Redox Reactions

Chapter 19

Electrochemistry and
Its Applications

Copper Screen Electrochemistry

Reacts
with Silver • the study of chemical reactions that produce
electrical currents or voltages and of the
Nitrate chemical reactions that are caused by the
action of currents or voltages.

Redox Reaction? Basic Definitions

• Is strong oxidizing or reducing agent
present?
• Is there a change in oxidation number?
• Is there an uncombined elemental reaction
or product?
reduction - gain of electrons
oxidation - loss of electrons
oxidation-reduction reaction (redox reaction) -
reaction in which one substance looses electrons
to another substance
half-reaction - half of a redox reaction; either the half
of the reaction where oxidation occurs; or, the half
reaction where reduction occurs

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 More Definitions
oxidizing agent - substance that causes oxidation
while undergoing reduction; attracts electrons
away from a substance
reducing agent - substance that causes reduction
while undergoing oxidation; looses electrons to
another a substance
Rules for Assigning
Oxidation States
1. zero for uncombined element
2. charge on monatomic ion
3. F is always -1; other halogens -1 except
when combined with more electronegative
halogen or oxygenon ion or molecule

Rules for Assigning Balancing Oxidation-Reduction

Oxidation States Equations
4. H is +1 except in metal hydrides, where H half-reaction technique
is -1 Fe+3 + Sn+2 => Fe+2 + Sn+4
5. O is -2 except when combined with F (then ox 1/2 rx
+1 or +2) or in peroxides, -1. Sn+2 => Sn+4 + 2e-
6. sum of oxidation states equals charge on red 1/2 rx.
ion or molecule Fe+3 + 1e- => Fe+2

Balancing Oxidation-Reduction Balancing Oxidation-Reduction

Equations Equations
half-reaction technique half-reaction technique
Fe+3 + Sn+2 => Fe+2 + Sn+4 Fe+2 + MnO4- + H+ => Mn+2 + Fe+3 + H2O
ox 1/2 rx ox 1/2 rx
1( Sn+2 => Sn+4 + 2e- ) Fe+2 => Fe+3 + 1e-
red 1/2 rx
red 1/2 rx. MnO4- + 8H+ + 5e- => Mn+2 + 4H2O
2( Fe+3 + 1e- => Fe+2 )
Sn+2 + 2Fe+3 => Sn+4 + 2Fe+2

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 Balancing Oxidation-Reduction
Equations Balancing Redox Reactions:
half-reaction technique acid solution
Fe+2 + MnO4- + H+ => Mn+2 + Fe+3 + H2O H+ => H2O or H2O => H+
ox 1/2 rx base solution
5(Fe+2 => Fe+3 + 1e-)
red 1/2 rx OH- => H2O or H2O => OH-
1 (MnO4- + 8H+ + 5e- => Mn+2 + 4H2O)
5Fe+2 + MnO4- + 8H+ => Mn+2 + 5Fe+3 + 4H2O

Electrochemical Cells Daniel's Cell

• harnessed chemical reaction which 1.10 v

produces an electric current • battery for telegraph

• called Voltaic Cells or Batteries • copper electrode
Zinc anode dipped into a
• anode - electrode where oxidation occurs
solution of copper(II)
• cathode - electrode where reduction occurs Zn+2 Zn+2
sulfate
Cu+2
• Cell Potential - the potential difference, in Cu+2
Zn+2 Zn+2 • zinc electrode
volts, between the electrodes of an dipped into a
Cu+2
electrochemical cell Cu+2
solution of zinc
Copper cathode sulfate

Daniel's Cell Simple Electrochemical Cell

Zn(s) + Cu+2(aq) => Zn+2(aq) + Cu(s)
oxidation half reaction
anode Zn(s) => Zn+2(aq) + 2 e-
reduction half reaction
cathode Cu+2(aq) + 2 e- => Cu(s)

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 Electrochemical Terminology Electrical Work
electrical work = charge × potential energy difference

coulombs = amperes × seconds

1 volt = 1 joule/coulomb

thus

1 joule = 1 volt × 1 coulomb

Standard Cell Potential

• the potential difference, in volts, between
Standard Hydrogen Electrode
the electrodes of an electrochemical cell
• consists of a platinum
when the all concentrations of all solutes is electrode covered with
1 molar, all the partial pressures of any a fine powder of
gases are 1 atm, and the temperature at platinum around
25oC which H2(g) is bubbled.
• direction of Oxidation-Reduction Reactions Its potential is defined
as zero volts.
• positive value indicates a spontaneous H2(g) = 2 H+(aq) + 2 e-
reaction
reversible reaction

Cell Diagram Standard

Reduction
• the shorthand representation of an Potentials
electrochemical cell showing the two half-
cells connected by a salt bridge or porous
barrier, such as:
Zn(s)/ZnSO4(aq)//CuSO4(aq)/Cu(s)
anode cathode

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 Redox Reaction Cell Potentials & ΔG
• the reduction half reaction is the half ΔG = -nFE or ΔGo = -nFEo
reaction with the more positive reduction where n × number of electrons
potential involved in reaction
• the half reaction with the lower reduction F × Faraday's constant,
potential is reverse and the sign of the 1 mole e- = 96,500 coulombs
potential is changed thus
• the cell potential is the sum of the half ΔG = ΔGo + RT ln Q
reaction potentials

Cell Potentials, ΔG, and Q Cell Potentials, ΔG, and K

ΔG = -nFE or ΔGo = -nFEo E = Eo - (RT/nF) ln Q
ΔG = ΔGo + RT ln Q at equilibrium
-nFE = -nFEo + RT ln Q 0 = Eo - (RT/nF) ln Keq
or and
E = Eo - (RT/nF) ln Q (nFEo)/(RT) = ln Keq
thus
Keq = e(nFE /RT)

Effect of Concentration on Cell Voltage: Relationships Linking:

The Nernst Equation ΔGo, Ecello, and Ko
Ecell = Eocell - (RT/nF)ln Q
Ecell = Eocell - (0.0592/n)log Q
where Q × reaction quotient
Q = [products]/[reactants]

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EXAMPLE: What is the cell potential for the
Daniel's cell when the [Zn+2] = 10 [Cu+2]?
Ecell = Eocell - (0.0257/n)ln Q
Q = ([Zn+2]/[Cu+2 ] = (10 [Cu+2])/[Cu+2]) = 10
Eo = (0.34 V)Cu couple + (-(-0.76 V)Zn couple
n = 2, 2 electron change
Ecell = (1.10 - (0.0257/2)ln 10) V
Ecell = (1.10 - (0.0257/2)2.303) V
Ecell = (1.10 - 0.0296) V = 1.07 V