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Redox & Oxidation States

Oxidation is electron loss (OIL), reduction is electron gain (RIG). Oxidation states track electrons - the algebraic bookkeeping of redox chemistry.

Rules for assigning oxidation states
1.Elements in their standard state have OS = 0 (e.g. Fe, Oโ‚‚, Clโ‚‚).
2.Monatomic ions have OS equal to their charge (Naโบ = +1, Clโป = -1).
3.In compounds, O is usually -2 (except peroxides: -1, and OFโ‚‚: +2).
4.H is usually +1 (except metal hydrides: -1, e.g. NaH).
5.The sum of oxidation states in a neutral compound = 0.
6.The sum in a polyatomic ion = the ion charge.
MnOโ‚„โป + 8Hโบ + 5Feยฒโบ โ†’ Mnยฒโบ + 4Hโ‚‚O + 5Feยณโบ

Mn goes from +7 to +2 (reduced, gains 5eโป). Each Fe goes from +2 to +3 (oxidised, loses 1eโป). 5 iron atoms balance 1 manganese: 5 ร— 1eโป = 5eโป.

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Electrochemical Cells

A galvanic (voltaic) cell converts chemical energy to electrical energy via spontaneous redox reactions. An electrolytic cell does the reverse - uses electrical energy to drive a non-spontaneous reaction.

Cell components
Anode

Oxidation occurs here. Negative terminal in galvanic cells. Connected to + terminal of battery in electrolytic cells.

Cathode

Reduction occurs here. Positive terminal in galvanic cells. Connected to - terminal of battery in electrolytic cells.

Salt bridge

Maintains electrical neutrality by allowing ion flow between half-cells without mixing solutions.

External circuit

Carries electron flow from anode to cathode. This electron flow is the electric current.

๐Ÿง  An Ox, Red Cat - ANode OXidation, REDuction CATHode.
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Electrode Potentials & EMF

Standard electrode potential (Eยฐ) measures the tendency of a half-reaction to occur as a reduction, relative to the standard hydrogen electrode (Eยฐ = 0.00 V).

Key relationships
Standard conditions 1
Cell EMF Eยฐcell
Spontaneous? Eยฐcell
Relationship to ฮ”G ฮ”Gยฐ
Electrochemical series (selected)
Half-reactionEยฐ (V)Note
Liโบ/Li -3.04 V Strongest reducing agent
Naโบ/Na -2.71 V
Mgยฒโบ/Mg -2.37 V
Alยณโบ/Al -1.66 V
Znยฒโบ/Zn -0.76 V Below Hโ‚‚ = reducing agent
Feยฒโบ/Fe -0.44 V
Hโบ/Hโ‚‚ 0.00 V Reference electrode
Cuยฒโบ/Cu +0.34 V Above Hโ‚‚ = oxidising agent
Agโบ/Ag +0.80 V
Auยณโบ/Au +1.50 V Strongest oxidising agent (common)
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Electrolysis

Using electrical energy to drive a non-spontaneous redox reaction. Critical for industrial chemistry: aluminium extraction, chlorine production, electroplating, and hydrogen fuel production.

Industrial applications
Aluminium extraction

Alยณโบ ions in molten cryolite reduced at cathode. Huge energy requirement - aluminium smelting uses ~5% of UK electricity.

Chlor-alkali process

Electrolysis of brine (NaCl solution): Clโ‚‚ at anode, Hโ‚‚ at cathode, NaOH in solution. Three essential industrial chemicals from one process.

Electroplating

The object is the cathode. Metal ions in solution deposit onto it. Used for corrosion protection, decoration, and electrical contacts.

Hydrogen production

Electrolysis of water: 2Hโ‚‚O โ†’ 2Hโ‚‚ + Oโ‚‚. "Green hydrogen" when powered by renewables. Hโ‚‚ is an energy carrier for fuel cells.

Faraday's Laws: Faraday's First Law: mass deposited โˆ charge passed. Faraday's Second Law: same charge deposits molar masses proportional to M/n (n = electrons per ion). Q = It (charge = current ร— time). Moles of electrons = Q/F (F = 96,485 C/mol).