Electrochemistry

Unit I

Electrochemistry
Electrochemistry
deals with interconversion between chemical and electrical energy

Electrochemistry
Electrochemistry
deals with the inter conversion between chemical and electrical energy involves redox reactions

Electrochemistry
Electrochemistry
deals with inter conversion between chemical and electrical energy involves redox reactions
electron transfer reactions

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
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

Redox Reactions
Direct redox reaction
Oxidizing and reducing agents are mixed together

Zn rod Zn rod CuSO4(aq) (Cu2+) CuSO4(aq) (Cu2+)

Deposit of Cu metal forms

Electrochemical Cells
ee-

Zn anode

Cu cathode

Salt bridge Zn2+ Zn Zn2+ + 2e-

Cu2+ Cu2+ + 2e- Cu

Electrochemical Cells
Voltaic Cell
cell in which a spontaneous redox reaction generates electricity chemical energy electrical energy

Electrochemical Cells
Electrolytic Cell
electrochemical cell in which an electric current drives a non-spontaneous redox reaction electrical energy chemical energy

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
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 be found.

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

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) E(V) 2.87 1.50 1.36 1.33 1.23 0.80 0.77 0.34 0.15 0.00 -0.14 -0.23 -0.44 -0.76 -1.66 -2.37 -3.04

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) i2+(aq) + 2e- i(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)

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

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 -

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

Cell Potential
Is there a relationship between Ecell and G for a redox reaction?

Cell Potential
Relationship between Ecell and G:
G = -nFEcell
F = Faraday constant = 96500 C/mol e-s, n = # e-s transferred redox rxn.

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

Equilibrium Constants from Ecell

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

Under standard state conditions:

G = -nFEcell

Equilibrium Constants from Ecell

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

Under standard state conditions:

G = -nFEcell

Equilibrium Constants from Ecell

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

Under standard state conditions:

G = -nFEcell

and
G = -RTlnK

so -nFEcell = -RTlnK

Calorimetric Data

H S
Composition Data Electrochemical Data

Ecell
Equilibrium constants

The Nernst Equation

G depends on concentrations
G = G + RTlnQ

and G = -nFEcell and G = -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

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

Alkaline Dry Cell

Alkaline Dry Cell

Plated steel (+) Cathode: Mixture of MnO2 and C (graphite)

Brass rod

Anode: Mixture of Zn and KOH(aq) Insulators

Paper or fabric Separator Plated steel (-)

Alkaline Dry Cell

Half-reactions

Alkaline Dry Cell

Half-reactions
anode: Zn(s) + 2OH-(aq) --> ZnO(s) + H2O(l) + 2e-

Alkaline Dry Cell

Half-reactions
anode: Zn(s) + 2OH-(aq) --> ZnO(s) + H2O(l) + 2ecathode: 2MnO2(s) + H2O(l) + 2e- --> Mn2O3(s) + 2OH-(aq)

Alkaline Dry Cell

Half-reactions
anode: Zn(s) + 2OH-(aq) --> ZnO(s) + H2O(l) + 2ecathode: 2MnO2(s) + H2O(l) + 2e- --> Mn2O3(s) + 2OH-(aq) overall: Zn(s) + 2MnO2(s) --> Mn2O3(s) + ZnO(s)

Ecell = 1.54 V

Lead Storage Battery

(anode)

(cathode) 6 x 2V = 12 V

Lead Storage Battery

Half-reactions

Lead Storage Battery

Half-reactions
anode: Pb(s) + SO42-(aq) --> PbSO4(s) + 2e-

Lead Storage Battery

Half-reactions
anode: Pb(s) + SO42-(aq) --> PbSO4(s) + 2ecathode: PbO2(s) + 4H+(aq) + SO42-(aq) + 2e- --> PbSO4(s) + 2H2O(l)

Lead Storage Battery

Half-reactions
anode: Pb(s) + SO42-(aq) --> PbSO4(s) + 2ecathode: PbO2(s) + 4H+(aq) + SO42-(aq) + 2e- --> PbSO4(s) + 2H2O(l) overall: Pb(s) + PbO2(s) + 2H2SO4(aq) --> 2PbSO4(s) + 2H2O(l)

Lead Storage Battery

Half-reactions
anode: Pb(s) + SO42-(aq) --> PbSO4(s) + 2ecathode: PbO2(s) + 4H+(aq) + SO42-(aq) + 2e- --> PbSO4(s) + 2H2O(l) overall: Pb(s) + PbO2(s) + 2H2SO4(aq) --> 2PbSO4(s) + 2H2O(l)

Cell reaction reversed during recharging.

2PbSO4(s) + 2H2O(l) --> Pb(s) + PbO2(s) + 2H2SO4(aq)

Lead Storage Battery

Half-reactions
anode: Pb(s) + HSO42-(aq) --> PbSO4(s) + H+ + 2ecathode: PbO2(s) + 3H+(aq) + HSO42-(aq) + 2e- --> PbSO4(s) + 2H2O(l) overall: Pb(s) + PbO2(s) + 2H+ + 2HSO4-(aq) --> 2PbSO4(s) + 2H2O(l)

Cell reaction reversed during recharging.

Lead Storage Battery

Half-reactions during recharging (nonspontaneous)
cathode: PbSO4(s) + H+ + 2e- --> Pb(s) + HSO42-(aq) anode: PbSO4(s) + 2H2O(l) --> PbO2(s) + 3H+(aq) + HSO42-(aq) + 2eoverall: 2PbSO4(s) + 2H2O(l) --> PbO2(s) + Pb(s) + 2H+ + 2HSO4-(aq) Cell converted into electrolytic cell via application of external electrical energy.

Fuel Cells
Voltaic-like cell that operates with continuous supply of energetic reactants (fuel) to the electrodes
utilize combustion reactions do not store chemical energy
Not self-contained since reactants must be supplied to the electrodes

Example: Hydrogen-Oxygen fuel cell

HydrogenHydrogen -Oxygen Fuel Cell

HydrogenHydrogen -Oxygen Fuel Cell

Half-reactions

HydrogenHydrogen -Oxygen Fuel Cell

Half-reactions
anode: 2H2(g) + 4OH-(aq) --> 4H2O(l) + 4e-

HydrogenHydrogen -Oxygen Fuel Cell

Half-reactions
anode: 2H2(g) + 4OH-(aq) --> 4H2O(l) + 4ecathode: O2(g) + 2H2O(l) + 4e- --> 4OH-(aq)

HydrogenHydrogen -Oxygen Fuel Cell

Half-reactions
anode: 2H2(g) + 4OH-(aq) --> 4H2O(l) + 4ecathode: O2(g) + 2H2O(l) + 4e- --> 4OH-(aq) overall: 2H2(g) + O2(g) --> 2H2O(l)

What is a Fuel Cell, and how does it work?

A fuel cell is an electrochemical device that combines hydrogen fuel and oxygen from air to produce electricity and water. In a Polymer Electrolyte Fuel Cell, Hydrogen ions form at the anode, and diffuse through the electrolyte and react with oxygen at the cathode. H2 H2 H2 H+ H2 H2

e-

eO2 H2 O O2 O2 O2 H2 O O2 O2 O2 H2 O

H2 H+

H2

Anode
Anode: H2 2H + (aq) Cathode: O2 + 2H + (aq) + 2e- H2O (l) +2e-

Electrolyte

Cathode

Uses of Fuel Cells

Transportation:
Phosphoric Acid Fuel Cell
Anode: H2(g) 2H + (aq) + 2e Cathode: O2 (g) + 2H+ (aq) + 2e- H2O(l)

Portable:
Proton Exchange Membrane Fuel Cell
Anode: H2(g) 2H + (aq) + 2e Cathode: Cathode: O2 (g) + 2H+ (aq) + 2e- H2O(l)

Stationary:
Solid Oxide Fuel Cells
Anode: H2(g) + O2 H2O(g) + 2e Cathode: O2 (g) + 2e- O2-

Fuel Cell uses

Fuel Cell transit buses in Chicago (Ballard Corp)
Anode: H2(g) 2H + (aq) + 2eCathode: O2 (g) + 2H+ (aq) + 2e- H2O(l)

Energy Research Corp.

Anode: H2(g) + 2CO3 H2O(g) + CO2(g) + 2eCathode: O2 (g) + CO2 + 2e- 2CO3

Solar Energy A Bright Idea!

Id put my money on the sun and solar energy. What a source of power! I hope we dont have to wait til oil and coal run out before we tackle that. - Thomas Edison

People have been harnessing solar energy for a long time!

Solar collector for heating water

A home in California in 1906

Sun Angles

Solar Electric (Photovoltaic)

Solar Electric Systems

Photovoltaic (PV) systems convert light energy directly into electricity. Commonly known as solar cells. The simplest systems power the small calculators we use every day. More complicated systems will provide a large portion of the electricity in the near future. PV represents one of the most promising means of maintaining our energy intensive standard of living while not contributing to global warming and pollution.

How Does it Work?

Sunlight is composed of photons, or bundles of radiant energy. When photons strike a PV cell, they may be reflected or absorbed (transmitted through the cell). Only the absorbed photons generate electricity. When the photons are absorbed, the energy of the photons is transferred to electrons in the atoms of the solar cell.

How Does it Work?

Solar cells are usually made of two thin pieces of silicon, the substance that makes up sand and the second most common substance on earth. One piece of silicon has a small amount of boron added to it, which gives it a tendency to attract electrons. It is called the player because of its positive tendency. The other piece of silicon has a small amount of phosphorous added to it, giving it an excess of free electrons. This is called the n-layer because it has a tendency to give up negatively charged electrons.

How Does it Work?

Best Place For Solar Panels?

South Facing roof, adequate space No shading (time of year, future tree growth) Roof structure, condition

Large Scale PV Power Plants

Prescott Airport Location: AZ Operator: Arizona Public Service Configuration: 1,450 kWp SGS Solar Location: AZ Operator: Tucson Electric Power Co Configuration: 3,200 kWp

Centralized WindWind-Solar Hybrid System

In hybrid energy systems more than a single source of energy supplies the electricity. Wind and Solar compliment one another

Various type of PV cell

Cell Module Array Volt 0.5V 20-30V 200-300V Ampere 5-6A 5-6A 50A-200A Watt 2-3W 100-200W 10-50kW Size about 10cm about 1m about 30m

Hierarchy of PV Array (10-50kW) Module, Panel (100200W) Cell (2-3W)

6x9=54 (cells)

100-300 (modules)

Installation example
Roof top of residence ( Grid connected ) Owner can sell excess power to power utility.

Most popular installation style in Japan. (Almost 85% PV in Japan )

Roof top of school ,community-center building. (For education and emergency power)

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Distant and independent power supply ( Off grid )

Relay station on top of mountain

Advertising sign beside highway 85

Mountain lodge ( Off grid )

Inverter and controller

1.2kW system

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