Electrochemistry Notes

• Reduction / Oxidation Review

Cu + 2Ag+  Cu2+ + 2Ag
– Cu is oxidized….loses electrons
– Ag+ is reduced….gains electrons
• What about the oxidation of a
carbohydrate?
CH2O + O2  CO2 + H2O
(reverse of photosynthesis)
• We examine the reaction
– CH2O  CO2 conversion is oxidation.
– O2  H2O is reduction
• The reaction is also a redox reaction
– Organic definition of oxidation / reduction
• Oxidation: Gain O and / or lose H
• Reduction: Gain H and / or lose O
• A redox reaction can be divided into 2 half
reactions (cannot proceed unless the two are
coupled)
• Reduction: O2 + 4e- + 4H+ ⇌ 2H2O
• Oxidation: CH2O + H2O ⇌ CO2 + 4H+ + 4e-
• We know photosynthesis converts solar energy to
chemical energy. The reverse reaction should convert
the stored chemical energy into a useable form of energy
that could be used to do work.
• A measure of a chemical rxn’s tendency to proceed is
the change in free energy, ΔG, for the reaction.
Remember,
• ΔGrxn = ∑ ΔGproducts - ∑ ΔGreactants
– If ΔG = (-), then the reaction can liberate chemical energy to do
some work….spontaneous
– If ΔG = (+), energy must be added from the surroundings to get
the rxn to proceed.
• If a reaction involves electron transfer, (a redox
reaction), liberated free energy can be converted into
electrical energy. A measure of a redox rxn’s tendency
to do electrical work is called the reactions redox
potential (E) and is measured in Volts (V).
• ΔG and E are related
ΔG = -nFE
E = reaction potential
F = Faraday’s Constant = 96,500 Coulombs/mole
n = # moles of electrons transferred
• Since ΔG (-) is spontaneous, E = (+) will be
spontaneous….a charged battery is an example
of E = (+). If E = (-), electrical work must be
done to get the rxn to proceed (charging a
battery).
• Although half reactions cannot proceed w/o a
second coupled half reaction, we can vary half
reactions and keep the other half the same (a
standard half reaction) in order to get a measure
or comparison of half reactions tendency to
proceed.
• Consider Fe3+ + e- ⇌ Fe2+
How easy is it to reduce Fe3+ compared to reduction
of Ag+? Ag+ + e- ⇌ Ag
• Set up two reactions and measure the
reactions potential (voltage)
Fe3+ + ½H2 ⇌ Fe2+ + H+ Eo = 0.77 V
Ag+ + ½H2 ⇌ Ag + H+ Eo = 0.80 V
Note: Eo  Voltage was measured under
standard state conditions….all solution
concentrations were 1 M, all gases present @ 1
atm partial pressure.
• The measured voltage (since the oxidation half reaction,
½H2 ⇌ H+ + e-, is the same) reflects the tendency of
Fe3+ + e- ⇌ Fe2+ compared to
Ag+ + e- ⇌ Ag
• We will assign an oxidation voltage of 0 Volts to the half reaction,
½H2 ⇌ H+ + e-.
• The overall reaction potential is the sum of the pontentials for the
reduction half reaction and the oxidation half reaction. If the
potential of the oxidation half reaction is assigned a value of 0 Volts,
then the measured reaction voltages (Eorxn) represent the standard
reduction potentials, respectively.
– By convention, the overall potential for a reaction is:
• ∴ Fe3+ + e- ⇌ Fe2+ Eored = +0.77 V
Ag+ + e- ⇌ Ag Eored = +0.80 V

• What about the reverse?

– Fe2+ ⇌ Fe3+ + e- Eooxd =
• The half reaction:
H+ + e- ⇌ ½H2 Eored = 0.0 V is called the
• Voltage measurements are made in an electrochemical cell. This diagram is actually
backwards according to convention. The cathode is placed on the left and anode on
the right. Nonetheless, the cell voltage of +0.34 V is measured. Since one the
electrodes is an SHE with a voltage of 0 V, the reduction potential of Cu2+ is
Cu2+ + 2e- ⇌ Cu Eored = +0.34 V
• Acid strength is measured or indicated by Ka
• Oxidizing or reducing strength is characterized
by Eo (Standard Reduction Potential)
O2 + 4e- + 4H+ ⇌ 2H2O Eo = +1.23 V
Fe3+ + e- ⇌ Fe2+ Eo = +0.77 V
S + 2H+ + 2e- ⇌ H2S Eo = +0.141 V
Na+ + 1e- ⇌ Na Eo = -2.71 V
It is difficult to reduce Na+. But Na ⇌ Na+ + 1e-
(Eooxd = +2.71 V) will occur readily.

• Considerations about Eo. Units are Volt ≡ Joule /

coulomb (an intensive unit). Its magnitude doesn’t with
the # of electrons.
H+ + e- ⇌ ½H2 Eo = 0.0 V
2H+ + 2e- ⇌ H2 Eo = 0.0 V
• The previous measurements were made under standard state
conditions. How does concentration effect oxidizing or reducing
strength? The Nernst Equation to the rescue

G  G o  RT ln Q (Q  reaction quotient )
G  nFE F  Faraday' s Constant (96,500 Coul/mol)
G o  nFE o
  nFE  nFE o  RT ln Q
RT
E  Eo  ln Q
nF
2.03RT
converting ln to log 10 E  E 
o
log Q
nF
Substituti ng values for R, T (298 K) and F
0.059
E  Eo  log Q (units on 0.059 are Volts)
n
• Apply the Nernst Equation
Consider: Fe3+ + e- ⇌ Fe2+ Eo = +0.77 V under standard
state conditions
[Fe3+] = 1 M, [Fe2+] = 1 M
What if the concentrations change????

2
0.059 [ Fe ] 0.059 [0.1 M ]
EE 
o
log 3
 0.77 V  log
n [ Fe ] 1 [1 M ]
0.059 [Products ]
EE 
o
log
n [Reactants ]
Balancing Consider: Cr2O72- + Fe2+ ⇌ Cr3+ + Fe3+
Redox a) Balance in acidic solution
Reactions: b) Balance in basic solution
• Look at both half reactions, find LCM of electrons
and balance # electrons

Combine and cancel like terms

• Convert to basic conditions….add OH- to neutralize H+ to

H2O