Chapter 9 Oxidation and Reduction

9.1 Oxidation and Reduction

Biochemical Oxygen Demand (BOD) and the Winkler Method
• BOD is used as a measure of the quality of water
• The concentration of dissolved oxygen (O2) in water is about 9 mgdm–3 at 20ºC
• The higher the BOD, the more organic waste is present in water – the more polluted it is
• BOD definition: the amount of dissolved O2 used or needed by aerobic biological
microorganisms in water to break down organic material present in a given water sample at a
certain temperature (usually 20 ºC) over a specific time period (usually 5 days)
• BOD levels:
- BOD of 1 to 2 is very good
- BOD of 3 to 5 is good
- BOD of 6 to 9 is poor
- BOD of 100 onwards is very polluted
• The basic principle in measuring BOD is to compare the amount of dissolved O2 in a sample of
water with the amount present when the sample has been incubated for 5 days at 20 ºC
• The Winkler Method is a technique used to measure dissolved O2 in freshwater systems
• Higher dissolved O2 concentrations –> lesser pollution
• The Winkler Method is performed on-site – delays will result in an alteration in O2 content due to
atmospheric equilibration
• Winkler Method
1. A sample bottle is filled completely with water – no air is left to skew the results
2. The dissolved O2 in the sample infixed by adding regents to form an acid compound – this
compound is then titrated with a neutralising compound to produce a colour change
3. The point of colour change is the endpoint – this coincides with the dissolved O2
concentration in the sample
• Winkler Method in alkaline conditions
- In alkaline conditions, Mn2+ ions are oxidised to Mn3+ by dissolved O2
- 4 Mn(OH)2 (s) + O2 (g) + 2 H2O (l) –> 4 Mn(OH)3 (s)
- The sample is shaken with excess Mn2+ and the resulting brown precipitate is reacted with
excess KI
- The KI is then oxidised to iodine
- 2 KI (aq) + 2 Mn(OH)3 (s) –> I2 (aq) + 2 Mn(OH)2 (s) + 2 KOH (aq)
- The I2 is then titrated with Na2S2O3 to determine the amount of O2 present (back titration)
- 2 S2O32– (aq) + I2 (aq) –> S4O62– (aq) + 2I– (aq)
• Winkler method in acidic conditions
- 2 Mn(OH)2 (s) + O2 (g) –> 2 MnO(OH)2 (s)
- MnO(OH)2 (s) + 4H+ (aq) + 2I– (aq) –> I2 (aq) + Mn2+ (aq) + 3 H2O (l)

Voltaic cells

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 • There are two types of

electrochemical cells – voltaic cells and electrolytic cells

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 • The potential difference between the metal and its aqueous solution may be positive or negative
depending on the position of the equilibrium

Standard hydrogen
electrode (SHE)
• A H+ / H2 half cell with an equilibrium established between H+ and H2 at standard conditions (298
K, 1.00 atm and 1.00 moldm–3)
• 2 H+ (aq) + 2 e– ⇌ H2 (g) – E = 0.00 V (arbitrarily assigned)
• Electrode potential varies with changes in temperature, partial pressure of gases and
concentration
of ions

Salt bridges
• A salt bridge is included to complete the electrical circuit by allowing the movement of ions
without introducing any more particles into the system
• It is also used to maintain electrical neutrality in the cell
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 • It consists if a glass type filled with an electrolyte solution with the ends stoppered by cotton wool
– this stops too much mixing of the contents of the salt bridge with the contents of the beakers
• The electrolyte is chosen that it does not react with the contents of either beaker – usually KCl,
NaCl or KNO3 is used

Standard electrode potential

• Standard electrode potential (E⦵) is defined as the potential difference between a standard
hydrogen electrode and a metal (the electrode) which is immersed in a solution containing the
metal ions at 1.00 moldm–3 concentration at 298 K and 1 atm
• Half cells can be classified into three main categories:
- A metal and its ions e.g. Cu2+ (aq) / Cu (s)
- A non-metal and its ions e.g. Pt (s) / Cl2 (g) / Cl– (aq)
- Two ions of the same element in different oxidation states e.g. Pt (s) / Fe3+ (aq), Fe2+

Notation
- Oxidation is written first and slashes represent phase boundaries
- Reduction is written second
- The double slash in the notation represents the salt bridge
- If more than one species in the same phase is present, a comma is used to separate them
- If there is no conducting solid species, platinum is used as the inert electrode

Standard cell potential

• Using the cell diagram, Ecell⦵ = ER⦵ – EL⦵where ER is the half cell on the right (reduction) and EL
is the half cell on the left (oxidation)
• If Ecell⦵> 0, the reaction is spontaneous
• ∆G⦵= – n x F x e where ∆G⦵ is the Gibbs free energy, n is the number of mol of electrons
involved, F is Faraday’s constant (96 500 Cmol–1) and e is the standard cell potential (the
Ecell⦵value determined earlier)

Uses of standard electrode potential (E⦵)

• Determining the strengths of oxidising and reducing agents
- Strong oxidising agents have high positive E⦵values and gain electrons easily
- Strong reducing agents have high negative E⦵values and lose electrons easily
• Predicting the direction of electron flow
- Electrons flow from the half cell with a more negative E⦵value to the half cell with a more
positive E⦵value
• Predicting the feasibility of a reaction
- E⦵cell > 0 – redox reaction is feasible
- E⦵cell = 0 – no net redox reaction
- E⦵cell < 0 – redox reaction is not feasible

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 - The reaction being unfeasible can be attributed to a high activation energy or the reaction not
taking place at standard conditions
- A positive E⦵cell value implies a negative ∆G⦵

Variation of electrode potential

• The variation of electrode potential is given by the Nernst equation
• At 298 K, E = E⦵+ (0.0592 / n) x log10 [ (oxidised form) / (reduced form) ]
• where E⦵is the standard electrode potential and
• n is the number of electrons transferred from the reduced form to the oxidised form

E⦵cell and the Gibbs free energy

• E⦵cell > 0 – redox reaction is feasible
• E⦵cell = 0 – no net redox reaction
• E⦵cell < 0 – redox reaction is not feasible
• ∆G⦵= – n x F x e where ∆ G is the Gibbs free energy, n is the number of mol of electrons
involved, F is Faraday’s constant (96 500 Cmol–1) and e is the standard cell potential (the
Ecell⦵value)

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