A Hydrogen Electrode

Cell potentials can be measured Half-cell potential cannot be measured An arbitrary choice sets the half cell potential of a standard hydrogen electrode = 0 Eo1/2 (H+/H2) = 0 V Half Reaction is always written as a reduction 2 H+ (aq) + 2 e- H2 (g)

Spontanteous Cell Reaction? 2H+ (aq) + Zn (s) H2 (g) + Zn2+ (aq)

Zn/H2 Voltaic Cell

Cell Potential = 0.763 V under standard conditions
Ox An Zn (s) Zn2+ (aq) + 2 e-

Zinc metal dissolves in 1 M H+

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

Questions Anode? Cathode?

Voltage of Voltaic Cells

All voltaic cells are based on a spontaneous chemical reaction Therefore, G for the reaction must be negative This means that the voltage of a voltaic cell is always positive. G = -nFe

Standard Potential of Zn/H2 Cell

2H+ (aq) + Zn (s) H2 (g) + Zn2+ (aq) Cathode: 2 H+ (aq) + 2e- H2 (g) Anode: Zn (s) Zn2+ (aq) + 2 eEo (cell) = E1/2o (H+/H2) E1/2o (Zn2+/Zn)=+0.763V
Cathode Anode

E0(cell) = 0 E1/2o (Zn2+/Zn) = 0.763 V E1/2o (Zn2+/Zn) = -0.763 V Zn2+ (s) + 2e- Zn(s) E1/2o = -0.763 V

Determination of Half-Cell Potentials

Cu/H2 Voltaic Cell
Anode and cathode? H+/H2 is anode and Cu2+/Cu is cathode H2 (g) + Cu2+ 2 H+ (aq) + Cu (s) E0 (cell) = E01/2 (Cu2+/Cu) E01/2(H+/H2) E0 (cell) = E01/2 (Cu2+/Cu) 0 = 0.340 V E01/2 (Cu2+/Cu) = +0.340 V

Cell Potential = 0.340 V under standard conditions

Cell EMF
Standard Reduction Potentials
The larger the difference between Ered values, the larger Ecell. In a voltaic cell (spontaneous) Ered(cathode) is more positive than Ered(anode). Recall Ecell = Ered(cathode) Ered(anode)

Halfreaction cells

Eo(cell) = 1.10 V (measured) E1/2o (Cu2+/Cu) E1/2o (Zn2+/Zn) Eo (cell) = 0.340 V (-0.763 V) Eo (cell) = 1.10 V (Calculated from E01/2)

Selected Standard oC Electrode Potentials at 25

Stronger Reducing Agents

Stronger Oxidizing Agents

EOS

Cell EMF
Oxidizing and Reducing Agents

Cell Potential
Determine the cell potential for a galvanic cell based on the redox reaction. Cu(s) + Fe+3(aq) Cu+2(aq) + Fe+2(aq)

E1/20 = 0.77 V Cu+2(aq)+2e- Cu(s) E1/20 = 0.34 V Cu(s) Cu+2(aq)+2e-E1/20 = -0.34 V 2Fe+3(aq) + 2e- 2Fe+2(aq) E1/20 = 0.77 V
Cu(s) + 2Fe3+ Cu2+ + 2Fe2+ Ecell0 = 0.43V

Fe+3(aq) + e- Fe+2(aq)

Shorthand Cell Notation eg: Cu(s) + Fe+3(aq) Cu+2(aq)

+ Fe+2(aq) solidAqueousAqueoussolid Anode on the leftCathode on the right Single line different phases. Double line porous disk or salt bridge. If all the substances on one side are aqueous, a platinum electrode is indicated.

Cu(s)Cu+2(aq)Fe+2(aq),Fe+3(aq)Pt(s)
Anode Solution Bridge Solution Cathode

Shorthand Notation Voltaic Cell

1.10 V e-

porous plate

End Here

Trip
Zn2+
1.00 M

Start Here

Cu2+
1.00 M

Cu2+ Cu (cathode)

Zn Zn2+ (anode)

Tell the story. What do you see during your trip from the anode to the cathode?

Zn(s)

Zn2+ (aq, 1M)

Cu2+ (aq, 1M)

Cu(s)

Practice
Completely describe the galvanic cell based on the following half-reactions under standard conditions. MnO4- + 8 H+ +5e- Mn+2 + 4H2O E=1.51 Fe+3 +3e- Fe(s) E=0.036V Anode? Cathode? Cell Potential? Oxidizing agent and reducing agent? Shorthand cell notation?

Practice
3 MnO4- + 24 H+ + 5 Fe(s) 3 Mn2+ + 12 H2O + 5 Fe3+
eeQuestions 1. Whats missing in Diagram? 2. Anode? 3. Cathode? 4. Cell Reaction? 5. Direction electron flow? 6. Cell Potential? 7. Shorthand Representation? Fe(s)Fe3+MnO4(aq H+), Mn2+Pt e-

Fe3+ (aq)

Fe+3 +3e- Fe(s)E1/2=0.036V MnO4- + 8 H+ +5e- Mn+2 + 4H2O E=1/2 1.51 Fe(s) Fe3+ + 3 e- -E1/2 o = -0.036V E0cell = 1.51V 0.036V = 1.47V

Spontaneity of Redox Reactions

Consider the displacement of silver by nickel: Ni(s) + 2Ag+(aq) Ni2+(aq) + 2Ag(s) E0 = E0red(Ag+/Ag) E0red(Ni2+/Ni) = (0.80 V) - (-0.28 V) = 1.08 V The positive E0 indicates a spontaneous process.

EMF and Free-Energy Change

G = -nFE

Spontaneity of Redox Reactions

EMF and Free-Energy Change
G is the change in free-energy, n is the number of moles of electrons transferred, F is Faradays constant, and E is the emf of the cell.

1F = 96,500 C/mol = 96,500 J/V - mol

Since n and F are positive, if G > 0 then E < 0.

Effect of Concentration on Cell EMF

A voltaic cell is functional until E = 0 at which point equilibrium has been reached. The point at which E = 0 is determined by the concentrations of the species involved in the redox reaction.

The Nernst Equation

The Nernst equation relates emf to concentration using

G = G + RT ln Q

nFE = nFE + RT ln Q