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Redox Reactions and
Electrochemistry
By Aktr
book 2
Loss of e
Gain of e
Reducing Agent
Oxidising agent
Oxidation
Reduction
Electrochemical cell occur both
SnCl2(aq) + 2FeCl3(aq) → SnCl4(aq) + 2FeCl2(aq)
CuO(s) + H2(g) → Cu(s) + H2O(l)
Example
+2 +3 +4 +2
+1
0
0
+2
Conductance in electrolytic
solution
Also act as a conductor
Conductance in electrolytic
solutions
Metallic conductor depend upon
• Nature and structure of metal.
• No. of valence electron per atom.
• Temperature of the sample.
conductivity aqueous solution
depend upon
• Nature of electrolyte.
• Size of ion.
• Solvation of ion.
• Concentration of electrolytic.
• Temperature.
One cell const. and resistivity
Known then we can find value
Easily.
Molar conductivity
Electrochemical cell
Chemical to electrical Electrical to chemical
2. Voltaic or Galvanic cells-
An electrochemical cell in which a spontaneous
reaction produces electricity.
Eg. Dry cell, lead storage cell etc.
1. Electrolytic cell-
An electrochemical cell in which a non spontaneous
reaction is forced to occur by passing a direct
current from an external source into the solution.
Eg. Refining metal(purify), electroplating &
production of many chemical substance.
Gets Smaller -> <- Gets Larger
Cell Notation
1. Anode
2. Salt Bridge
3. Cathode
Anode | Salt Bridge | Cathode
| : symbol is used whenever there is a different phase
19.2
Cell Notation
Zn (s) + Cu2+
(aq) Cu (s) + Zn2+
(aq)
[Cu2+
] = 1 M & [Zn2+
] = 1 M
Zn (s) | Zn2+
(1 M) || Cu2+
(1 M) | Cu (s)
anode cathode
Zn (s)| Zn+2
(aq, 1M)| K(NO3) (saturated)|Cu+2
(aq, 1M)|Cu(s)
anode cathode
Salt bridge
More detail..
K(NO3)
Zn (s) + 2 H+
(aq) -> H2 (g) + Zn+2
(aq)
Zn(s)| Zn+2
|KNO3|H+
(aq)|H2(g)|Pt
Electrochemical Cells
19.2
The difference in electrical
potential between the anode and
cathode is called:
• cell voltage
• electromotive force (emf)
• cell potential
0
0
0
reduction
oxidation
Cell E
E
E +
=
UNITS: Volts Volt (V) = Joule (J)
Coulomb, C
Standard Electrode Potentials
19.3
Standard reduction potential (E0
) is the voltage associated with a
reduction reaction at an electrode when all solutes are 1 M and
all gases are at 1 atm.
Ε0
= 0 V
Standard hydrogen electrode (SHE)
2e−
+ 2Η+
(1 Μ) Η2 (1 atm)
Reduction Reaction
Determining if Redox Reaction is Spontaneous
• + E°CELL ; spontaneous
reaction
• E°CELL = 0; equilibrium
• - E°CELL; nonspontaneous
reaction
More positive E°CELL ;
stronger oxidizing agent or
more likely to be reduced
Relating E0
Cell to ∆G0
e
ch
work
ECell
arg
=
Units
work, Joule
charge, Coulomb
Ecell; Volts
charge = nF
Faraday, F; charge on 1 mole e-
F = 96485 C/mole
work = (charge)Ecell = -nFEcell
∆G = work (maximum)
∆G = -nFEcell
Relating Εο
CELL to the
Equilibrium Constant, K
∆G0
= -RT ln K
∆G0
= -nFE0
cell
-RT ln K = -nFE0
cell
K
nF
RT
ECell ln
0
=
( )
0257
.
0
96485
298
31
.
8
=






=
mole
C
K
molK
J
F
RT
K
n
K
n
ECell log
0592
.
0
ln
0257
.
0
0
=
=
Effect of Concentration on Cell Potential
∆G =∆G0
+ RTlnQ
∆G0
= -nFE0
cell
-nFEcell= -nFE0
cell +RTln Q
Ecell= E0
cell - RTln Q
nF
Ecell= E0
cell - 0.0257ln Q
n
Ecell= E0
cell – 0.0592log Q
n
Corrosion – Deterioration of Metals
by Electrochemical Process
Corrosion – Deterioration of Metals
by Electrochemical Process
Corrosion – Deterioration of Metals
by Electrochemical Process
Cathodic Protection
Abbreviated Standard Reduction
Potential Table
Batteries
19.6
Leclanché cell
Dry cell
Zn (s) Zn2+
(aq) + 2e-
Anode:
Cathode: 2NH4
+
(aq) + 2MnO2 (s) + 2e-
Mn2O3 (s) + 2NH3 (aq) + H2O (l)
Zn (s) + 2NH4 (aq) + 2MnO2 (s) Zn2+
(aq) + 2NH3 (aq) + H2O (l) + Mn2O3 (s)
Batteries
Zn(Hg) + 2OH-
(aq) ZnO (s) + H2O (l) + 2e-
Anode:
Cathode: HgO (s) + H2O (l) + 2e-
Hg (l) + 2OH-
(aq)
Zn(Hg) + HgO (s) ZnO (s) + Hg (l)
Mercury Battery
19.6
Batteries
19.6
Anode:
Cathode:
Lead storage
battery
PbO2 (s) + 4H+
(aq) + SO4
2-
(aq) + 2e-
PbSO4 (s) + 2H2O (l)
Pb (s) + SO4
2-
(aq) PbSO4 (s) + 2e-
Pb (s) + PbO2 (s) + 4H+
(aq) + 2SO4
2-
(aq) 2PbSO4 (s) + 2H2O (l)
Fuel Cell vs. Battery
• Battery; Energy storage device
– Reactant chemicals already in device
– Once Chemicals used up; discard (unless rechargeable)
• Fuel Cell; Energy conversion device
– Won’t work unless reactants supplied
– Reactants continuously supplied; products continuously
removed
Fuel Cell
A fuel cell is an
electrochemical cell
that requires a
continuous supply of
reactants to keep
functioning
Anode:
Cathode: O2 (g) + 2H2O (l) + 4e-
4OH-
(aq)
2H2 (g) + 4OH-
(aq) 4H2O (l) + 4e-
2H2 (g) + O2 (g) 2H2O (l)
Types of Electrochemical Cells
• Voltaic/Galvanic Cell; Energy released
from spontaneous redox reaction can be
transformed into electrical energy.
• Electrolytic Cell; Electrical energy is used
to drive a nonspontaneous redox reaction.
Faraday’s Constant
Redox Eqn
Molar Mass
Charge =(Current)(Time)

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electrochemistry12.pdf

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  • 4. Loss of e Gain of e Reducing Agent Oxidising agent
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  • 11. SnCl2(aq) + 2FeCl3(aq) → SnCl4(aq) + 2FeCl2(aq) CuO(s) + H2(g) → Cu(s) + H2O(l) Example +2 +3 +4 +2 +1 0 0 +2
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  • 27. Also act as a conductor
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  • 36. Metallic conductor depend upon • Nature and structure of metal. • No. of valence electron per atom. • Temperature of the sample.
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  • 40. conductivity aqueous solution depend upon • Nature of electrolyte. • Size of ion. • Solvation of ion. • Concentration of electrolytic. • Temperature.
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  • 48. One cell const. and resistivity Known then we can find value Easily.
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  • 65. Chemical to electrical Electrical to chemical
  • 66. 2. Voltaic or Galvanic cells- An electrochemical cell in which a spontaneous reaction produces electricity. Eg. Dry cell, lead storage cell etc.
  • 67. 1. Electrolytic cell- An electrochemical cell in which a non spontaneous reaction is forced to occur by passing a direct current from an external source into the solution. Eg. Refining metal(purify), electroplating & production of many chemical substance.
  • 68. Gets Smaller -> <- Gets Larger
  • 69. Cell Notation 1. Anode 2. Salt Bridge 3. Cathode Anode | Salt Bridge | Cathode | : symbol is used whenever there is a different phase
  • 70. 19.2 Cell Notation Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq) [Cu2+ ] = 1 M & [Zn2+ ] = 1 M Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s) anode cathode Zn (s)| Zn+2 (aq, 1M)| K(NO3) (saturated)|Cu+2 (aq, 1M)|Cu(s) anode cathode Salt bridge More detail..
  • 71. K(NO3) Zn (s) + 2 H+ (aq) -> H2 (g) + Zn+2 (aq) Zn(s)| Zn+2 |KNO3|H+ (aq)|H2(g)|Pt
  • 72. Electrochemical Cells 19.2 The difference in electrical potential between the anode and cathode is called: • cell voltage • electromotive force (emf) • cell potential 0 0 0 reduction oxidation Cell E E E + = UNITS: Volts Volt (V) = Joule (J) Coulomb, C
  • 73. Standard Electrode Potentials 19.3 Standard reduction potential (E0 ) is the voltage associated with a reduction reaction at an electrode when all solutes are 1 M and all gases are at 1 atm. Ε0 = 0 V Standard hydrogen electrode (SHE) 2e− + 2Η+ (1 Μ) Η2 (1 atm) Reduction Reaction
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  • 75. Determining if Redox Reaction is Spontaneous • + E°CELL ; spontaneous reaction • E°CELL = 0; equilibrium • - E°CELL; nonspontaneous reaction More positive E°CELL ; stronger oxidizing agent or more likely to be reduced
  • 76. Relating E0 Cell to ∆G0 e ch work ECell arg = Units work, Joule charge, Coulomb Ecell; Volts charge = nF Faraday, F; charge on 1 mole e- F = 96485 C/mole work = (charge)Ecell = -nFEcell ∆G = work (maximum) ∆G = -nFEcell
  • 77. Relating Εο CELL to the Equilibrium Constant, K ∆G0 = -RT ln K ∆G0 = -nFE0 cell -RT ln K = -nFE0 cell K nF RT ECell ln 0 = ( ) 0257 . 0 96485 298 31 . 8 =       = mole C K molK J F RT K n K n ECell log 0592 . 0 ln 0257 . 0 0 = =
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  • 80. Effect of Concentration on Cell Potential ∆G =∆G0 + RTlnQ ∆G0 = -nFE0 cell -nFEcell= -nFE0 cell +RTln Q Ecell= E0 cell - RTln Q nF Ecell= E0 cell - 0.0257ln Q n Ecell= E0 cell – 0.0592log Q n
  • 81. Corrosion – Deterioration of Metals by Electrochemical Process
  • 82. Corrosion – Deterioration of Metals by Electrochemical Process
  • 83. Corrosion – Deterioration of Metals by Electrochemical Process
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  • 88. Batteries 19.6 Leclanché cell Dry cell Zn (s) Zn2+ (aq) + 2e- Anode: Cathode: 2NH4 + (aq) + 2MnO2 (s) + 2e- Mn2O3 (s) + 2NH3 (aq) + H2O (l) Zn (s) + 2NH4 (aq) + 2MnO2 (s) Zn2+ (aq) + 2NH3 (aq) + H2O (l) + Mn2O3 (s)
  • 89. Batteries Zn(Hg) + 2OH- (aq) ZnO (s) + H2O (l) + 2e- Anode: Cathode: HgO (s) + H2O (l) + 2e- Hg (l) + 2OH- (aq) Zn(Hg) + HgO (s) ZnO (s) + Hg (l) Mercury Battery 19.6
  • 90. Batteries 19.6 Anode: Cathode: Lead storage battery PbO2 (s) + 4H+ (aq) + SO4 2- (aq) + 2e- PbSO4 (s) + 2H2O (l) Pb (s) + SO4 2- (aq) PbSO4 (s) + 2e- Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO4 2- (aq) 2PbSO4 (s) + 2H2O (l)
  • 91. Fuel Cell vs. Battery • Battery; Energy storage device – Reactant chemicals already in device – Once Chemicals used up; discard (unless rechargeable) • Fuel Cell; Energy conversion device – Won’t work unless reactants supplied – Reactants continuously supplied; products continuously removed
  • 92. Fuel Cell A fuel cell is an electrochemical cell that requires a continuous supply of reactants to keep functioning Anode: Cathode: O2 (g) + 2H2O (l) + 4e- 4OH- (aq) 2H2 (g) + 4OH- (aq) 4H2O (l) + 4e- 2H2 (g) + O2 (g) 2H2O (l)
  • 93. Types of Electrochemical Cells • Voltaic/Galvanic Cell; Energy released from spontaneous redox reaction can be transformed into electrical energy. • Electrolytic Cell; Electrical energy is used to drive a nonspontaneous redox reaction.
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  • 95. Faraday’s Constant Redox Eqn Molar Mass Charge =(Current)(Time)