CHEM 160 General Chemistry II Lecture Presentation Electrochemistry

Chapter 20

Electrochemistry
Electrochemistry

deals with interconversion between chemical and electrical energy

Electrochemistry
Electrochemistry

deals with the interconversion between chemical and electrical energy involves redox reactions

Electrochemistry
Electrochemistry

deals with interconversion between chemical and electrical energy involves redox reactions
electron transfer reactions

Oh No! Theyre back!

Redox reactions (quick review)

Oxidation Reduction Reducing agent Oxidizing agent

Redox reactions (quick review)

Oxidation

loss of electrons
Reduction Reducing agent Oxidizing agent

Redox reactions (quick review)

Oxidation

loss of electrons
Reduction

gain of electrons
Reducing agent Oxidizing agent

Redox reactions (quick review)

Oxidation

loss of electrons
Reduction

gain of electrons
Reducing agent

donates the electrons and is oxidized

Oxidizing agent

Redox reactions (quick review)

Oxidation

loss of electrons
Reduction

gain of electrons
Reducing agent

donates the electrons and is oxidized

Oxidizing agent

accepts electrons and is reduced

Redox Reactions
Direct redox reaction

Redox Reactions
Direct redox reaction

Oxidizing and reducing agents are mixed together

Direct Redox Reaction

Zn rod

CuSO4(aq) (Cu2+)

Direct Redox Reaction

Zn rod CuSO4(aq) (Cu2+) Deposit of Cu metal forms

Redox Reactions
Direct redox reaction

Oxidizing and reducing agents are mixed together

Indirect redox reaction

Oxidizing and reducing agents are separated but connected electrically

Example
Zn and Cu2+ can be reacted indirectly

Basis for electrochemistry

Electrochemical cell

Electrochemical Cells

Electrochemical Cells
Voltaic Cell

cell in which a spontaneous redox reaction generates electricity chemical energy electrical energy

Electrochemical Cells

Electrochemical Cells
Voltaic Cell

Electrochemical Cells
Electrolytic Cell

electrochemical cell in which an electric current drives a nonspontaneous redox reaction electrical energy chemical energy

Cell Potential

Cell Potential
Cell Potential (electromotive force), Ecell (V)

electrical potential difference between the two electrodes or half-cells

Depends on specific half-reactions, concentrations, and temperature Under standard state conditions ([solutes] = 1 M, Psolutes = 1 atm), emf = standard cell potential, Ecell 1 V = 1 J/C

driving force of the redox reaction

Cell Potential

high electrical potential

low electrical potential

Cell Potential
Ecell = Ecathode - Eanode = Eredn - Eox Ecell = Ecathode - Eanode = Eredn - Eox
(Ecathode and Eanode are reduction potentials by definition.)

Cell Potential
Ecell = Ecathode - Eanode = Eredn - Eox Ecell can be measured
Absolute Ecathode and Eanode values cannot

Reference electrode has arbitrarily assigned E used to measure relative Ecathode and Eanode for halfcell reactions Standard hydrogen electrode (S.H.E.) conventional reference electrode

Standard Hydrogen Electrode

E = 0 V (by

definition; arbitrarily selected) 2H+ + 2e- H2

Example 1
A voltaic cell is made by connecting a standard Cu/Cu2+ electrode to a S.H.E. The cell potential is 0.34 V. The Cu electrode is the cathode. What is the standard reduction potential of the Cu/Cu2+ electrode?

Example 2
A voltaic cell is made by connecting a standard Zn/Zn2+ electrode to a S.H.E. The cell potential is 0.76 V. The Zn electrode is the anode of the cell. What is the standard reduction potential of the Zn/Zn2+ electrode?

Standard Electrode Potentials

Standard Reduction Potentials, E

Ecell measured relative to S.H.E. (0 V)

electrode of interest = cathode

If E < 0 V:
Oxidizing agent is harder to reduce than H+

If E > 0 V:
Oxidizing agent is easier to reduce than H+

Standard Reduction Potentials

Reduction Half-Reaction
F2(g) + 2e- 2F-(aq) Au3+(aq) + 3e- Au(s) Cl2(g) + 2 e- 2Cl-(aq) Cr2O72-(aq) + 14H+(aq) + 6e- 2Cr3+(aq) + 7H2O O2(g) + 4H+ + 4e- 2H2O(l) Ag+(aq) + e- Ag(s) Fe3+(aq) + e- Fe2+(aq) Cu2+(aq) + 2e- Cu(s) Sn4+(aq) + 2e- Sn2+(aq)

E(V)
2.87 1.50 1.36 1.33 1.23 0.80 0.77 0.34 0.15

2H+(aq) + 2e- H2(g)

Sn2+(aq) + 2e- Sn(s) Ni2+(aq) + 2e- Ni(s) Fe2+(aq) + 2e- Fe(s) Zn2+(aq) + 2e- Zn(s) Al3+(aq) + 3e- Al(s) Mg2+(aq) + 2e- Mg(s) Li+(aq) + e- Li(s)

0.00
-0.14 -0.23 -0.44 -0.76 -1.66 -2.37 -3.04

Uses of Standard Reduction Potentials

Compare strengths of reducing/oxidizing agents.

the more - E, stronger the red. agent the more + E, stronger the ox. agent

Standard Reduction Potentials

Reduction Half-Reaction
F2(g) + 2e- 2F-(aq) Au3+(aq) + 3e- Au(s) Cl2(g) + 2 e- 2Cl-(aq)

E(V)
2.87 1.50 1.36 1.33 1.23 0.80 0.77 0.34 0.15

Red. agent strength increases

Ox. agent strength increases

Cr2O72-(aq) + 14H+(aq) + 6e- 2Cr3+(aq) + 7H2O O2(g) + 4H+ + 4e- 2H2O(l) Ag+(aq) + e- Ag(s) Fe3+(aq) + e- Fe2+(aq) Cu2+(aq) + 2e- Cu(s) Sn4+(aq) + 2e- Sn2+(aq)

2H+(aq) + 2e- H2(g)

Sn2+(aq) + 2e- Sn(s) Ni2+(aq) + 2e- Ni(s) Fe2+(aq) + 2e- Fe(s) Zn2+(aq) + 2e- Zn(s) Al3+(aq) + 3e- Al(s) Mg2+(aq) + 2e- Mg(s) Li+(aq) + e- Li(s)

0.00
-0.14 -0.23 -0.44 -0.76 -1.66 -2.37 -3.04

Uses of Standard Reduction Potentials

Determine if oxidizing and reducing agent react

spontaneously
diagonal rule

ox. agent

red. agent

Uses of Standard Reduction Potentials

Determine if oxidizing and reducing agent react

spontaneously
more +

Cathode (reduction)
Anode (oxidation) more -

Standard Reduction Potentials

Reduction Half-Reaction
F2(g) + 2e- 2F-(aq) Au3+(aq) + 3e- Au(s) Cl2(g) + 2 e- 2Cl-(aq) Cr2O72-(aq) + 14H+(aq) + 6e- 2Cr3+(aq) + 7H2O O2(g) + 4H+ + 4e- 2H2O(l) Ag+(aq) + e- Ag(s) Fe3+(aq) + e- Fe2+(aq) Cu2+(aq) + 2e- Cu(s) Sn4+(aq) + 2e- Sn2+(aq)

E(V)
2.87 1.50 1.36 1.33 1.23 0.80 0.77 0.34 0.15

2H+(aq) + 2e- H2(g)

Sn2+(aq) + 2e- Sn(s) Ni2+(aq) + 2e- Ni(s) Fe2+(aq) + 2e- Fe(s) Zn2+(aq) + 2e- Zn(s) Al3+(aq) + 3e- Al(s) Mg2+(aq) + 2e- Mg(s) Li+(aq) + e- Li(s)

0.00
-0.14 -0.23 -0.44 -0.76 -1.66 -2.37 -3.04

Uses of Standard Reduction Potentials

Calculate Ecell

Ecell = Ecathode - Eanode

Greater Ecell, greater the driving force

Ecell > 0 : spontaneous redox reactions Ecell < 0 : nonspontaeous redox reactions

Example 3
A voltaic cell consists of a Ag electrode in 1.0 M AgNO3 and a Cu electrode in 1 M Cu(NO3)2. Calculate Ecell for the spontaneous cell reaction at 25C.

Standard Reduction Potentials

Reduction Half-Reaction
F2(g) + 2e- 2F-(aq) Au3+(aq) + 3e- Au(s) Cl2(g) + 2 e- 2Cl-(aq) Cr2O72-(aq) + 14H+(aq) + 6e- 2Cr3+(aq) + 7H2O O2(g) + 4H+ + 4e- 2H2O(l) Ag+(aq) + e- Ag(s) Fe3+(aq) + e- Fe2+(aq) Cu2+(aq) + 2e- Cu(s) Sn4+(aq) + 2e- Sn2+(aq)

E(V)
2.87 1.50 1.36 1.33 1.23 0.80 0.77 0.34 0.15

2H+(aq) + 2e- H2(g)

Sn2+(aq) + 2e- Sn(s) Ni2+(aq) + 2e- Ni(s) Fe2+(aq) + 2e- Fe(s) Zn2+(aq) + 2e- Zn(s) Al3+(aq) + 3e- Al(s) Mg2+(aq) + 2e- Mg(s) Li+(aq) + e- Li(s)

0.00
-0.14 -0.23 -0.44 -0.76 -1.66 -2.37 -3.04

Example 4
A voltaic cell consists of a Ni electrode in 1.0 M Ni(NO3)2 and an Fe electrode in 1 M Fe(NO3)2. Calculate Ecell for the spontaneous cell reaction at 25C.

Standard Reduction Potentials

Reduction Half-Reaction
F2(g) + 2e- 2F-(aq) Au3+(aq) + 3e- Au(s) Cl2(g) + 2 e- 2Cl-(aq) Cr2O72-(aq) + 14H+(aq) + 6e- 2Cr3+(aq) + 7H2O O2(g) + 4H+ + 4e- 2H2O(l) Ag+(aq) + e- Ag(s) Fe3+(aq) + e- Fe2+(aq) Cu2+(aq) + 2e- Cu(s) Sn4+(aq) + 2e- Sn2+(aq)

E(V)
2.87 1.50 1.36 1.33 1.23 0.80 0.77 0.34 0.15

2H+(aq) + 2e- H2(g)

Sn2+(aq) + 2e- Sn(s) Ni2+(aq) + 2e- Ni(s) Fe2+(aq) + 2e- Fe(s) Zn2+(aq) + 2e- Zn(s) Al3+(aq) + 3e- Al(s) Mg2+(aq) + 2e- Mg(s) Li+(aq) + e- Li(s)

0.00
-0.14 -0.23 -0.44 -0.76 -1.66 -2.37 -3.04

Cell Potential
Is there a relationship between Ecell and DG for a

redox reaction?

Cell Potential
Relationship between Ecell and DG:

DG = -nFEcell
F = Faraday constant = 96500 C/mol e-s, n = # e-s transferred redox rxn.

Cell Potential
Relationship between Ecell and DG:

DG = -nFEcell
F = Faraday constant = 96500 C/mol e-s, n = # e-s transferred redox rxn. 1 J = CV DG < 0, Ecell > 0 = spontaneous

Equilibrium Constants from Ecell

Relationship between Ecell and DG:

DG = -nFEcell
F = Faraday constant = 96500 C/mol e-s, n = # e-s transferred redox rxn 1 J = CV DG < 0, Ecell > 0 = spontaneous

Under standard state conditions:

DG = -nFEcell

Equilibrium Constants from Ecell

Relationship between Ecell and DG:

DG = -nFEcell
F = Faraday constant = 96500 C/mol e-s, n = # e-s transferred redox rxn 1 J = CV DG < 0, Ecell > 0 = spontaneous

Under standard state conditions:

DG = -nFEcell

Equilibrium Constants from Ecell

Relationship between Ecell and DG: DG = -nFEcell
F = Faraday constant = 96500 C/mol e-s, n = # e-s transferred redox rxn 1 J = CV DG < 0, Ecell > 0 = spontaneous

Under standard state conditions: DG = -nFEcell

and
DG = -RTlnK

so
-nFEcell = -RTlnK

Calorimetric Data

DH DS
Composition Data Electrochemical Data

DG

Ecell
Equilibrium constants

Example 5
Calculate Ecell, DG, and K for the voltaic cell that uses the reaction between Ag and Cl2 under standard state conditions at 25C.

The Nernst Equation

DG depends on concentrations

DG = DG + RTlnQ

and DG = -nFEcell and DG = -nFEcell thus -nFEcell = -nFEcell + RTlnQ or Ecell = Ecell - (RT/nF)lnQ (Nernst eqn.)

The Nernst Equation

Ecell = Ecell - (RT/nF)lnQ (Nernst eqn.)

At 298 K (25C), RT/F = 0.0257 V

so Ecell = Ecell - (0.0257/n)lnQ or Ecell = Ecell - (0.0592/n)logQ

Example 7
Calculate the voltage produced by the galvanic

cell which uses the reaction below if [Ag+] = 0.001 M and [Cu2+] = 1.3 M. 2Ag+(aq) + Cu(s) 2Ag(s) + Cu2+(aq)

Standard Reduction Potentials

Reduction Half-Reaction
F2(g) + 2e- 2F-(aq) Au3+(aq) + 3e- Au(s) Cl2(g) + 2 e- 2Cl-(aq)

E(V)
2.87 1.50 1.36 1.33 1.23 0.80 0.77 0.34 0.15

Red. agent strength increases

Ox. agent strength increases

Cr2O72-(aq) + 14H+(aq) + 6e- 2Cr3+(aq) + 7H2O O2(g) + 4H+ + 4e- 2H2O(l) Ag+(aq) + e- Ag(s) Fe3+(aq) + e- Fe2+(aq) Cu2+(aq) + 2e- Cu(s) Sn4+(aq) + 2e- Sn2+(aq)

2H+(aq) + 2e- H2(g)

Sn2+(aq) + 2e- Sn(s) Ni2+(aq) + 2e- Ni(s) Fe2+(aq) + 2e- Fe(s) Zn2+(aq) + 2e- Zn(s) Al3+(aq) + 3e- Al(s) Mg2+(aq) + 2e- Mg(s) Li+(aq) + e- Li(s)

0.00
-0.14 -0.23 -0.44 -0.76 -1.66 -2.37 -3.04

Commercial Voltaic Cells

Battery

commercial voltaic cell used as portable source of electrical energy

types

primary cell
Nonrechargeable Example: Alkaline battery

secondary cell
Rechargeable Example: Lead storage battery

How Does a Battery Work

Assume a generalized battery Seal/cap

cathode (+) Electrolyte Paste

anode (-)

Battery
Placing the battery into a flashlight, etc., and turning the power on completes the circuit and allows electron flow to occur

Electrolyte paste: ion migration occurs here cathode (+): Reduction occurs here anode (-): oxidation occurs here

e- flow

How Does a Battery Work

Battery reaction when producing electricity

(spontaneous):
Cathode: O1 + e- R1 Anode: R2 O2 + eOverall: O1 + R2 R1 + O2
Recharging a secondary cell Redox reaction must be reversed, i.e., current is reversed (nonspontaneous) Recharge: O2 + R1 R2 + O1 Performed using electrical energy from an external power source

Batteries
Read the textbook to fill in the details on

specific batteries.
Alkaline battery Lead storage battery Nicad battery Fuel cell

Corrosion
Corrosion

deterioration of metals by a spontaneous redox reaction

Attacked by species in environment
Metal becomes a voltaic cell

Metal is often lost to a solution as an ion

Rusting of Iron

Corrosion of Iron

Corrosion of Iron
Half-reactions anode: Fe(s) Fe2+(aq) + 2ecathode: O2(g) + 4H+(aq) + 4e- 2H2O(l) overall: 2Fe(s) + O2(g) + 4H+(aq) 2Fe2+(aq) + 2H2O(l) Ecell > 0 (Ecell = 0.8 to 1.2 V), so process is spontaneous!

Corrosion of Iron
Rust formation:
4Fe2+(aq) + O2(g) + 4H+(aq) 4Fe3+(aq) + 2H2O(l) 2Fe3+(aq) + 4H2O(l) Fe2O3H2O(s) + 6H+(aq)

Prevention of Corrosion
Cover the Fe surface with a protective coating

Paint Passivation
surface atoms made inactive via oxidation 2Fe(s) + 2Na2CrO4(aq) + 2H2O(l) --> Fe2O3(s) + Cr2O3(s) + 4NaOH(aq)

Other metal
Tin Zn
Galvanized iron

Prevention of Corrosion
Cathodic Protection

metal to be protected is brought into contact with a more easily oxidized metal sacrificial metal becomes the anode
Corrodes preferentially over the iron Iron serves only as the cathode

Standard Electrode Potentials

Half-reaction
F2(g) + 2e- -> 2F-(aq) Ag+(aq) + e- -> Ag(s) Cu2+(aq) + 2e- -> Cu(s) 2H+(aq) + 2e- -> H2(g) Ni2+(aq) + 2e- -> Ni(s) Fe2+(aq) + 2e- -> Fe(s) Zn2+(aq) + 2e- -> Zn(s) Al3+(aq) + 3e- -> Al(s) Mg2+(aq) + 2e- ->Mg(s)

E
+2.87 V +0.80 V +0.34 V 0V -0.25 V -0.44 V -0.76 V Metals more -1.66 V easily oxidized -2.38 V than Fe have

more negative Es

Cathodic Protection
galvanized steel (Fe)

Cathodic Protection
(anode)

(cathode) (electrolyte)

Electrolysis
Electrolysis

process in which electrical energy drives a nonspontaneous redox reaction

electrical energy is converted into chemical energy

Electrolytic cell

electrochemical cell in which an electric current drives a nonspontaneous redox reaction

Electrolysis
Same principles apply to both electrolytic and

voltaic cells
oxidation occurs at the anode reduction occurs at the cathode electrons flow from anode to cathode in the external circuit
In an electrolytic cell, an external power source pumps the electrons through the external circuit

Electrolysis of Molten NaCl

Quantitative Aspects of Electrochemical Cells

For any half-reaction, the amount of a substance

oxidized or reduced at an electrode is proportional to the number of electrons passed through the cell
Faradays law of electrolysis Examples
Na+ + 1e- Na Al3+ + 3e- Al

Number of electrons passing through cell is measured by determining the quantity of charge (coulombs) that has passed
1C=1Ax1s 1 F = 1 mole e- = 96500 C

Steps for Quantitative Electrolysis Calculations

current (A) and time (s), A x s charge in coulombs (C)

Number of moles of e-

moles of substance oxidized or reduced

mass of substance oxidized or reduced

Example 8
What mass of copper metal can be produced by

a 3.00 A current flowing through a copper(II) sulfate (CuSO4) solution for 5.00 hours?

Example 9
An aqueous solution of an iron salt is

electrolyzed by passing a current of 2.50 A for 3.50 hours. As a result, 6.1 g of iron metal are formed at the cathode. Calculate the charge on the iron ions in the solution.