ELECTROCHEMISTRY

Brief Review

OXIDATIONloss of electron(s) by a species; increase in oxidation number; increase in oxygen. REDUCTIONgain of electron(s); decrease in oxidation number; decrease in oxygen; increase in hydrogen. OXIDIZING AGENTelectron acceptor; species is reduced. REDUCING AGENTelectron donor; species is oxidized.

Electron Transfer Reactions

Electron transfer reactions are oxidation-

reduction or redox reactions.

Results in the generation of an electric current (electricity) or be caused by imposing an electric current.

Therefore, this field of chemistry is often called

ELECTROCHEMISTRY.

OXIDATION-REDUCTION REACTIONS
Direct Redox Reaction Oxidizing and reducing agents in direct contact. Cu(s) + 2 Ag+(aq) ---> Cu2+(aq) + 2 Ag(s)

OXIDATION-REDUCTION REACTIONS
Indirect Redox Reaction

A battery functions by transferring electrons through an external wire from the reducing agent to the oxidizing agent.

CHEMICAL CHANGE ELECTRIC CURRENT

Mg metal

With time, Cu plates out onto Mg metal strip, and Mg strip disappears.
Cu2+ ions

Mg

is oxidized and is the reducing agent Mg(s) ---> Mg2+(aq) + 2eis reduced and is the oxidizing agent Cu2+(aq) + 2e- ---> Cu(s)

Cu2+

Basic Concepts of Electrochemical Cells

wire

e le c t r o n s

Mg

salt bridge

Cu

Mg 2+ ions

Cu

2+

ions

Anode

Cathode

CHEMICAL CHANGE ELECTRIC CURRENT

To

obtain a useful current, we separate the oxidizing and reducing agents so that electron transfer occurs thru an external wire.

wire

e le c t r o n s

Mg

salt bridge

Cu

Mg2+ ions

Cu2+ ions

This is accomplished in a GALVANIC or VOLTAIC cell. A group of such cells is called a battery.

Mg --> Mg2+ + 2eOxidation Anode Negative

wire

Cu2+ + 2e- --> Cu

Reduction Cathode Positive

e lect rons

Mg

salt bridge

Cu

<--Anions Cations-->

Mg ions

2+

Cu2+ ions

Electrons travel thru external wire. Salt bridge allows anions and cations to move between electrode compartments.

CELL POTENTIAL, (E )
0
Mg

wire

elect rons
salt bridge

Cu
Cu2+ ions

For Mg/Cu cell, potential is 2.71V at 25 C

Mg2+ ions

This is the STANDARD CELL POTENTIAL, Eo E0 a quantitative measure of the tendency of reactants to proceed to products when all are in their standard states at 25 C.

If E0 is positive the reaction is spontaneous on the otherwise the reaction is non- spontaneous.

Calculating Cell Voltage

Balanced half-reactions can be added together to get overall, balanced equation.

If we know E0 for each half-reaction, we could get E0 for net reaction.

Cu2+(aq) + 2e- ---> Cu(s) Mg(s) ---> Mg2+(aq) + 2e-------------------------------------------Cu2+(aq) + Mg(s) ---> Mg2+(aq) + Cu(s)

Note that this is the reduction potential. In the reaction, Mg underwent oxidation such that the sign of the E0 from -2.73.

reduction potential E0 of Cu is + 0.34

Mg/Cu Electrochemical Cell

wire

Anode, negative, source of electrons

e le c t r o n s

Mg
2+ Mg ions

salt bridge

Cu
Cu2+ ions

Cathode, positive, sink for electrons

Cu2+(aq) + 2e- ---> Cu(s) Eo = +0.34 V Mg(s) ---> Mg2+(aq) + 2eEo = - 2.37 V --------------------------------------------------------------Cu2+(aq) + Zn(s) Zn2+(aq) + Cu(s) Eo = +2.71 V

+-

KIaq K+1 + I -1
electrolysis

There are three possible species: K+1 + e- K (s) I2 + 2e- 2IH2O + 2e- H2(g) + 2OH Add: Phenolphthalein base indicator (pink) Starch - test for iodine (blue violet)

KI (aq)

Which has higher SRP?

There are three possible species: K+1 + e- K (s) I2 + 2e- 2IH2O + 2e- H2(g) + 2OH -

Eo = -2.925
= + 0.535 = - 0.828

Cathode : H2O + 2e- H2(g) + 2OH Anode : 2I- I2 + 2e-

Eo = - 0.828 E0 = + 0.535

H2O + 2I- I2 + H2(g) + 2OH -

E0 cell = E0 cat - E0 an = (-0.828) - (+ 0.535) = - 1.363 V

e+Anode Cathode

K+ I-

More About Calculating Cell Voltage

Assume I- ion can reduce water.
2 H2O + 2e- ---> H2 + 2 OHCathode 2 I- ---> I2 + 2eAnode ------------------------------------------------2 I- + 2 H2O --> I2 + 2 OH- + H2 Assuming reaction occurs as written, E = Ecat- Ean= (-0.828 V) (+0.535 V) = -1.363 V
Minus E means rxn. occurs in opposite direction (the connection is backwards or you are recharging the battery)

Eo for a Voltaic Cell

All ingredients are present. Which way does reaction proceed?

B A Cd Cd2+ + 2e- Fe Fe2+ + 2eFe2+ + 2e- Fe Cd2+ + 2e- Cd Write the full equation and its net reduction potential.

Eo for a Voltaic Cell

Cd2+ + 2e- Cd Fe Fe2+ + 2e-

E0 = -0.40 E0 = -0.44 --------------------------------------------Fe + Cd2+ Fe+2 + Cd E0 = 0.04

From the table, you see Fe is a better reducing agent than Cd Cd2+ is a better oxidizing agent than Fe2+