A typical cell consists of:
- Two different metal electrodes (e.g. Mg and Cu).
- Each metal placed in a solution containing its own ions (e.g. Mg in MgSO₄(aq), Cu in CuSO₄(aq)).
- A salt bridge connecting the two solutions.
- A metal wire and external circuit connecting the two electrodes (possibly with a voltmeter or bulb).
- Consider a cell made from magnesium and copper: $$\mathrm{Mg}(\mathrm{~s})+\mathrm{Cu}^{2+}(\mathrm{aq}) \rightarrow \mathrm{Mg}^{2+}(\mathrm{aq})+\mathrm{Cu}(\mathrm{~s})$$
- This overall reaction is spontaneous (favourable), and the cell uses it to generate a current.
- At the magnesium electrode (anode): oxidation $$\operatorname{Mg}(\mathrm{s}) \rightarrow \operatorname{Mg}^{2+}(\mathrm{aq})+2 e^{-}$$
- Mg loses electrons → it is oxidised.
- This electrode is the anode (oxidation always occurs at the anode).
- Released electrons enter the external wire.
- At the copper electrode (cathode): reduction $$\mathrm{Cu}^{2+}(\mathrm{aq})+2 e^{-} \rightarrow \mathrm{Cu}(\mathrm{~s})$$
- Cu²⁺ gains electrons → it is reduced.
- This electrode is the cathode (reduction always occurs at the cathode).
- Solid copper is deposited on the copper electrode.
- Electron Flow and Energy Conversion
- Electrons flow from anode to cathode through the external circuit (Mg → Cu).
- This flow of electrons provides electrical energy that can power a device (e.g. a light bulb).
- The driving force is the difference in tendency of the two metals to lose/gain electrons (their reduction potentials).
- So, a voltaic cell converts the chemical energy of a spontaneous redox reaction into electrical energy (a current in the wire).
- The salt bridge is usually a tube or strip filled with an inert electrolyte (e.g. KNO₃ or K₂SO₄ in gel or solution).
- It does not conduct electrons – those travel in the external wire.
- Instead, the salt bridge:
- Allows ions to move between the half-cells.
- Maintains electrical neutrality (charge balance) in each solution.
In the Mg/Cu cell:
- At the anode half-cell:
- Mg²⁺ ions build up in solution → the solution becomes positively charged.
- Negative ions (e.g. SO₄²⁻ from the salt bridge) move into the Mg²⁺ solution to balance the charge.
- At the cathode half-cell:
- Cu²⁺ ions are removed from solution as they plate onto the cathode → solution becomes relatively negative.
- Positive ions from the salt bridge (e.g. K⁺ or Na⁺) move into this half-cell to balance the charge.
Key idea: The salt bridge keeps each half-cell electrically neutral, allowing the redox reaction (and electron flow) to continue.
Without it, charge would build up and the cell would quickly stop working.
- Not all metals are equally willing to lose electrons.
- This tendency is described by standard reduction potentials, E°, typically listed in an electrochemical series.
- Reactions are written as reductions (gain of electrons).
- A more positive E° value → species is more easily reduced (better oxidising agent).
- A more negative E° value → species is more easily oxidised (better reducing agent).
- When two half-cells are combined into a cell:
- The half-cell with the higher E° becomes the cathode (reduction).
- The half-cell with the lower E° becomes the anode (oxidation).
- For a cell: $$\text { anode ||cathode }$$
- The standard cell potential is: $$E_{\text {cell }}^{\circ}=E_{\text {cathode }}^{\circ}-E_{\text {anode }}^{\circ}$$
- If E°cell is positive, the cell reaction is spontaneous under standard conditions.
Zn/Cu Cell
Overall reaction: $$\mathrm{Zn}(\mathrm{~s})+\mathrm{Cu}^{2+}(\mathrm{aq}) \rightarrow \mathrm{Zn}^{2+}(\mathrm{aq})+\mathrm{Cu}(\mathrm{~s})$$
Suppose:
- $E^{\circ}\left(\mathrm{Cu}^{2+} / \mathrm{Cu}\right)=+0.34 \mathrm{~V}$
- $E^{\circ}\left(\mathrm{Zn}^{2+} / \mathrm{Zn}\right)=-0.76 \mathrm{~V}$
Then:
- Cathode (reduction): $\mathrm{Cu}^{2+} / \mathrm{Cu}, E^{\circ}=+0.34 \mathrm{~V}$
- Anode (oxidation): $\mathrm{Zn} / \mathrm{Zn}^{2+}, E^{\circ}=-0.76 \mathrm{~V}$ $$E^{\ominus}_{\text {cell }}=(+0.34)-(-0.76)=+1.10 \mathrm{~V}$$
- Positive $E^{\ominus}_{\text {cell }}$ → reaction is spontaneous.
- The cell can produce around 1.1 V under standard conditions.
Students sometimes add the reduction potentials incorrectly or forget which is anode/cathode. Always use: $$E_{\text {cell }}^{\circ}=E_{\text {cathode }}^{\circ}-E_{\text {anode }}^{\circ}$$ and remember that the anode is the electrode where oxidation occurs.
- The electrolyte is the ionic solution in each half-cell and inside the salt bridge. Its properties affect:
- The concentration of ions near each electrode.
- The rate of the redox reactions.
- The actual cell voltage (which can deviate from E° if concentrations differ).
- Important points:
- The electrolyte must be compatible with the half-cells (no unwanted side reactions).
- It should be reasonably concentrated to allow good ion movement.
- It should be inert – it should not itself be easily oxidised or reduced.
Electrochemical cells are at the heart of many devices: from TV remotes and phones to electric cars and medical implants.
We broadly divide them into:
- Primary cells – non-rechargeable.
- Secondary cells – rechargeable.
- Fuel cells – continuously supplied with fuel.
- Example: Alkaline batteries (Zn–MnO₂)
- Common in remote controls, toys, torches.
- Zinc (anode) is oxidised, manganese dioxide (cathode) is reduced.
- Electrolyte is an alkaline paste (often KOH).
- Advantages:
- Cheap and widely available.
- Good shelf life.
- Convenient for low-power, intermittent use.
- Limitations:
- Not rechargeable → become waste after use.
- Contain materials that must be disposed of properly to avoid pollution.
- Examples:
- Lead–acid batteries – used in car starter batteries.
- Nickel–cadmium (NiCd) – older power tools (now less common due to toxicity issues).
- Lithium-ion batteries – phones, laptops, electric vehicles.
- Advantages:
- Rechargeable – can be used many times, reducing waste.
- Can deliver high current for power tools or car starters.
- Li-ion has high energy density → lots of energy for its mass (ideal for portable electronics and EVs).
- Limitations:
- Limited lifetime (number of charge–discharge cycles).
- Some use toxic or rare metals (e.g. cadmium, cobalt).
- Require careful charging control to avoid overheating or damage.
- Recycling and disposal must be handled properly to avoid environmental harm.
- Fuel cells use a continuous supply of fuel (like hydrogen) and an oxidant (usually oxygen from air) to produce:
- Electricity
- Water (often the main by-product)
- Advantages:
- High efficiency compared to combustion engines.
- Low emissions – hydrogen fuel cells produce mainly water vapour.
- Useful for vehicles, backup power systems, and portable power.
- Limitations:
- Hydrogen production often requires a lot of energy (e.g. electrolysis), which may not be from renewable sources.
- Requires infrastructure for safe storage and distribution of hydrogen.
- Fuel cell systems can be expensive and complex.
Advantages
- Convert chemical energy directly to electrical energy (no moving parts in the cell).
- Can be portable and used far from the power grid.
- Can be tailored:
- small cells for electronics,
- large packs for EVs,
- fuel cells for clean power.
- Potential for low-emission energy systems when combined with renewable fuel sources.
Limitations
- Energy losses as heat; efficiency is not 100%.
- Dependence on finite or rare materials (e.g. lithium, cobalt, platinum).
- Environmental issues with mining, manufacturing, and disposal.
- Limited lifetime for rechargeable cells; performance degrades over time.
- Infrastructure challenges (especially for hydrogen fuel cells).
- In a Mg/Cu electrochemical cell,
- which electrode is the anode and which is the cathode?
- which species is oxidised and which is reduced?
- Compare primary, secondary and fuel cells in terms of:
- rechargeability
- typical uses
- at least one advantage and one limitation for each.