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Electrolysis

infoWhy this? Electrolysis shows how electrical energy can drive chemical change, producing useful metals and other substances from ionic compounds. Explaining electrode reactions through electron transfer helps us understand industrial extraction and its energy demands.

scheduleWhy now? Having studied ionic bonding and electrical circuits, we can now distinguish charge carried by ions in an electrolyte from charge carried by electrons in wires. Electrolysis brings these ideas together to explain how current produces chemical changes at electrodes.

neurologyYou need to know

  • Electrolysis is the decomposition of an ionic compound, called an electrolyte, using direct current electricity.
  • An electrolyte is a molten ionic compound or an ionic solution that contains mobile ions which can carry charge.
  • Electricity is the flow of electric charge, usually carried by moving electrons in wires and moving ions in electrolytes.
  • Ionic compounds must be molten or dissolved in water for electrolysis because their ions must be free to move to the electrodes.
  • The cathode is the negative electrode in electrolysis and attracts positive ions, called cations.
  • The anode is the positive electrode in electrolysis and attracts negative ions, called anions.
  • During electrolysis, cations gain electrons at the cathode, so cathode reactions are reductions.
  • During electrolysis, anions lose electrons at the anode, so anode reactions are oxidations.
  • Oxidation is loss of electrons and reduction is gain of electrons.
  • Metals more reactive than carbon are extracted by electrolysis, while many metals less reactive than carbon can be extracted by reduction with carbon or carbon monoxide.
  • In molten electrolysis, the metal forms at the cathode and the non-metal forms at the anode.
  • Aluminium is extracted by electrolysis of aluminium oxide dissolved in molten cryolite.
  • Cryolite lowers the melting point of aluminium oxide, reducing the energy needed for aluminium extraction.
  • In aluminium extraction, aluminium ions gain electrons at the cathode to form aluminium metal: `Al^{3+} + 3e^- \rightarrow Al`.
  • In aluminium extraction, oxide ions lose electrons at the anode to form oxygen gas: `2O^{2-} \rightarrow O_2 + 4e^-`.
  • The positive carbon anodes in aluminium extraction must be continually replaced because oxygen reacts with the hot carbon to form carbon dioxide.
  • In aqueous electrolysis, hydrogen is produced at the cathode if the metal ion is from a metal more reactive than hydrogen.
  • In aqueous electrolysis, the metal is produced at the cathode if the metal ion is from a metal less reactive than hydrogen.
  • In aqueous electrolysis, oxygen is produced at the anode unless the solution contains halide ions.
  • Halide ions are discharged at the anode in preference to hydroxide ions, producing chlorine, bromine, or iodine depending on the halide present.

rocket_launchYou must be able to

  • Identify the cathode and anode in an electrolysis cell by using the cathode as the negative electrode and the anode as the positive electrode.
  • Explain why an ionic compound must be molten or dissolved before electrolysis by referring to mobile ions carrying charge.
  • Classify electrode reactions as oxidation or reduction by checking whether electrons are lost or gained.
  • Write balanced half equations for cathode reactions by showing positive ions gaining the correct number of electrons.
  • Write balanced half equations for anode reactions by showing negative ions losing the correct number of electrons.
  • Predict the product at the cathode in aqueous electrolysis by comparing the metal ion with hydrogen in the reactivity series.
  • Predict the product at the anode in aqueous electrolysis by checking whether halide ions are present before predicting oxygen.
  • Describe aluminium extraction by naming aluminium oxide, molten cryolite, the cathode product, the anode product, and the need to replace carbon anodes.
  • Decide whether a metal should be extracted by electrolysis or reduction by comparing its position in the reactivity series with carbon.
  • Predict the products of electrolysis for a named aqueous ionic compound by applying the cathode and anode discharge rules.


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