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Oxygen can be obtained by decomposing an oxygen-rich chemical compound, or by separating it from air. For the historical laboratory, heating potassium chlorate, heating certain metal oxides, and electrolysis of water are useful examples. The substance collected is molecular oxygen, ${\mathrm{O}}_2$.

A common preparation heats potassium chlorate, often with manganese dioxide as a catalyst:A heat-resistant vessel and delivery tube conduct the evolved gas to an inverted collecting vessel over water, after the initial displaced air has been excluded. Oxygen is only slightly soluble in water, making this collection principle useful. The manganese dioxide changes the reaction rate and required heating conditions; it is not the net source of the oxygen in this catalysed balance. Without the catalyst, potassium perchlorate can occur as an intermediate.

Two older preparations use heated metal oxides:The first explains the historical decomposition of mercury(II) oxide, with metallic Mercury deposited on cooler parts of the apparatus. It is historical chemistry, not a preferred present-day teaching preparation. The second is one stage in the reduction of manganese dioxide; at still higher temperature further oxygen loss can give ${\mathrm{Mn}}_3{\mathrm{O}}_4$, so the oxide residue depends on the conditions. Strong heating of potassium nitrate provides another net balance:In electrolysis, suitable separated electrodes collect oxygen at the anode and hydrogen at the cathode. With a suitable electrolyte and electrodes, the net chemical equation isThe gases must be kept in separate collecting spaces if the experiment is to demonstrate their separate identities and the approximately $2:1$ volume ratio. Choice of electrolyte matters: a chloride-containing electrolyte can give chlorine instead of clean oxygen evolution.

For a modern small-scale comparison, catalytic decomposition of hydrogen peroxide givesThis is a different feedstock from potassium chlorate. Large-scale separation of oxygen from air by cryogenic fractionation belongs to later industrial practice and should not be substituted for an 1866 laboratory answer. A collected sample can be tested by its vigorous support of combustion, conventionally the relighting of a glowing splint; this observation identifies a property, while the preparation and exclusion of interfering gases establish the sample's provenance.

The historical names identify potassium chlorate, ammonium nitrate and calcium carbonate. Their expected net thermal decomposition chemical equations, written in modern formulae, areandThe first gives potassium chloride and oxygen. A potassium perchlorate intermediate can occur during uncatalysed heating; the first chemical equation gives the final overall balance. The second represents the familiar nitrous oxide pathway, with hot water initially as vapour. It does not mean that ammonium nitrate has only one decomposition pathway: conditions, impurities and confinement can produce different gases and violent decomposition.^[ref]

The third is calcination of limestone to quicklime. Its extent depends on temperature and the partial pressure of carbon dioxide; removing carbon dioxide favours further decomposition. Reversing the process gives carbonation of calcium oxide.

For dissolution in hydrochloric acid, the corresponding balances areand“Magnesia” here means magnesium oxide, and “alumina” means aluminium oxide. Zinc undergoes an oxidation-reduction reaction, reducing hydrogen ions to molecular hydrogen. The oxides instead undergo acid-base reactions: hydrogen ions convert oxide into water, without hydrogen evolution. The chlorides are dissolved species in water, rather than anhydrous molecular salts necessarily existing intact in the solution. Strongly ignited aluminium oxide may dissolve slowly; the balance does not determine the rate.