Redox chemistry

Redox Chemistry
Oxidation
A  An+ + ne‾ Anode Cathode
Ion migration
Oxidation Reduction
A + Bn+  An+ + B
Electron flow
Bn+ + ne‾  B
Reduction

Anode rxn: Zn(s)  Zn2+(aq) + 2e‾

Cathode rxn: Cu2+(aq) + 2e‾  Cu(s)

Ecell = ΔV = (Eright – Eleft) ΔG = - nFEcell

= (Ecathode – Eanode)
= (Ered – Eox)

ΔG = Negative for a spontaneous reaction

Ecell = Positive for spontaneous cell reaction
Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)
 Redox Chemistry
o As any oxidation or reduction can not take place independently, so it is difficult to get the absolute reduction potential for a
particular reaction
o The reference cell that has universally been adopted for this purpose is the hydrogen half
o Potential of the reference half-cell is arbitrarily defined as zero to measure the potentials of various other electrode systems
against this reference cell

 If the E° values for two half reactions are

given, how can you predict potential
difference of the corresponding cell?

• Note the E° values for both half-cell reactions

Oxidize easily

• Predict which will oxidize and which undergo

reduction

• E°cell = (E°red – E°ox)

 Redox Chemistry
 Latimer diagram

𝑬𝒐𝟏 𝑬𝒐𝟐 𝑬𝒐𝟑 𝑬𝒐𝟒

An+7 An+6 An+4 An+3 An+2
𝑬𝒐𝟓

ΔG° is a state function but E° is not a state function i.e

ΔG =∑ ΔG but E ≠∑ E ΔG =∑ ΔG and ΔG° = - nFE°

nFE = -F ∑ 𝑛 E ⇒ E = ∑ 𝑛 E
 Redox Chemistry

nE = - 0.86
+ 5.17 + 0.09

1
E = 𝑛 E
𝑛
 Redox Chemistry
 Frost diagram

𝑬𝒐𝟏 𝑬𝒐𝟐
An+7 An+6 An+5
Disproportionation reaction
An+6  An+7 + An+5

Ox: An+6  An+7 + e ; 𝐸

Red: An+6 + e  An+5 ; 𝐸

ΔG° = (-)ve for a spontaneous reaction

E° = (+)ve for spontaneous cell reaction

E° = E𝒐𝑹𝒆𝒅 ‐ E𝒐𝑶𝒙 E𝒐𝟐 − E𝒐𝟏

E𝒐𝟐 > E𝒐𝟏

 Redox Chemistry
Write equations for the following reactions with the help of Frost diagram: N2O is bubbled into aqueous NaOH solution?