ELECTROCHEMISTRY

Q Galvanic cells (batteries): chemical reaction used to produce electricity QStandard reduction potentials: prediction of the voltage of galvanic cells, prediction of the direction of redox processes CuSO4 + Zn ZnSO4 + Cu (No reaction in the opposite direction) Q Electrolysis: electricity used to bring about chemical reactions

Experiment:

CuSO4 + Zn ZnSO4 + Cu (No reaction in the opposite direction)

Half reactions: Zn Zn2+ + 2eCu2+ + 2e- Cu oxidation reduction

Chemistry: oxidation and reduction are not separated (redox reactions) Galvanic cells: oxidation and reduction are separated (flow of electrons capability of work) [In principle: all redox reactions can be used to prepare a galvanic cell]

Galvanic cells
Galvanic cells ( Voltaic cells): producing electricity using the energy of spontaneous chemical reactions Luigi Galvani (1737 1798) Alessandro Volta (1745 1827) Daniell cell Zn plate Cu plate

Zn plate ZnSO4 solution

1.10 V
salt bridge

+
Cu plate CuSO4 solution

Italian scientists

Zn-electrode

Cu electrode

Half-reaction on the Zn electrode: Zn Zn2+ + 2e oxidation ANODE

Half-reaction on the Cu electrode: ZnSO4 solution CuSO4 solution Cu2+ + 2e Cu reduction CATHODE

Electric potential
electric potential =
joule (J) energy electric charge coulomb (C)

Anode (oxidation) cathode (reduction) Overall reaction

Zn Zn2+ + 2e Cu2+ + 2e Cu Cu2+ + Zn Cu + Zn2+

volt (V)

The absolute electric potential can never be measured, only differences in potential are available The difference in electric potential is very easily measured in electronics and has a name on its own

Shorthand notation for galvanic cells anode Zn (s) Zn2+ salt bridge (aq) Cu2+ cathode (aq) Cu (s)

VOLTAGE (U or E)
the sign of the difference in two potentials is also easily determined (positive negative)

phase boundary electron flow

phase boundary

The voltage of a galvanic cell

electromotive force: the maximum voltage of a galvanic cell, measurable under conditions when no electric current flows standard electrode potential: the potential of an electrode when the concentration of the solution is 1.0 M voltage = standard potential of electrode 1 standard potential of electrode 2 potentials cannot be measured reference point needed

Standard hydrogen electrode (S.H.E.)

H2 gas, pressure: 1.0 bar Pt plate 1.0 M solution of H+ (e.g. HCl) Half-reaction on the standard hydrogen electrode can be both reduction and oxidation: H2 2H+ + 2e 2H+ + 2e H2 oxidation reduction

The standard hydrogen electrode is the reference point, it has a potential of 0 V by definition.

Standard reduction potentials

electrode potential of any electrode other than the S.H.E.: the voltage of a galvanic cell composed of the studied electrode and S.H.E. sign convention: positive (+) if S.H.E. is the anode negative () if S.H.E. is the cathode standard reduction potential (E): the electrode potential of a redox system when the concentrations of all solutes are 1.0 M weakly reducing less active strongly reducing more active

Li K Ca Na Mg Al Zn Cr Fe Co Sn H2 Cu Ag Hg Pt Au

REMINDER: Activity series of elements

Li+ + e Li K+ + e K Ca2+ + 2e Ca Na+ + e Na Mg2+ + 2e Mg Al3+ + 3e Al Zn2+ + 2e Zn Cr3+ + 3e Cr Fe2+ + 2e Fe Co2+ + 2e Co Sn2+ + 2e Sn 2H+ + 2e H2 Cu2+ + 2e Cu Ag+ + e Ag Hg2+ + 2e Hg Pt2+ + 2e Pt Au3+ + 3e Au

E = 3.04 V E = 2.92 V E = 2.87 V E = 2.71 V E = 2.37 V E = 1.66 V E = 0.76 V E = 0.71 V E = 0.45 V E = 0.28 V E = 0.14 V E = 0.00 V E = 0.34 V E = 0.80 V E = 0.86 V E = 1.20 V E = 1.38 V

standard reduction potentials

N2 + 4H2O + 4e N2H4 2H2O + 2e H2 + 2OH NH4+ + e NH3 + H2 Cr3+ + e Cr2+ 2H+ + 2e H2 Sn4+ + 2e Sn2+ O2 + 2H2O + 4e 4OH I2 + 2e 2I O2 + 2H+ + 2e H2O2 Fe3+ + e Fe2+ Br2 + 2e 2Br O2 + 4H+ + 4e 2H2O Cr2O72 + 14H+ + 6e 2Cr3+ + 7H2O Cl2 + 2e 2Cl MnO4 + 8H+ + 5e Mn2+ + 4H2O H2O2 + 2H+ + 2e 2H2O F2 + 2e 2F

E = 1.15 V E = 0.83 V E = 0.55 V E = 0.41 V E = 0.00 V E = 0.15 V E = 0.40 V E = 0.54 V E = 0.70 V E = 0.77 V E = 1.09 V E = 1.23 V E = 1.33 V E = 1.36 V E = 1.51 V E = 1.78 V E = 2.87 V

Strength of reducing and oxidizing agents

convention: half-reactions are always written as reductions oxidizing agent + ne reducing agent higher (more positive) E: stronger oxidizing agent F2: the strongest oxidizing agent lower (more negative) E: stronger reducing agent Li: the strongest reducing agent Based on standard reduction potentials (E values), it is possible to decide if a particular possible redox reaction is spontaneous or not.

Connection with free energy

spontaneous or nonspontaneous process in thermochemistry: free energy is decisive for ANY PROCESS

G < 0 spontaneous G > 0 nonspontaneous

How can E be decisive for redox reactions?

G = nFE
number of electrons transferred Faraday constant = 96485 Cmol1

positive E negative G negative E positive G

spontaneous process nonspontaneous process

An oxidizing agent oxidizes the reduced form of an oxidation-reduction couple that has more negative standard electrode potential A reducing agent reduces the oxidized form of an oxidation-reduction couple that has more positive standard electrode potential. Two reducing agents do not react with each other. Two oxidizing agents do not react with each other. Some substances can be both reducing and oxidizing agents depending on the other reactant(s)!

Examples
Zn + Au3+ ????? Zn is a reducing agent, Au3+ is an oxidizing agent. The redox system has a more negative standard potential than the Au3+/Au redox system spontaneous reaction occurs 3Zn + 2Au3+ 3Zn2+ + 2Au Zn is a more powerful reducing agent than Au Au3+ is a more powerful oxidizing agent than Zn2+ Zn2+/Zn

Examples
3Zn + 2Au3+ 3Zn2+ + 2Au Another line of thought: write the two half reactions Zn2+ + 2e Zn Au3+ + 3e Au E = 0.76 V E = 1.38 V

Examples
Cu + Co2+ Cu2+ + Co

E = E(Co2+/Co) E(Cu2+/Cu) = 0.28 V (+0.34 V) =

= 0.62 V < 0 nonspontaneous process Cr2O72 + 6Br + 14H+ 2Cr3+ + 3Br2 + 7H2O

In the above reaction, the reaction for Au occurs in the same direction as in the half reaction + direction opposite to the half reaction

sign sign

E = E(Cr2O72/2Cr3+) E(Br2/2Br) = +1.33 V (+1.09 V) =

= +0.24 V Cr2O72 > 0 spontaneous process

In the above reaction, the reaction for Zn occurs in the Calculate E taking the signs into account:

+ 6Cl + 14H+ 2Cr3+ + 3Cl2 + 7H2O < 0 nonspontaneous process

E = 1.38 V (0.76 V) = 2.14 V > 0 spontaneous process

E = E(Cr2O72/2Cr3+) E(Cl2/2Cl) = +1.33 V (+1.36 V) =

= 0.03 V

Examples
+ F2 ???? Two oxidizing agents! nonspontaneous process K+ Mg + Cl ???? Two reducing agents! nonspontaneous process 2H2O + Ca Ca2+ + H2 + 2OH

Examples
Sn2+ + H2O2 ????? Sn2+ + 2e Sn Sn4+ + 2e Sn2+ O2 + 2H+ + 2e H2O2 H2O2 + 2H+ + 2e 2H2O E = 0.14 V E = 0.15 V E = 0.70 V E = 1.78 V

Sn2+ and H2O2 can both be reducing and oxidizing agents depending on the other reactant(s) possibility 1: Sn2+ + 2H+ + H2O2 Sn4+ + 2H2O Sn2+ + H2O2 Sn + 2H+ + O2

E = E(H2O/2OH) E(Ca2+/Ca) = 0.83 V (2.87 V) =

= +2.04 V > 0 spontaneous process 2H2O + Co Co2+ + H2 + 2OH

E = 1.78 V (0.15 V) = 1.63 V > 0 spontaneous process

possibility 2:

E = E(H2O/2OH) E(Co2+/Co) = 0.83 V (0.28 V) =

= 0.55 V < 0 nonspontaneous process

E = 0.14 V (0.70 V) = 0.84 V< 0 nonspontaneous process

The Nernst equation

What if the concentrations of solutions used for electrodes are not 1.0 M? Dependence of reduction potentials (or electrode potentials) on the composition of solutions. NERNST EQUATION: R: gas constant T: temperature

half reaction: Ca2+ + 2e Ca NERNST EQUATION:

E = E

RT 1 ln nF [Ca 2+ ]

E = E

RT ln Q nF

half reaction: Cr2O72 + 14 H+ + 6e 2Cr3+ +7H2O NERNST EQUATION:

F: Faraday constant n: number of electrons transferred

Q: reaction quotient (see chemical equilibria) [red]/[ox] Q = 1/[Cu2+] or 1/[Zn2+] for the components of Daniell cell

E = E

[Cr 3 + ]2 RT ln nF [Cr2O7 2 ][H+ ]14

Batteries in practice
An extremely important everyday application of electrochemistry, a multibillion $ industry. Batteries Non-rechargeable dry cell (Leclanch cell) alkaline dry cell mercury battery fuel cells Rechargeable lead storage battery nickel-cadmium battery lithium battery

Dry cell (Leclanch cell): Anode: Zn(s) Zn2+(aq) + 2e Cathode: 2MnO2(s) + 2NH4+(aq) + 2e Mn2O3(s) + 2NH3(aq) + H2O(l) most common battery in everyday use Alkaline dry cell: Anode: Zn(s) + 2OH(aq) ZnO(s) + H2O(l) + 2e Cathode: 2MnO2(s) + H2O(l) + 2e Mn2O3(s) + 2OH(aq) more efficient than the dry cell Mercury battery: Anode: Zn(s) + 2OH(aq) ZnO(s) + H2O(l) + 2e Cathode: HgO(s) + H2O(l) + 2e Hg(l) + 2OH(aq) very small size

Lead storage battery: Anode: Pb(s) + HSO4(aq) PbSO4 + H+(aq) + 2e Cathode: PbO2(s) + 3H+(aq) + HSO4(aq) + 2e PbSO4(s) + 2H2O(l) standard battery in cars Nickel-Cadmium battery: Anode: Cd(s) + 2OH(aq) Cd(OH)2(s) + 2e Cathode: NiO(OH)(s) + H2O(l) + e Ni(OH)2(s) + OH(aq) looks like a normal small battery but rechargeable Lithium battery: Anode: Li(s) Li+ + e Cathode: MnO2(s) + Li+ + e LiMnO2(s) cell phones, laptops, cameras

Fuel cells
fuel cell = a galvanic cell in which one of the reactants is a traditional fuel (hydrogen, methane, ....) The energy-producing chemical reaction is the same as the burning of the fuel, but without the need for high temperature. Hydrogen fuel cell: Anode: 2H2(g) + 4OH(aq) 4H2O(l) + 4e Cathode: O2(g) + H2O(l) + 4e 4OH(aq) overall reaction: 2H2(g) + O2(g) 2H2O(l)

Electrolysis
How can batteries be recharged? How can F2 be produced? F2 is the strongest oxidizing agent. How can Li be produced? Li is the strongest reducing agent. ELECTROLYSIS: a nonspontaneous chemical reaction brought about by electric current galvanic cells: electrolytic cells: chemical energy electricity electricity chemical energy

Recharging batteries: The chemical reaction is exactly the opposite of the spontaneous reaction in the working battery. e.g. lead storage battery recharging: Cathode: Anode: PbSO4 + H+(aq) + 2e Pb(s) + HSO4(aq)

PbSO4(s) + 2H2O(l) PbO2(s) + 3H+(aq) + HSO4(aq) + 2e overall: 2PbSO4 (s) + 2H2O (l) PbO2 (s) + Pb (s) + 2H+ (aq) + 2HSO4 (aq)

Electrolysis: industrial importance is similar to the importance of batteries production of chlorine and NaOH production of plastic PVC (= polyvinyl chloride) production of aluminum electrolysis: passage of electrical current through the reaction medium the medium must be an electric conductor: molten salt or solution of an electrolyte the actual reactions occurring in complicated mixtures depend on voltage, current, electrode materials, ....

Electrolysis of molten sodium chloride: only possible electrode reactions anode: Cl Cl2 + e oxidation reduction cathode: Na+ + e Na overall process: NaCl Na + Cl2 production of Na and Cl2 from NaCl Electrolysis of aqueous sodium chloride solution: possible electrode reactions overvoltage E = +1.36 V anode: 2Cl Cl2 + 2e 2H2O O2 + 4H+ + 4e E = +1.23 V cathode: Na+ + e Na E = 2.71 V E = 0.83 V 2H2O + 2e H2 + 2OH production of NaOH and Cl2

Quantitative aspects of electrolysis

Production of aluminum: Hall-Heroult process early 1800s: Al was more expensive than Au today: Al is one of the cheapest metals Al2O3 dissolved in molten cryolite (Na3AlF6) 1000C, graphite electrodes anode: cathode: O2 O2 + 2e Al3+ + 3e Al oxidation reduction Voltage, current, time Voltage: should be higher than the voltage of the galvanic cell represented by the reverse reaction e.g. electrolysis of molten NaCl 2Cl Cl2 + 2e E = +1.36 V E = 2.71 V Na+ + e Na E = 4.08 V voltage of electrolysis should be higher than 4.08 V anode: cathode:

overall process: Al2O3 2Al + 1.5O2

Quantitative aspects of electrolysis

Michael Faraday (1830s): the amount of substance produced at an electrode by electrolysis is proportional to the charge passed through the electrolytic cell Charge = Current time 1 coulomb = 1 amper 1 second cathode: Na+ + e Na 1 mol e needed to produce 1 mol Na charge of 1 mol e: 96485 C (Faraday constant) 96485 C charge needed to produce 1 mol Na