Tutorial On Electrolysis and Faraday's Law.: Prepared by Lawrence Kok

Tutorial on Electrolysis and Faraday’s Law.
Prepared by
Lawrence Kok
http://lawrencekok.blogspot.com
Electrochemistry
Chemical and electrical energy
Voltaic cell Electrolytic cell

Redox rxn
Conversion chemical energy Conversion electrical energy (Oxidation/reduction)
to electrical energy to chemical energy Movement electron
Produce electricity
Chemical
rxn
Electric current
Electrodes – different metal (Half cell) Electrodes – same metal (Half cell)
Types voltaic cell
Primary cell (Non rechargeable)

Secondary cell (Rechargeable)
Daniell cell Dry cell Alkaline cell Nickel cadmium cell
NH4CI and ZnCI2 MnO2 and KOH

Electrochemistry
Voltaic cell Electrolytic cell
Conversion chemical to electrical energy Vs Conversion electrical to chemical energy
Spontaneous rxn Non Spontaneous rxn
-e
-e
Cathode
О
Anode
+ -
О
-
О
О
+
Anode (-ve) – Oxidation Cathode (+ve) - Reduction Anode (+ve) – Oxidation Cathode (-ve) - Reduction
Electron flow from anode (-ve) to cathode (+ve) electrode Electron flow from anode (+ve) to cathode (-ve) electrode
- Zn Zn 2+
- - -e + -
Anode
- → Zn Cu2+ + Cathode X Anode Cathode
- Y+
+ +
2+
-e X -e
(-ve) - - Zn (+ve) - (+ve) (-ve) - Y+
2+
2+
Cu2+ -e + X -e + -e Y+
Cu2+ X-→ X + -e Y+ + e- → Y
Zn → Zn 2+ + 2e Cu2+ + 2e → Cu
(oxidized) (reduced) (oxidized) (reduced)
Anion (-ve ion) to anode (+ve) Cation (+ve ion) to cathode (-ve)
Voltaic Cell Electrolytic Cell

Anode Oxidation Negative (-ve) Oxidation Positive (+ve)
Cathode Reduction Positive (+ve) Reduction Negative (-ve)
Electrochemistry
Zn/Cu Voltaic Cell PbBr2 molten Electrolytic Cell
1.10Volt -e -e
-e
- +
+ -
О
+ Br - Pb2+
- Br - Pb2+
- + Br - Pb2+
+
-
Anode Cathode
Zn half cell (-ve) Cu half cell (+ve) Anode (+ve) Cathode (-ve)
Oxidation Reduction Oxidation Reduction
Zn → Zn 2+ + 2e Cu2+ + 2e → Cu 2Br- → Br2 + 2e Pb2+ + 2e → Pb
Zn + Cu2+ → Zn2+ + Cu PbBr2 → Pb + Br2
Electron flow from anode (-ve) to cathode (+ve) electrode Electron flow from anode (+ve) to cathode (-ve) electrode
-e
- - Zn Zn2+
- + Anode Cathode - Pb2+
Anode 2+
Cu2+ ++ + -
-- →Zn Zn Cathode Br -e -e Pb2+
-e - (+ve) (-ve)
(-ve) 2+
2+
Cu2+ -e + (+ve) Br + - -e Pb2+
- 2Br-→ Br2 + 2e- Pb2+ + 2e- → Pb
Cu2+ Br
Zn → Zn + 2e2+
Cu2+ + 2e → Cu (oxidized) (reduced)
(oxidized) (reduced) Anion (-ve ion) to anode (+ve) Cation (+ve ion) to cathode (-ve)
Electrochemistry
Zn/Cu Voltaic Cell PbBr2 molten Electrolytic Cell
-e -e
-e
1.10 Volt - +
+ -
О
+ Br - Pb2+
- Br - Pb2+
- + Br - Pb2+
+
-
Anode Cathode
Zn half cell (-ve) Cu half cell (+ve) Anode (+ve) Cathode (-ve)
Oxidation Reduction Oxidation Reduction
Zn 2+ + 2e ↔ Zn Eθ = -0.76V Pb2+ + 2e ↔ Pb Eθ = -0.13V

Cu2+ + 2e ↔ Cu Eθ = +0.34V Br + e
-
↔ Br Eθ = +1.07V
-
Find Eθcell (use reduction potential) Find Eθcell (use reduction potential)
Zn + Cu2+ → Zn2+ + Cu Eθ = ????? PbBr2 → Pb + Br2 Eθ = ???
Zn ↔ Zn2+ + 2e Eθ = +0.76 2Br - ↔ Br2+ 2e Eθ = -1.07

Cu2+ + 2e ↔ Cu E θ = +0.34 Pb2+ + 2e ↔ Pb E θ = -0.13
Zn + Cu → Zn + Cu Eθ = +1.10V
2+ 2+
Pb2+ + 2Br - → Pb +Br2 Eθ = -1.20V
Compound broken down
Eθ = +1.10V θ
(LYSIS)
E = -1.20V
+ve (spontaneous) energy needed
-ve (NON spontaneous)
Conversion chemical to electrical energy Conversion electrical to chemical energy

Energy needed to decompose compound!!!!!!!!
Factor affecting ion discharged
(Selective Discharge) Discharge of ions
Electrolysis (Molten Salt) ↓
- Molten/aqueous 1 Cation + 1 Anion
- Relative E values of ion
PbBr2 molten Electrolytic Cell
- Conc ion – conc/diluted Pb2+ Br -
- Nature of electrode
Oxidized sp ↔ Reduced sp Eθ/V
Liquid – Pb2+ and Br- ions
Li + e-
+
↔ Li -3.04
- K+ + e- ↔ K -2.93
+ Ca2+ + 2e- ↔ Ca -2.87
+ - Na+ + e- ↔ Na -2.71
Br - Pb2+
+ Pb2+
- Mg 2+ + 2e- ↔ Mg -2.37
Br -
Inert electrode + Br -
Pb2+ - Al3+ + 3e- ↔ AI -1.66
Carbon/graphite Mn2+ + 2e- ↔ Mn -1.19
+ - H2O + e- ↔ 1/2H2 + OH- -0.83
Zn2+ + 2e- ↔ Zn -0.76
Oxidation ← Anode (+ve) ← Anion
+ Cation → Cathode (-ve) → Reduction
Fe2+ + 2e- ↔ Fe -0.45
Ni2+ + 2e- ↔ Ni -0.26
Discharged Br- ion Br2 gas (brown gas seen) Discharged Pb2+ ion to Pb (grey deposit)
Sn2+ + 2e- ↔ Sn -0.14
О
Pb2+ + 2e- ↔ Pb -0.13
2Br - ↔ Br2+ 2e Pb2+ + 2e ↔ Pb
3
-0.1 Cu2+ + e- ↔ Cu+ +0.15
n= SO4 + 4H + 2e- ↔ H2SO3 + H2O +0.17
2- +
o
Find Eθcell (use reduction potential) cti
edu Cu2+ + 2e- ↔ Cu +0.34
θ R
Pb2+ + 2e ↔ Pb Eθ = -0.13 E 1/2O2 + H2O +2e- ↔ 2OH- +0.40
2Br -
↔ Br2+ 2e Eθ = -1.07 E θ Oxid Cu+ + e- ↔ Cu +0.52
ation =
Pb2+ + 2Br - → Pb +Br2 Eθ = -1.20V -1.07 1/2I2 + e- ↔ I -
+0.54
Fe 3+
+ e- ↔ Fe 2+
+ 0.77
Ag +
+ e- ↔ Ag +0.80
О
Eθ = -1.20V (LYSIS)
-ve (NON spontaneous) energy needed 1/2Br2 + e- ↔ Br- +1.07
Conversion electrical to chemical energy Cr2O72-+14H+ +6e- ↔ 2Cr3+ + 7H2O +1.33

Energy needed to decompose compound!!!!!!!! 1/2CI2 + e- ↔ CI- +1.36
MnO4 + 8H + 5e- ↔ Mn + 4H2O +1.51
- + 2+
Eθ =-ve → supply +1.20v to breakdown PbBr2 → Pb + Br2 1/2F2 + e- ↔ F- +2.87

(Selective Discharge) Discharge of ions
↓
Electrolysis (Molten Salt) - Molten/aqueous 1 Cation + 1 Anion
- Relative E values of ion
CaCI2 molten Electrolytic Cell - Conc ion – conc/diluted Ca2+ CI -
Liquid – Ca2+ and CI- ions
Li + e-
+
↔ Li -3.04
- K+ + e- ↔ K -2.93
О
+ Ca2+ + 2e- ↔ Ca -2.87
+ -
CI - Ca2+ - ↔ Mg
+ CI - Ca2+
Mg 2+ + 2e- -2.37
Inert electrode + CI - Ca2+ - Al3+ + 3e- ↔ AI -1.66
+ - H2O + e- ↔ 1/2H2 + OH- -0.83
Zn2+ + 2e- ↔ Zn -0.76
Fe + 2e-
2+
↔ Fe -0.45
Discharged CI- ion CI2 gas (yellow gas) Discharged Ca2+ ion to Ca
Ni + 2e-
2+
↔ Ni -0.26
Sn2+ + 2e- ↔ Sn -0.14
87
Pb2+ + 2e- ↔ Pb -0.13
-2.
2CI - ↔ CI2+ 2e Ca2+ + 2e ↔ Ca H+ + e- ↔ 1/2H 2 0.00
=
↔ Cu+
n
Cu2+ + e- +0.15
t io
SO4 + 4H + 2e- ↔ H2SO3 + H2O +0.17
uc
2- +
Find Eθcell (use reduction potential) Re
d Cu2+ + 2e- ↔ Cu +0.34
Eθ
Ca2+ + 2e ↔ Ca E θ = -2.87 1/2O2 + H2O +2e- ↔ 2OH -

+0.40
2CI -
↔ CI2+ 2e Eθ = -1.36 Eθ O
xida Cu +
+ e- ↔ Cu +0.52
t ion
Ca2+ + 2CI - → Ca +CI2 Eθ = -4.23V = -1.3 1/2I2 + e- ↔ I- +0.54
6 Fe3+ + e- ↔ Fe2+ + 0.77
Eθ = -4.23V (LYSIS) Ag +
+ e- ↔ Ag +0.80
-ve (NON spontaneous) energy needed 1/2Br2 + e- ↔ Br -
+1.07
Cr2O7 +14H +6e- ↔ 2Cr + 7H2O +1.33
2- + 3+
О
Conversion electrical to chemical energy
MnO4 + 8H+ + 5e- ↔ Mn2+ + 4H2O
-
+1.51
Eθ =-ve → supply +4.23v to breakdown CaCI2 → Ca + CI2 1/2F2 + e- ↔ F- +2.87
Factor affecting ion discharged Discharge of ions
(Selective Discharge)
Electrolysis (Aqueous Salt)
↓ 2 Cation + 2 Anion
NaCI aqueous Electrolytic Cell

- Molten/aqueous
- Relative E values of ion Na+/H+ CI-/OH-
- Conc ion – conc/diluted
Na+ , CI- + H+ , OH- (from water)
Li+
+ e- ↔ Li -3.04
- K+ + e- ↔ K -2.93
+ Ca2+ + 2e- ↔ Ca -2.87
-
О О
+ CI - Na+ Na+ + e- ↔ Na -2.71
+
CI - Na+ -
OH- H+
Inert electrode + OH- H+
- Al3+ + 3e- ↔ AI -1.66
+ - 2H2O +2e- ↔ H2 + 2OH- -0.83

Fe2+ + 2e- ↔ Fe -0.45
Ni + 2e-
2+
↔ Ni -0.26
Oxidation Reduction Sn2+ + 2e- ↔ Sn -0.14
Eθ > more +ve easier to lose e Eθ > more +ve easier gain e
4OH- ↔ 2H2O + O2 + 4e Eθ = -1.23
Pb2+ + 2e- ↔ Pb -0.13
Na+ + e ↔ Na Eθ = -2.71
2H2O ↔ 4H+ + O2 + 4e Eθ = -1.23 2H+ + 2e ↔ H2 Eθ = -0.83 H+ + e- ↔ 1/2H 2 0.00
2CI- ↔ CI2 + 2e Eθ = -1.36 2H2O +2e- ↔ H2 + 2OH- Eθ = -0.83 Cu2+ + e- ↔ Cu+ +0.15
SO4 + 4H + 2e- ↔ H2SO3 + H2O +0.17
2- +
Discharged OH- ion O2 gas Discharged H+ ion to H2 gas Cu2+ + 2e- ↔ Cu +0.34
1/2O2 + H2O +2e- ↔ 2OH -
+0.40
2H+ + 2e ↔ H2 Eθ = -0.83
Cu +
+ e- ↔ Cu +0.52
4OH - ↔ 2H2O + O2 + 4e Eθ = -1.23
1/2I2 + e- ↔ I- +0.54
2H2O → 2H2 + O2 Eθ = -2.06V
Fe3+ + e- ↔ Fe2+ + 0.77
Eθ = -2.06V Ag +
+ e- ↔ Ag +0.80
ОО
O2 + 4H+ +4e- ↔ H2O +1.23
Conversion electrical to chemical energy Cr2O72-+14H+ +6e- ↔ 2Cr3+ +1.33
Eθ =-ve → supply +2.06v to breakdown NaCI → H2 + O2 1/2F2 + e- ↔ F- +2.87

Electrolysis (Aqueous Salt) (Selective Discharge)
- Molten/aqueous
NaI aqueous Electrolytic Cell
- Relative E values of ion Na+/H+ I-/OH-
Na+ , I- + H+ , OH- (from water)
Li+
+ e- ↔ Li -3.04
- K+ + e- ↔ K -2.93
+ Ca2+ + 2e- ↔ Ca -2.87
-
О О
+ I- Na+ Na+ + e- ↔ Na -2.71
+
I- Na+ -
Inert electrode + OH- H+ - Al3+ + 3e- ↔ AI -1.66
Carbon/graphite OH- H+ Mn2+ + 2e- ↔ Mn -1.19
+ - 2H2O +2e- ↔ H2 + 2OH- -0.83

Fe2+ + 2e- ↔ Fe -0.45
Ni + 2e-
2+
↔ Ni -0.26
↔ I2
Pb2+ + 2e- ↔ Pb -0.13
2I- + 2e Eθ = -0.54 Na+ + e ↔ Na Eθ = -2.71
4OH- ↔ 2H2O + O2 + 4e Eθ = -1.23 2H+ + 2e ↔ H2 Eθ = -0.83 H+ + e- ↔ 1/2H 2 0.00
2H2O ↔ 4H+ + O2 + 4e Eθ = -1.23 2H2O +2e- ↔ H2 + 2OH- Eθ = -0.83 Cu2+ + e- ↔ Cu+ +0.15
SO4 + 4H + 2e- ↔ H2SO3 + H2O +0.17
2- +
Discharged I- ion I2 Discharged H+ ion to H2 gas Cu2+ + 2e- ↔ Cu +0.34

1/2O2 + H2O +2e- ↔ 2OH -
+0.40
2H+ + 2e ↔ H2 Eθ = -0.83
О О
2I - ↔ I2 + 2e Eθ = -0.54
I2 + 2e- ↔ 2I- +0.54
NaI → H2 + I2 Eθ = -1.37V
Fe3+ + e- ↔ Fe2+ +0.77
Eθ = -1.37V Ag+ + e- ↔ Ag +0.80
-ve (NON spontaneous) 1/2Br2 + e- ↔ Br- +1.07
O2 + 4H+ +4e- ↔ H2 O +1.23
MnO4 + 8H+ + 5e- ↔ Mn2+ + 4H2O
-
+1.51
Eθ = -ve → supply +1.37 v to breakdown NaI → H2 + I2 1/2F2 + e- ↔ F- +2.87
Discharge of ions
Electrolysis (Aqueous Salt) ↓ 2 Cation + 2 Anion
- Molten/aqueous
- Relative E values of ion Cu2+/H+ CI-/OH-
CuCI2 aqueous Electrolytic Cell - Conc ion – conc/diluted

Cu2+ , CI- + H+ , OH- (from water)
Li + e-
+
↔ Li -3.04
- K+ + e- ↔ K -2.93
+ Ca2+ + 2e- ↔ Ca -2.87
+ CI - Cu2+ - Na+ + e- ↔ Na -2.71
+
CI - Cu2+ - Mg 2+ + 2e- ↔ Mg -2.37
Inert electrode OH- H+ - Al3+ + 3e- ↔ AI -1.66
+ H+
Carbon/graphite OH- Mn2+ + 2e- ↔ Mn -1.19
О
+ - 2H2O +2e- ↔ H2 + 2OH- -0.83

Fe2+ + 2e- ↔ Fe -0.45
Ni + 2e-
2+
↔ Ni -0.26
4OH- ↔ 2H2O + O2 + 4e Eθ = -1.23
Pb2+ + 2e- ↔ Pb -0.13
2H+ + 2e ↔ H2 Eθ = -0.83
2H2O ↔ 4H+ + O2 + 4e Eθ = -1.23 2H2O +2e- ↔ H2 + 2OH Eθ = -0.83
- H+ + e- ↔ 1/2H 2 0.00
2CI- ↔ CI2 + 2e Eθ = -1.36 Cu2+ + 2e ↔ Cu Eθ = +0.34 Cu2+ + e- ↔ Cu+ +0.15
SO4 + 4H + 2e- ↔ H2SO3 + H2O +0.17
2- +
О
Discharged OH- ion O2 Discharged Cu2+ ion to Cu metal Cu2+ + 2e- ↔ Cu +0.34
Cu2+ + 2e ↔ Cu Eθ = +0.34
Cu+ + e- ↔ Cu +0.52
4OH- ↔ 2H2O + O2 + 4e Eθ = -1.23 I2 + 2e- ↔ 2I- +0.54
CuCI2 → Cu + O2 Eθ = -0.89V Fe 3+
+ e- ↔ Fe2+ +0.77
Eθ = -0.89V Ag +
+ e- ↔ Ag +0.80
ОО
O2 + 4H+ +4e- ↔ H2O +1.23
Eθ = -ve → supply +0.89 v to breakdown CuCI2 → Cu + O2 1/2F2 + e- ↔ F- +2.87

- Molten/aqueous
- Relative E values of ion Cu2+/H+ Br-/OH-
CuBr2 aqueous Electrolytic Cell - Conc ion – conc/diluted
Cu2+ , Br- + H+ , OH- (from water)
Li+
+ e- ↔ Li -3.04
- K+ + e- ↔ K -2.93
+ Ca2+ + 2e- ↔ Ca -2.87
+ OH- H+ - Na+ + e- ↔ Na -2.71
+
OH- H+ -
Br- Cu2+
Inert electrode + Br- Cu2+
- Al3+ + 3e- ↔ AI -1.66
О
+ - 2H2O +2e- ↔ H2 + 2OH- -0.83

Fe2+ + 2e- ↔ Fe -0.45
Ni + 2e-
2+
↔ Ni -0.26
2Br- ↔ Br2 + 2e
Pb2+ + 2e- ↔ Pb -0.13
Eθ = -1.07 2H+ + 2e ↔ H2 Eθ = -0.83
4OH- ↔ 2H2O + O2 + 4e Eθ = -1.23 2H2O +2e- ↔ H2 + 2OH Eθ = -0.83
- H+ + e- ↔ 1/2H 2 0.00
2H2O ↔ 4H+ + O2 + 4e Eθ = -1.23 Cu2+ + 2e ↔ Cu Eθ = +0.34 Cu2+ + e- ↔ Cu+ +0.15
SO4 + 4H + 2e- ↔ H2SO3 + H2O +0.17
2- +
О
Discharged Br- ion Br2 Discharged Cu2+ ion to Cu Cu2+ + 2e- ↔ Cu +0.34
Cu2+ + 2e ↔ Cu Eθ = +0.34
Cu+ + e- ↔ Cu +0.52
2Br- ↔ Br2 + 2e Eθ = -1.07 I2 + 2e- ↔ 2I- +0.54
CuBr2 → Cu + Br2 Eθ = -0.73V Fe 3+
+ e- ↔ Fe2+ +0.77
Eθ = -0.73V
O2 + 4H+ +4e- ↔ H2 O +1.23
MnO4 + 8H + 5e- ↔ Mn + 4H2O +1.51
- + 2+
Eθ = -ve → supply +0.73 v to breakdown CuBr2 → Cu + Br2 1/2F2 + e- ↔ F- +2.87

Electrolysis (Aqueous Salt)
- Molten/aqueous
- Relative E values of ion K+/H+ I-/OH-
KI aqueous Electrolytic Cell - Conc ion – conc/diluted
K+ , I- + H+ , OH- (from water)
Li+
+ e- ↔ Li -3.04
О
- K+ + e- ↔ K -2.93
+
+ I- - Na+ + e- ↔ Na -2.71
K+
+
I-
K+ - Mg 2+ + 2e- ↔ Mg -2.37
Inert electrode + OH- H+ - Al3+ + 3e- ↔ AI -1.66
Carbon/graphite OH- H+ Mn2+ + 2e- ↔ Mn -1.19
О
+ - 2H2O +2e- ↔ H2 + 2OH- -0.83

Fe2+ + 2e- ↔ Fe -0.45
Ni + 2e-
2+
↔ Ni -0.26
↔ I2 + 2e
Pb2+ + 2e- ↔ Pb -0.13
2I- Eθ = -0.54 K+ + e ↔ K Eθ = -2.93
SO4 + 4H + 2e- ↔ H2SO3 + H2O +0.17
2- +
Discharged I- ion I2 Discharged H+ ion to H2 Cu2+ + 2e- ↔ Cu +0.34

1/2O2 + H2O +2e- ↔ 2OH -
+0.40
2H+ + 2e ↔ H2 Eθ = -0.83
О О
2I- ↔ I2 + 2e Eθ = -0.54
I2 + 2e- ↔ 2I- +0.54
KI → H2+ Br2 Eθ = -1.37V
Fe3+ + e- ↔ Fe2+ +0.77
Eθ = -1.37V Ag+ + e- ↔ Ag +0.80
O2 + 4H+ +4e- ↔ H2O +1.23
MnO4 + 8H+ + 5e- ↔ Mn2+ + 4H2O +1.51
-
Eθ = -ve → supply +1.37 v to breakdown KI→ H2 + I2 1/2F2 + e- ↔ F- +2.87

- Molten/aqueous
- Relative E values of ion K+/H+ SO42-/OH-
K2SO4 aqueous Electrolytic Cell - Conc ion – conc/diluted
K+ , SO42- + H+ , OH- (from water) Li+ + e- ↔ Li -3.04
О
K+ + e- ↔ K -2.93
-
+
+ H+ - Na+ + e- ↔ Na -2.71
SO42- ↔ Mg
+ SO42-
H+ - Mg 2+ + 2e- -2.37
K+ Al3+ + 3e- ↔ AI -1.66
Inert electrode + OH- - Mn2+ + 2e- ↔ Mn -1.19
О
Carbon/graphite K+
+ OH- - 2H2O +2e- ↔ H2 + 2OH- -0.83

+ Cation → Cathode (-ve) → Reduction Fe2+ + 2e- ↔ Fe -0.45
Ni + 2e-
2+
↔ Ni -0.26
Oxidation Reduction Sn + 2e-
2+
↔ Sn -0.14
Eθ > more +ve easier to lose e Eθ > more +ve easier gain e Pb2+ + 2e- ↔ Pb -0.13
4OH- ↔ 2H2O + O2 + 4e Eθ = -1.23 K+ + e ↔ K Eθ = -2.93 H+ + e- ↔ 1/2H 2 0.00
2H2O ↔ 4H+ + O2 + 4e Eθ = -1.23 2H+ + 2e ↔ H2 Eθ = -0.83
Cu + e-
2+
↔ Cu +
+0.15
2SO42- ↔ S2O82- + 2e Eθ = -2.01 2H2O +2e- ↔ H2 + 2OH Eθ = -0.83
-
SO4 + 4H + 2e- ↔ H2SO3 + H2O +0.17
2- +
Cu2+ + 2e- ↔ Cu +0.34

Discharged OH- ion O2 Discharged H+ ion to H2
1/2O2 + H2O +2e- ↔ 2OH- +0.40
Ratio 1:2 2H+ + 2e ↔ H2 Eθ = -0.83 I2 + 2e- ↔ 2I- +0.54
4OH- ↔ 2H2O+ O2 + 4e Eθ = -1.23 Fe 3+
+ e- ↔ Fe 2+
+0.77
O2 gas K SO4 → H2+ O2 Eθ = -2.06V Ag +
+ e- ↔ Ag +0.80
H2 gas 2
О О
1/2Br2 + e- ↔ Br -
+1.07
Eθ = -2.06V
-ve (NON spontaneous) O2 + 4H +4e-
+
↔ H2O +1.23
Conversion electrical to chemical energy 1/2CI2 + e- ↔ CI- +1.36

Energy needed to decompose compound!!!!!!!! MnO4 + 8H+ + 5e- ↔ Mn2+ + 4H2O +1.51
-
S2 O82- + 2e ↔ SO42- +2.01

Eθ = -ve → supply +2.06 v to breakdown K2SO4→ H2 + O2
-
AgNO3 aqueous Electrolytic Cell

- Molten/aqueous
- Relative E values of ion Ag+/H+ NO3-/OH-
Ag+ , NO3- + H+ , OH- (from water) Li+ + e- ↔ Li -3.04
K+ + e- ↔ K -2.93
- Ca2+ + 2e- ↔ Ca -2.87
+
+ NO3- Ag+ - Na+ + e- ↔ Na -2.71
NO3- Ag+ - Mg 2+ + 2e- ↔ Mg -2.37
+ Al3+ + 3e- ↔ AI -1.66
Inert electrode + OH- H+ - Mn2+ + 2e- ↔ Mn -1.19
О
Carbon/graphite OH- H+
+ - 2H2O +2e- ↔ H2 + 2OH- -0.83

Ni + 2e-
2+
↔ Ni -0.26
Oxidation Reduction Sn + 2e-
2+
↔ Sn -0.14
-
Cu + e-
2+
↔ Cu +
+0.15
NO3- cannot be discharged Ag+ + e ↔ Ag Eθ = +0.80
SO4 + 4H + 2e- ↔ H2SO3 + H2O +0.17
2- +
Cu2+ + 2e- ↔ Cu +0.34

Discharged OH- ion O2 Discharged Ag+ ion to Ag
1/2O2 + H2O +2e- ↔ 2OH- +0.40
Ag+ + e ↔ Ag E θ = +0.80 I2 + 2e- ↔ 2I- +0.54
4OH -
↔ 2H2O+ O2 + 4e Eθ = -1.23
О
AgNO3 → Ag + O2 Eθ = -0.43V Ag+ + e- ↔ Ag +0.80
1/2Br2 + e- ↔ Br- +1.07
Eθ = -0.43V
-ve (NON spontaneous) O2 + 4H+ +4e- ↔ H2O +1.23
Conversion electrical to chemical energy 1/2CI2 + e- ↔ CI- +1.36

Energy needed to decompose compound!!!!!!!! MnO4 + 8H + 5e- ↔ Mn + 4H2O +1.51
- + 2+
S2 O82- + 2e ↔ SO42- +2.01

Eθ = -ve → supply +0.43 v to breakdown AgNO3→ Ag + O2 MnO4- + 8H+ + 5e- ↔ Mn2+ + 4H2O +1.51
- Molten/aqueous
- Relative E values of ion H+ SO42-/OH-
H2SO4 aqueous Electrolytic Cell - Conc ion – conc/diluted
H+ , SO42- + H+ , OH- (from water) Li + e-
+
↔ Li -3.04
K+ + e- ↔ K -2.93
- Ca2+ + 2e- ↔ Ca -2.87
+ SO42-
+ H+ - Na+ + e- ↔ Na -2.71
SO42- Mg 2+ + 2e- ↔ Mg -2.37
+
H+ - Al3+ + 3e- ↔ AI -1.66
OH- H+
Inert electrode + OH-
- Mn2+ + 2e- ↔ Mn -1.19
О
Carbon/graphite H+
+ - 2H2O +2e- ↔ H2 + 2OH- -0.83

Ni + 2e-
2+
↔ Ni -0.26
Oxidation Sn2+ + 2e- ↔ Sn -0.14
Reduction
2SO42- ↔ S2O82- + 2e Eθ = -2.01 SO4 + 4H + 2e- ↔ H2SO3 + H2O +0.17
2- +
Cu2+ + 2e- ↔ Cu +0.34

Discharged OH- ion O2 gas Discharged H+ ion to H2 gas 1/2O2 + H2O +2e- ↔ 2OH -
+0.40
Ratio 1:2 2H+ + 2e ↔ H2 Eθ = -0.83 Cu +
+ e- ↔ Cu +0.52
4OH - ↔ 2H2O + O2 + 4e Eθ = -1.23 1/2I2 + e- ↔ I- +0.54
O2 gas 2H2O → 2H2 + O2 Eθ = -2.06V Fe3+ + e- ↔ Fe2+ + 0.77
H2 gas
Ag +
+ e- ↔ Ag +0.80
О О
Eθ = -2.06V
O2 + 4H+ +4e- ↔ H2O +1.23
Cr2O72-+14H+ +6e- ↔ 2Cr3+ +1.33
Eθ =-ve → supply +2.06v to breakdown H2SO4 → H2 + O2 S2 O82- + 2e ↔ SO42- +2.01

1/2F + e- ↔ F- +2.87
Discharge of ions
Electrolysis (Concentrated Salt) ↓ 2 Cation + 2 Anion
- Molten/aqueous
- Relative E values of ion Na+/H+ CI-/OH-
Conc NaCI Electrolytic Cell - Conc ion – conc/diluted

Na+ , CI- + H+ , OH- (from water)
Li+
+ e- ↔ Li -3.04
- K+ + e- ↔ K -2.93
+ CI - Ca2+ + 2e- ↔ Ca -2.87
Na +
-
О О
+ CI - Na+ Na+ + e- ↔ Na -2.71
+ -
OH- H+
Inert electrode + OH- H+
- Al3+ + 3e- ↔ AI -1.66
+ - 2H2O +2e- ↔ H2 + 2OH- -0.83

Fe2+ + 2e- ↔ Fe -0.45
Ni + 2e-
2+
↔ Ni -0.26
4OH- ↔ 2H2O + O2 + 4e Eθ = -1.23
Pb2+ + 2e- ↔ Pb -0.13
Na+ + e ↔ Na Eθ = -2.71
2H2O ↔ 4H+ + O2 + 4e Eθ = -1.23 2H+ + 2e ↔ H2 Eθ = -0.83 H+ + e- ↔ 1/2H 2 0.00
2CI- ↔ CI2 + 2e Eθ = -1.36 2H2O +2e- ↔ H2 + 2OH- Eθ = -0.83 Cu2+ + e- ↔ Cu+ +0.15
SO4 + 4H + 2e- ↔ H2SO3 + H2O +0.17
2- +
Discharged CI- ion CI2 gas Discharged H+ ion to H2 gas Cu2+ + 2e- ↔ Cu +0.34
1/2O2 + H2O +2e- ↔ 2OH -
+0.40
Ratio 1:2 2H+ + 2e ↔ H2 E θ = -0.83
Cu +
+ e- ↔ Cu +0.52
2CI - ↔ CI2 + 2e E θ = -1.36
1/2I2 + e- ↔ I- +0.54
CI2 gas NaCI → 2H2 + CI2 + NaOH Eθ = -2.19
H2 gas Fe3+ + e- ↔ Fe2+ + 0.77
Ag +
+ e- ↔ Ag +0.80
ОО
Dilute NaCI – OH- discharged due to Eθ value
Conc NaCI – CI- discharged due to overpotential factor
Discharged of H+ and OH- ion need addition voltage O2 + 4H+ +4e- ↔ H2O +1.23
due to high activation energy for H2/O2 production Cr2O72-+14H+ +6e- ↔ 2Cr3+ +1.33
If Conc CI- is high ↑ – it is preferred !!!!!! 1/2CI2 + e- ↔ CI- +1.36
Eθ =-ve → supply +2.19v to breakdown NaCI → H2 + CI2 + NaOH 1/2F2 + e- ↔ F- +2.87

Discharge of ions
Electrolysis (Concentrated Salt) ↓ 2 Cation + 2 Anion
- Molten/aqueous
Conc CuCI2 Electrolytic Cell - Conc ion – conc/diluted

Cu2+ , CI- + H+ , OH- (from water)
Li+
+ e- ↔ Li -3.04
- K+ + e- ↔ K -2.93
+ CI - Ca2+ + 2e- ↔ Ca -2.87
+
Cu 2+
- Na+ + e- ↔ Na -2.71
CI - Cu2+
+ H+ -
OH -
Inert electrode + OH -
H+ - Al3+ + 3e- ↔ AI -1.66
О
+ - 2H2O +2e- ↔ H2 + 2OH- -0.83

Fe2+ + 2e- ↔ Fe -0.45
Ni + 2e-
2+
↔ Ni -0.26
4OH- ↔ 2H2O + O2 + 4e Eθ = -1.23
Pb2+ + 2e- ↔ Pb -0.13
2H+ + 2e ↔ H2 Eθ = -0.83
- H+ + e- ↔ 1/2H2 0.00
2CI- ↔ CI2 + 2e Eθ = -1.36 Cu2+ + 2e ↔ Cu Eθ = +0.34 Cu2+ + e- ↔ Cu+ +0.15
SO4 + 4H + 2e- ↔ H2SO3 + H2O +0.17
2- +
О
Discharged CI- ion CI2 Discharged Cu2+ ion to Cu metal Cu2+ + 2e- ↔ Cu +0.34
Cu2+ + 2e ↔ Cu Eθ = +0.34
Cu+ + e- ↔ Cu +0.52
2CI- ↔ CI2 + 2e Eθ = -1.36 I2 + 2e- ↔ 2I- +0.54
CI2 gas CuCI2 → Cu + O2 Eθ = -0.89V
copper Fe 3+
+ e- ↔ Fe2+ +0.77
Dilute CuCI2 – OH- discharged due to Eθ value Ag +
+ e- ↔ Ag +0.80
ОО
Conc CuCI2 – CI- discharged due to overpotential factor 1/2Br2 + e- ↔ Br- +1.07
Discharged of H+ and OH- ion need addition voltage O2 + 4H+ +4e- ↔ H2O +1.23
due to high activation energy for H2/O2 production
If Conc CI- is high ↑ – it is preferred !!!!!!
1/2CI2 + e- ↔ CI- +1.36
Eθ = -ve → supply +0.89 v to breakdown CuCI2 → Cu + O2 1/2F2 + e- ↔ F- +2.87

Discharge of ions
Electrolysis (Aqueous Salt) ↓ 2 Cation 2 Anion
- Molten/aqueous
CuCI2 aqueous Electrolytic Cell - Conc ion – conc/diluted
Cu2+ , CI- + H+ , OH- (from water) Oxidized sp ↔ Reduced sp Eθ/V

Li+
+ e- ↔ Li -3.04
- K+ + e- ↔ K -2.93
+ CI - Ca2+ + 2e- ↔ Ca -2.87
+
Cu 2+
- Na+ + e- ↔ Na -2.71
CI - Cu2+
+ OH- H+
-
Copper electrode + OH- H+ - Al3+ + 3e- ↔ AI -1.66
as anode Mn2+ + 2e- ↔ Mn -1.19
О
+ - 2H2O +2e- ↔ H2 + 2OH- -0.83
Oxidation ← Anode (+ve) ← Anion + Cation → Cathode (-ve) → Reduction

Fe2+ + 2e- ↔ Fe -0.45
Carbon electrode Copper electrode Ni + 2e-
2+
↔ Ni -0.26
Reduction Sn2+ + 2e- ↔ Sn -0.14
Eθ > more +ve easier gain e
OH- discharged Cu easier discharge Pb2+ + 2e- ↔ Pb -0.13
↓ ↓ 2H+ + 2e ↔ H2 Eθ = -0.83
2H2O +2e- ↔ H2 + 2OH Eθ = -0.83
- H+ + e- ↔ 1/2H 2 0.00
due to Eθ value due nature electrode
↓ ↓ Cu2+ + 2e ↔ Cu Eθ = +0.34 Cu2+ + e- ↔ Cu+ +0.15
4OH- ↔ 2H2O+O2 + 4e Cu → Cu2+ + 2e SO4 + 4H + 2e- ↔ H2SO3 + H2O +0.17
2- +
О
↓ ↓
O2 gas Cu electrode dissolve Discharged Cu2+ ion to Cu metal Cu2+ + 2e- ↔ Cu +0.34
e- e- e - Cu+ + e- ↔ Cu +0.52
e- I2 + 2e- ↔ 2I -
+0.54
e-
ee + Cu2+
Fe 3+
+ e- ↔ Fe 2+
+0.77
+ Cu2+ Cu2+ Ag +
+ e- ↔ Ag +0.80
2+ +
Cu2+ 1/2Br2 + e- ↔ Br- +1.07
Cu → 2e + Cu
Cu2+ Cu2+ O2 + 4H+ +4e- ↔ H2O +1.23
+ Cu2+ Cu2+
At Anode
Cu → 2e + Cu2+ Cr2O7 +14H +6e- ↔ 2Cr
2- + 3+
+1.33
+ Copper electrode oxidizes/dissolve
Cu → 2e + Cu 2+ Cu2+ Conc copper ions unchanged 1/2CI2 + e- ↔ CI- +1.36
Mass of Cu anode decreased
MnO4 + 8H+ + 5e- ↔ Mn2+ + 4H2O +1.51
-
copper Mass of Cu cathode increased
Cu → Cu2+ + 2e 1/2F2 + e- ↔ F- +2.87
electrode
Discharge of ions
Electrolysis (Aqueous Salt) ↓ 2 Anion
- Molten/aqueous
- Relative E values of ion Ag+/H+ NO3-/OH-
AgNO3 aqueous Electrolytic Cell - Conc ion – conc/diluted
Ag , NO
+
3
-
+ H , OH (from water)
+ -
Li+ + e- ↔ Li -3.04
K+ + e- ↔ K -2.93
- Ca2+ + 2e- ↔ Ca -2.87
+ NO3- Ag+
+ NO3- Ag+ - Na+ + e- ↔ Na -2.71
OH - H+ - Mg 2+ + 2e- ↔ Mg -2.37
+ Al3+ + 3e- ↔ AI -1.66
OH - H+
Copper electrode + - Mn2+ + 2e- ↔ Mn -1.19
О
as anode
+ - 2H2O +2e- ↔ H2 + 2OH- -0.83
Oxidation ← Anode (+ve) ← Anion + Cation → Cathode (-ve) → Reduction Fe2+ + 2e- ↔ Fe -0.45
Ni + 2e-
2+
↔ Ni -0.26
Carbon electrode Silver electrode Sn + 2e-
2+
↔ Sn -0.14
Reduction
OH- discharged Ag easier discharge
Eθ > more +ve easier gain e Pb2+ + 2e- ↔ Pb -0.13
↓ ↓ 2H+ + 2e ↔ H2 Eθ = -0.83 H+ + e- ↔ 1/2H 2 0.00
due to Eθ value due nature electrode 2H2O +2e- ↔ H2 + 2OH Eθ = -0.83
-
Cu + e-
2+
↔ Cu +
+0.15
↓ ↓ Ag+ + e ↔ Ag Eθ = +0.80
4OH- ↔ 2H2O+O2 + 4e Ag → Ag+ + e SO4 + 4H + 2e- ↔ H2SO3 + H2O +0.17
2- +
↓ ↓ Cu2+ + 2e- ↔ Cu +0.34

Ag electrode dissolve Discharged Ag+ ion to Ag
O2 gas 1/2O2 + H2O +2e- ↔ 2OH- +0.40
I2 + 2e- ↔ 2I- +0.54
e- e- e -
e-
О
e-
ee + - Ag+ + e- ↔ Ag +0.80
Ag +
1/2Br2 + e- ↔ Br- +1.07
+ Ag+ Ag+ -
Ag+ O2 + 4H+ +4e- ↔ H2O +1.23
Ag → e + Ag+ + - Cr2O7 +14H +6e- ↔ 2Cr3+
2- +
+1.33
Ag+ Ag+
+ Ag+ Ag+ - At Anode
Ag → e + Ag+ 1/2CI2 + e- ↔ CI- +1.36
+ -
Silver electrode oxidizes/dissolve
MnO4- + 8H+ + 5e- ↔ Mn2+ + 4H2O
Ag → e + Ag+ Ag+ Conc silver ions unchanged +1.51
Mass of Ag anode decreased S2 O82- + 2e ↔ SO42- +2.01
silver Mass of Ag cathode increased
Ag → Ag+ + e MnO4- + 8H+ + 5e- ↔ Mn2+ + 4H2O +1.51
electrode
Electrolyte Electrode Ions Cathode (-) Anode (+) Electrolytic cell
PbBr2 (molten) Carbon Pb / Br
2+ -
Pb + 2e → Pb
2+
2Br → Br2 + 2e
-
Pb Br2 Conversion electrical to chemical energy
CaCI2 (molten) Carbon Ca2+ /CI- Ca2+ +2e → Ca 2CI- → CI2 + 2e

Ca CI2
NaCI Carbon Na+/ CI – 2H+ + 2e → H2 4OH- ↔ 2H2O +O2 + 4e

H+/OH- H2 O2
Anode
+ - Cathode
NaCI Carbon Na+/ CI– 2H+ + 2e → H2 2CI- → CI2 + 2e

(conc) H+/OH- H2 CI2
NaI Carbon Na+/ I– 2H+ + 2e → H2 2I- → I2 + 2e

H+/OH- H2 I2
Anode (+ve) Cathode (-ve)
CuCI2 Carbon Cu2+/ CI– 2H+ + 2e → H2 4OH- ↔ 2H2O +O2 + 4e Oxidation Reduction
H+/OH- H2 O2
CuCI2 Carbon Cu2+/CI- 2H+ + 2e → H2 2CI- → CI2 + 2e

PANIC
(conc) H+/OH - H2 CI2
CuCI2 Copper Cu2+/CI- Cu2+ +2e → Cu Cu → Cu2+ + 2e Positive is Anode, Negative Is Cathode
Cu Cu
CuBr2 Carbon Cu2+ /Br- 2H+ + 2e → H2 2Br- → Br2 + 2e
H+/OH - H2 Br2
KI Carbon K+/I - 2H+ + 2e → H2 2I- → I2 + 2e Relative E Conc ion Nature of

H+/OH - H2 I2 values of ion conc/diluted electrode
AgNO3 Carbon Ag+/NO3- Ag+ + e → Ag 4OH- ↔ 2H2O +O2 + 4e
H+/OH - Ag O2 Ease Cation discharged Ease Anion discharged
K+ NO3–
AgNO3 Silver Ag+/NO3- Ag + e → Ag
+
Ag → Ag + e
+
Ca2+ SO42-
Na+ CI–
K2SO4 Carbon K+/SO42- 2H+ + 2e → H2 4OH- ↔ 2H2O +O2 + 4e Mg2+ Br–
H+/OH - H2 O2 Al 3+ I–
Zn2+ easier
OH–
H2SO4 Carbon H+/SO42- 2H+ + 2e → H2 4OH- ↔ 2H2O +O2 + 4e Fe2+
H+/OH - H2 O2 Sn2+
NO3– - diff to discharge
Pb2+
HCI Carbon H+/CI- 2H+ + 2e → H2 4OH- ↔ 2H2O +O2 + 4e H+ - ON for N is +5 (very high)
H+/OH - Cu2+ - Diff to lose e to get higher
H2 O2 easier
Ag+
+ - + -
Electric current
Current
Current – measured in Amperes or Coulombs per second
1A = 1 Coulomb charge pass through a point in 1 second = 1C/s
Flow electric charges (electron)
1 Coulomb charge (electron) = 6.28 x 10 18 electrons passing in 1 second
From High electric potential – low potential
Flow of
charges
1A = 6.28 x 1018 e
- 1Coulomb 6.28  1018.electron
1 second
Q  It 1A  
- 1sec ond 1. sec ond
- 1 electron
6.28 x 10 electron
18
- carry charge of – 1.6 x 10 - 19 C
- carry charge of - 1 C 1A
6.02 x 10 electron (1 Mol) - carry charge of - 96500C
23
1F
Faraday’s constant (F) – charge on 1 mol of electron 96500 C mol -1

Find amt charges pass through a sol if
Current is 2.ooA, time is 15 mins F  Le L = Avogadro constant
Q = Amt Charges/ C F  6.02  10 23  1.6  10 19 C
I = Current/ A
1F  96500Cmol 1
Q  It t = Time/ s
Q  2.00  15  60  1800C 1 Faraday – Quantity charge 96500C supply to 1 mol electron
Faraday's 1st Law Electrolysis Faraday's 2nd Law Electrolysis
Mass produce is directly proportional Mass produce is inversely proportional

to the quantity of electricity/charges ( C ) to
charges on ion
Factor affecting mass substance liberated
+1 +2 +3
Amt charges (Q) Q  It Ag+ + e ↔ Ag Cu2+ + 2e ↔ Cu AI3+ + 3e ↔ AI
1 mol e → 1 mol Ag 2 mol e → 1 mol Cu 3 mol e → 1 mol AI
Current Time
Charge on ion Pass 1 mol e 1 mol e → 1 mol Ag 1 mol e → 1/2 mol Cu 1 mol e → 1/3 mol AI
Electric current
Current
Current – measured in Amperes or Coulombs per second
Flow electric charges (electron) 1A = 1 Coulomb charge pass through a point in 1 second = 1C/s
From High electric potential – low potential 1 Coulomb charge (electron) = 6.28 x 10 18 electrons passing in 1 second
Flow of
charges
- 1A = 6.28 x 1018 e
Q  It 1Coulomb 6.28  10 .electron18 1 second
- 1A  
1sec ond 1. sec ond
- 1 electron - carry charge of – 1.6 x 10 - 19 C
6.28 x 10 electron
18
- carry charge of - 1 C 1A
6.02 x 10 23 electron (1 Mol) - carry charge of - 96500C 1F
Find amt charges pass through a sol if Faraday’s constant (F) – charge on 1 mol of electron 96500 C mol -1
Current is 2.ooA, time is 15 mins
F  Le L = Avogadro constant
Q = Amt Charges/ C
I = Current/ A F  6.02  10  1.6  10 19 C
23
Q  It t = Time/ s 1F  96500Cmol 1
Q  2.00  15  60  1800C 1 Faraday – Quantity charge 96500C supply to 1 mol electron
1 Copper (II) sulfate electrolyzed using current -- 0.150A for 5 hrs. Cal mass of Cu deposited
Mass deposited
(Cathode)
Find Current/I → Find Charge/Q → Find mol electron → Find Mass deposited
use Faraday’s constant
Cu2+ + 2e ↔ Cu
Q  It Cu
96500C  1.mol..e 2 mol e → 1 mol Cu
Q  0.150  5  60  60 0.028 mol e → 0.014 mol Cu
2700
Q  2700C 2700C   0.028.mol ..e Mass = mol x RAM Cu2+
96500 Cu2+
Mass = 0.014 x 63.5
Mass = 0.889 g
Electrolysis
2 Electrolysis Cr2(SO4)3 yield 0.86g of Cr after passing current for 12.5 min. Find amt of current used.
Mass deposited
Find Mass → Find mol electron → Find Charges/Q → Find current/I (Cathode)
Cr3+ + 3e ↔ Cr use Faraday’s constant Q  It

Cr
Q 4787
1 mol Cr → 3 mol e 1 mol e → 96500C I 
0.0165 mol Cr → 0.0495 mol e 0.0495 mol e → 96500 x 0.0495 t 12.5  60
= 4787 C
Mass = mol x RAM
I  6.4 A Cr3+
Cr3+
0.86 = mol x 52.00
mol = 0.0165
3 Find time /hrs need to produce 25g of Cr from Cr2(SO4)3 with current of 1.1A Mass deposited
(Cathode)
Find Mass → Find mol electron → Find Charges/Q →Find current/I
Cr
Cr3+ + 3e ↔ Cr use Faraday’s constant Q  It
1 mol Cr → 3 mol e 1 mol e → 96500C
Q 138960
0.48 mol Cr → 1.44 mol e 1.44 mol e → 96500 x 1.44 t  Cr3+
= 138960 C I 1. 1 Cr3+
Mass = mol x RAM
25 = mol x 52.00 t  35.1
mol = 0.48
4 Find vol of H2 gas collect at cathode when aq sol Na2SO4 electrolyzed for 2.00 hours with a 10A.
H2 O2
Find Current/I → Find Charge/Q → Find mol electron → Find Vol

use Faraday’s constant 2H+ + 2e ↔ H2
Q  It 96500C  1.mol..e
2 mol e → 1 mol H2
0.746 mol e → 0.373 mol H2
Q  2.00  2  60  60 72000
72000C   0.746.mol..e
Q  72000C 96500
Vol = 8.35 dm3
Faraday's 2nd Law Electrolysis
Faraday's 1st Law Electrolysis
Mass produce is inversely proportional to charges on ion
Mass produce is directly proportional
to the quantity of electricity/charges ( C )
+1 +2 +3
Factor affecting mass substance liberated Ag+ + e ↔ Ag Cu2+ + 2e ↔ Cu AI3+ + 3e ↔ AI
Q  It
Amt charges (Q)
Current Time 1 mol e → 1 mol Ag 1 mol e → 1/2 mol Cu 1 mol e → 1/3 mol AI
Charge on ion
Pass 1 mol electron across
O2
H2
-
Ag+
- Ag+ - + - + - +
Ag+ + + AI3+ +
- Ag+
- Cu 2+
- AI3+
Cu2+
AgNO3, H3SO4 connect in series. Same amt current used AgNO3,CuSO4, AICI3 connect in series. Same amt current used.
Cal vol H2,O2 when 10.8 g Ag deposited. Cal mass Cu and Al when 10.8 g Ag deposited.
Ag+ + e ↔ Ag 2H+ + 2e ↔ H2 Ag+ + e ↔ Ag Cu2+ + 2e ↔ Cu AI3+ + 3e ↔ AI

1 mol Ag → 1 mol e 2 mol e → 1 mol H2
1 mol Ag → 1 mol e 2 mol e → 1 mol Cu 3 mol e → 1 mol AI
0.1 mol Ag → 0.1 mol e 0.1 mol e → 0.05 mol H2 0.1 mol Ag →0.1 mol e 0.1 mol e → 0.05 mol Cu 0.1 mol e → 0.03 mol AI
2.24 dm3
Mass = mol x RAM
4OH- ↔ 2H2O +O2 + 4e 10.8 = mol x 108
4 mol e → 1 mol O2 mol = 0.1 Mass Cu = 0.05 mol Mass AI = 0.03 mol
0.1 mol e → 0.025 mol O2
Mass = mol x RAM
10.8 = mol x 108
mol = 0.1 0.56 dm3
Mass produce is directly proportional Mass produce is inversely proportional to charges on ion
to the quantity of electricity/charges ( C )
+1 +2 +3
Factor affecting mass substance liberated Ag+ + e ↔ Ag Cu2+ + 2e ↔ Cu AI3+ + 3e ↔ AI
Q  It
Amt charges (Q)
Current Time 1 mol e → 1 mol Ag 1 mol e → 1/2 mol Cu 1 mol e → 1/3 mol AI
Charge on ion
Pass 1 mol electron across
Application of Electrolysis
- Prevent corrosion
Extraction reactive metal Electroplating - Improve appearance
Copper, chromium, silver
Aluminium Sodium
AI2O3 NaCI + ve
+ + +
+ + + 2CI- -2e → CI2
- - Anode (+ve) Cathode (-ve)
- + + + Object
- + + +
Plating metal
- -
- - Purification of metal
-
-
-
-
Al3+ + 3e → Al Na+ + e → Na - ve
- ve Aluminium Sodium
electrode metal metal
Anode (+ve) + - Cathode (-ve)
Impure Cu metal + Cu2+ - Pure Cu metal
Mass decrease Cu2+ Mass increase
Cu2+
Cu ↔ Cu2+ + 2e Cu2+ + 2e ↔ Cu
Electrolytic cell
Mass produce is directly proportional Mass produce is inversely proportional
to the quantity of electricity/charges ( C ) to charges on ion
Factor affecting mass substance liberated +1 +2

Ag+ + e ↔ Ag Cu2+ + 2e ↔ Cu + -
Amt charges (Q) Q  It 1 mol e → 1 mol Ag 2 mol e → 1 mol Cu
Current Time
1 mol e → 1 mol Ag 1 mol e → 1/2 mol Cu
Charge on ion
Anode (+ve) Cathode (-ve)
Pass 1 mol electron across Oxidation Reduction
PANIC
Positive is Anode, Negative Is Cathode

Relative E Conc ion Nature of

values of ion conc/diluted electrode
Excellent Silver crystal formation Electrolysis of water
Ease Cation discharged Ease Anion discharged
K+ NO3–
Ca2+ SO42-
Na+ CI–
Mg2+ Br–
Al 3+ I–
Zn2+ easier
OH–
Fe2+
Sn2+
NO3– - diff to discharge
Pb2+
Galvanizing Iron with Zinc H+ - ON for N is +5 (very high)
Electrolysis of KI - Diff to lose e to get higher
Cu2+
easier
Ag+
Acknowledgements
Thanks to source of pictures and video used in this presentation
Thanks to Creative Commons for excellent contribution on licenses

http://creativecommons.org/licenses/
http://spmchemistry.onlinetuition.com.my/2013/10/electrolytic-cell.html
http://www.chemguide.co.uk/physical/redoxeqia/introduction.html
http://educationia.tk/reduction-potential-table
http://2012books.lardbucket.org/books/principles-of-general-chemistry-v1.0/s23-
electrochemistry.html
Prepared by Lawrence Kok
Check out more video tutorials from my site and hope you enjoy this tutorial
http://lawrencekok.blogspot.com

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Tutorial on Electrolysis and Faraday’s Law.

Voltaic cell Electrolytic cell

Types voltaic cell

Primary cell (Non rechargeable)

Daniell cell Dry cell Alkaline cell Nickel cadmium cell

NH4CI and ZnCI2 MnO2 and KOH

Voltaic cell Electrolytic cell

Conversion chemical to electrical energy Vs Conversion electrical to chemical energy

Spontaneous rxn Non Spontaneous rxn

Voltaic Cell Electrolytic Cell

Zn/Cu Voltaic Cell PbBr2 molten Electrolytic Cell

Conversion chemical to electrical energy Vs Conversion electrical to chemical energy

Spontaneous rxn Non Spontaneous rxn

Zn → Zn 2+ + 2e Cu2+ + 2e → Cu 2Br- → Br2 + 2e Pb2+ + 2e → Pb

Zn + Cu2+ → Zn2+ + Cu PbBr2 → Pb + Br2

Zn/Cu Voltaic Cell PbBr2 molten Electrolytic Cell

Conversion chemical to electrical energy Vs Conversion electrical to chemical energy

Spontaneous rxn Non Spontaneous rxn

Zn 2+ + 2e ↔ Zn Eθ = -0.76V Pb2+ + 2e ↔ Pb Eθ = -0.13V

Zn + Cu2+ → Zn2+ + Cu Eθ = ????? PbBr2 → Pb + Br2 Eθ = ???

Zn ↔ Zn2+ + 2e Eθ = +0.76 2Br - ↔ Br2+ 2e Eθ = -1.07

Conversion chemical to electrical energy Conversion electrical to chemical energy

Conversion electrical to chemical energy Cr2O72-+14H+ +6e- ↔ 2Cr3+ + 7H2O +1.33

Eθ =-ve → supply +1.20v to breakdown PbBr2 → Pb + Br2 1/2F2 + e- ↔ F- +2.87

Ca2+ + 2e ↔ Ca E θ = -2.87 1/2O2 + H2O +2e- ↔ 2OH -

NaCI aqueous Electrolytic Cell

Oxidation ← Anode (+ve) ← Anion

Eθ =-ve → supply +2.06v to breakdown NaCI → H2 + O2 1/2F2 + e- ↔ F- +2.87

Oxidation ← Anode (+ve) ← Anion

Discharged I- ion I2 Discharged H+ ion to H2 gas Cu2+ + 2e- ↔ Cu +0.34

Oxidized sp ↔ Reduced sp Eθ/V

Oxidation ← Anode (+ve) ← Anion

Eθ = -ve → supply +0.89 v to breakdown CuCI2 → Cu + O2 1/2F2 + e- ↔ F- +2.87

Oxidation ← Anode (+ve) ← Anion

Eθ = -ve → supply +0.73 v to breakdown CuBr2 → Cu + Br2 1/2F2 + e- ↔ F- +2.87

Oxidation ← Anode (+ve) ← Anion

Discharged I- ion I2 Discharged H+ ion to H2 Cu2+ + 2e- ↔ Cu +0.34

Eθ = -ve → supply +1.37 v to breakdown KI→ H2 + I2 1/2F2 + e- ↔ F- +2.87

Oxidation ← Anode (+ve) ← Anion

Cu2+ + 2e- ↔ Cu +0.34

Conversion electrical to chemical energy 1/2CI2 + e- ↔ CI- +1.36

S2 O82- + 2e ↔ SO42- +2.01

AgNO3 aqueous Electrolytic Cell

Oxidation ← Anode (+ve) ← Anion

Cu2+ + 2e- ↔ Cu +0.34

Conversion electrical to chemical energy 1/2CI2 + e- ↔ CI- +1.36

S2 O82- + 2e ↔ SO42- +2.01

Oxidation ← Anode (+ve) ← Anion

Cu2+ + 2e- ↔ Cu +0.34

Eθ =-ve → supply +2.06v to breakdown H2SO4 → H2 + O2 S2 O82- + 2e ↔ SO42- +2.01

Oxidized sp ↔ Reduced sp Eθ/V

Oxidation ← Anode (+ve) ← Anion

Eθ =-ve → supply +2.19v to breakdown NaCI → H2 + CI2 + NaOH 1/2F2 + e- ↔ F- +2.87

Oxidized sp ↔ Reduced sp Eθ/V

Oxidation ← Anode (+ve) ← Anion

Eθ = -ve → supply +0.89 v to breakdown CuCI2 → Cu + O2 1/2F2 + e- ↔ F- +2.87

Cu2+ , CI- + H+ , OH- (from water) Oxidized sp ↔ Reduced sp Eθ/V

Oxidation ← Anode (+ve) ← Anion + Cation → Cathode (-ve) → Reduction

↓ ↓ Cu2+ + 2e- ↔ Cu +0.34