Lecture 1 Module 1 PDF
Lecture 1 Module 1 PDF
Objective:
To introduce the basic principles of Electrochemistry and Corrosion
Tarnish on silver
Rust on iron
Good side :
Bio degradable materials
Computer chips can be replaced by
https://doi.org/10.1038/ncomms8170 cellulose nanofibril (CNF)
What is Corrosion?
Corrosion is the process of gradual and irreversible damage or deterioration of a material due to the
unwanted chemical or electro chemical interaction with its environment.
➢ Metals get oxidized
➢ Ceramic refractories get dissolved in molten materials
➢ Materials may undergo irradiation damage
➢ Waste is produced
➢ Polymers react with oxygen and degrade
➢ Machineries get damaged
➢ Structures get damaged
Ore of iron :
Oxides, sufides Rusting of iron :
Fe2O3 formation
➢ RPB < 1, Tensile stresses in oxide film, thin film can crack (Non Protective)
➢ RPB > 1, (1~2), Compressive stresses in oxide film → uniformly cover metal surface and is protective
➢ RPB >> 1, Too much compressive stresses in oxide film → oxide cracks
Pilling-Bedworth ratio for some oxides
K2O Na2O MgO Al2O3 NiO Cu2O Cr2O3 Fe2O3
0.41 0.58 0.79 1.38 1.60 1.71 2.03 2.16
1. Some metals form Stable oxides (Protective), Al, Sn, Pb, Cu, Pt
2. Unstable or Reversible oxide formation (Non-Corrosive), Metal Metal oxide, Ag, Au, Pt
3. Formation of Volatile oxide Leads to extensive corrosion Mo ==> MoO3
4. Porous oxide formation leads to rapid corrosion, Fe2O, Fe2O3
Oxygen diffuse through the porous metal oxide bringing further corrosion.
B .Corrosion by other gases (SO2, CO2, Cl2, H2S, F2)
➢ Extend of corrosion depends on the affinity of the metal towards gas
➢ Degree of attach depends on protective or non protective layer formed
➢ Ag forms non-porous protective AgCl layer
➢ H2S gas leads steel to form porous FeS scale→ affect petroleum industry
Corrosion affects
• Suction pumps
• Drinking water pipes
• Sewage pipes
C. Liquid metal corrosion
➢ Chemical action of flowing liquid metal on solid metal or alloy at high temperature
➢ Corrosion cause weakening solid metal (Components of the Machinery)
❖ Dissolution of solid metal by liquid metal
❖ Internal penetration of the liquid metal to solid
https://materials.nuc.berkeley.edu/sunshot
Corrosion
Direct Chemical attack Electro chemical attack
(By environment) Electrochemical or
Chemical or Dry corrosion Wet corrosion
Zinc metal
Zn Zn2+(Concentration)
𝑴 We know that,
𝒏𝑭𝑬𝒆𝒍 = 𝒏𝑭𝑬𝟎𝒆𝒍 − 𝑹𝑻𝒍𝒏 ---(2) −∆𝑮 = 𝒏𝑭𝑬𝒆𝒍, 𝒂𝒏𝒅
𝑴𝒏+ 𝒂𝒒
−∆𝑮𝟎 = 𝒏𝑭𝑬𝟎𝒆𝒍
𝑬𝒆𝒍 = 𝑬𝟎𝒆𝒍 −
𝟐.𝟑𝟎𝟑 𝑹𝑻
𝒍𝒐𝒈 𝒏+
𝟏
---(3) “Standard electrode potential E0
𝒏𝑭 𝑴 𝒂𝒒 [M] = 1
𝑬𝒆𝒍 = 𝑬𝟎𝒆𝒍 +
𝟐.𝟑𝟎𝟑 𝑹𝑻
𝒍𝒐𝒈[𝑴𝒏+
𝒂𝒒 ] ---(4)
The Nernst’s Equation
𝒏𝑭
𝟎.𝟎𝟓𝟗𝟏
𝑬𝒆𝒍 = 𝑬𝟎𝒆𝒍 + 𝒍𝒐𝒈[𝑴𝒏+ 𝒂𝒒 ] ---(5) at 298K
𝒏
The cell, its Representation and its emf
Zn Zn2+(Conc.) Cu Cu2+(Conc.)
Reference electrode
Characteristics of a reference electrode
➢ An electrode half cell with a known half cell potential Eref
➢ The value of Eref will not change with the concentration of
the analyte solution (Eref is constant throughout)
➢ Always function at left hand side of the potentiometric cell
➢ E0 of an electrode can
be measured with
reference to SHE
𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑆𝐶𝐸 , 𝐻𝑔2 𝐶𝑙2 𝑠 ⇌ 𝐻𝑔2 2+ 𝑎𝑞 + 2𝐶𝑙 − Electrode is reversible with respect to Cl- ions
0 0.0591
𝑁𝑒𝑟𝑛𝑠𝑡 𝑒𝑞𝑛 𝐸 = 𝐸𝐻𝑔2𝐶𝑙2/𝐻𝑔 − 𝑙𝑜𝑔 𝑎𝐶𝑙− 2
2
0.0591
= +0.268 𝑉 − 𝑙𝑜𝑔 𝑎𝐶𝑙− 2
2
3. Ag/AgCl Electrode
Vycor plug
Calculate the potential of silver electrode in contact with a 0.01 M sodium chloride solution
𝑵𝒆𝒓𝒏𝒔𝒕 𝒆𝒒𝒏,
𝑬 = 𝑬𝟎𝑨𝒈𝑪𝒍/𝑨𝒈 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈 𝒂𝑪𝒍−
𝑬 = 𝟎. 𝟏𝟗𝟗 𝑽 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈 𝒂𝑪𝒍−
𝑬 = 𝟎. 𝟏𝟗𝟗 𝑽 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈 𝟎. 𝟎𝟏
𝑬 = 𝟎. 𝟏𝟗𝟗 𝑽 − 𝟎. 𝟎𝟓𝟗𝟏 ∗ −𝟐
= 0.199+0.1182 = 0.3172 V
Determining E0 for a half cell or single electrode using SHE:
E0 is relative with respect to Standard Hydrogen electrode (for SHE, E0 = 0)
0.26 V (SHE)
Sign of Standard electrode potential E0
SHE act as Anode SHE act as Cathode
Pt, H2 (1 atm) H+(1 M) Mn+(xM) M M Mn+(xM) H+(1 M) Pt, H2 (1 atm)
❖For reduction at an electrode “+” ve sign. ❖For oxidation at the electrode “-” sign.
Pt, H2 (1 atm) H+(1 M) Cu Cu2+ (1M) Zn Zn2+(1M) H+(1 M) H2 (1 atm) Pt
E0 for Cu is +0.34 V E0 for Zn is -0.76 V
1
𝐸𝑐𝑒𝑙𝑙 = E° (Ag+ /Ag) − 0.0591 log − 𝐸𝑆𝐶𝐸
[Ag+]
1
𝐸𝑐𝑒𝑙𝑙 = 0.80 𝑉 − 0.0591 log − 0.242 𝑉
[0.01 M]
Ecell = 0.4398 V
Applications of measuring Cell emf
1. Determining equilibrium constant of a reaction
The Van’t hoff reaction isotherm −∆𝑮° = 𝑹𝑻 𝒍𝒏 𝑲 = 𝒏𝑭𝑬𝟎𝒄𝒆𝒍𝒍
𝒏𝑭𝑬𝟎 𝒄𝒆𝒍𝒍
𝑻𝒉𝒆𝒓𝒆𝒇𝒐𝒓𝒆, 𝒍𝒏 K =
𝑹𝑻
Problem 2
For a cell reaction: Ni(s)Ni2+ (aq)Ag+ (aq) Ag(s)
Write the cell reactions and calculate the equilibrium constant at 25 ℃, E° (Ni2+ /Ni) = -0.25V; E° (Ag+ /Ag) = 0.80V
The solubility product of the salt is given by Ksp = [M+ ][X-], for very dilute solution
L.H. E,
M M +X-
(sat. soln.) MX (S) M R.H.E.
M ⇋ M+ (aq.) + e- MX (S) + e- ⇋ M + X-
𝒏𝑭𝑬𝟎 𝒄𝒆𝒍𝒍
𝒍og Ksp =
𝟐. 𝟑𝟎𝟑𝑹𝑻
𝑬𝟎 −𝟎.𝟕𝟑
𝒍og Ksp = =
𝟎.𝟎𝟓𝟗𝟏 𝟎.𝟎𝟓𝟗𝟏
Combine hydrogen electrode with a reference electrode, Eg SCE PtH2(1 atm) H+(unknown conc.) SCE
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝑹 − 𝑬𝑳 = 𝟎. 𝟐𝟒𝟐𝟐 − (−𝟎. 𝟎𝟓𝟗𝟏𝒑𝑯)
= 𝟎. 𝟐𝟒𝟐𝟐 + 𝟎. 𝟎𝟓𝟗𝟏𝒑𝑯)
𝑬−𝟎.𝟐𝟒𝟐𝟐
pH =
𝟎.𝟎𝟓𝟗𝟏
Calculate the potential of a hydrogen electrode when connected with a standard calomel electrode is measured to be +0.715 V.
Calculate the pH of the solution used in hydrogen electrode
𝑬−𝟎.𝟐𝟒𝟐𝟐 𝟎.𝟕𝟏𝟓−𝟎.𝟐𝟒𝟐𝟐 𝟎.𝟒𝟕𝟐𝟖
pH = = = =𝟖
𝟎.𝟎𝟓𝟗𝟏 𝟎.𝟎𝟓𝟗𝟏 𝟎.𝟎𝟓𝟗𝟏