.
!
𝜇/ = 𝜇/ + 𝑅𝑇 𝑙𝑛𝑎/

2$% 2&
'
∆G = {𝑐𝜇.! !
+ 𝑑𝜇/ − 𝑎𝜇0! !
− 𝑏𝜇1 } + 𝑅𝑇 ln ) +
2( 2*

2$% 2&
'
∆G = ∆𝐺 ! + 𝑅𝑇 ln ) +
2( 2*

With ∆𝐺 = −𝑛𝐹𝐸 𝑎𝑛𝑑 ∆𝐺 ! = −𝑛𝐹𝐸 !

3) 2$% 2&
'
𝐸= 𝐸! − (4 ln ) +
2( 2*

2.303𝑅𝑇 𝑎.5 𝑎/
&
𝐸= 𝐸! − log 2 6
𝑛𝐹 𝑎0 𝑎1 59
Thermodynamics of corrosion – Electrochemical cells and galvanic corrosion

Two unconnected cells…

Zinc ions in equilibrium with solid Zn electrode

Zn2+ + 2e- à Zn(s) E0 = - 0.762 V vs SHE

Copper ions in equilibrium with solid copper electrode

Cu2+ + 2e- à Cu(s) E0 = + 0.342 V vs SHE

60
Thermodynamics of corrosion – Electrochemical cells and galvanic corrosion
When connected becomes an electrochemical cell…

§ More negative the electrode potential in emf series, more active the
metal

§ More active metal corrodes (undergoes oxidation), at the anode,

'
§ Zn(s) à Zn2+(aq) + 2e- -𝐸"#$%& = -(- 0.762 V)

§ less active metal of the two electrodes undergoes reduction at

cathode

'
§ Cu2+(aq) + 2e- à Cu(s) 𝐸(")*$%& = + 0.342 V

§ Net reaction – Cu2+(aq) + Zn(s) à Zn2+(aq) + Cu(s)

' ' '

§ 𝐸(&++ = 𝐸(")*$%& − 𝐸"#$%& = 0.342 -(- 0.762 ) = 1.104V

§ DG 0 = - nFE cell
0
< 0 : spontaneous
61
Thermodynamics of corrosion – Nernst equation – Practice problems

An electrochemical cell consists of copper immersed in a solution of 0.01 M Cu2+ ions and
nickel immersed in a solution of 0.1 M Ni2+ ions at 25◦C.

(a) Which electrode will corrode when the cell is short-circuited?

(b) Calculate the cell emf

(c) Write the overall cell reaction

62