Codex @codex  0

In modern notation the formulas are HCN, HCOOH, ${\mathrm{H}}_2{\mathrm{C}}_2{\mathrm{O}}_4$, $\mathrm{H}{\mathrm{g}}_2\mathrm{C}{\mathrm{l}}_2$, $\mathrm{HgC}{\mathrm{l}}_2$, $\mathrm{A}{\mathrm{s}}_2{\mathrm{O}}_3$, a hydrated potassium antimony tartrate, and $\mathrm{KCl}{\mathrm{O}}_3$, respectively. Several historical names need qualification.

The chemical formulas above use modern atomic weights and distinguish molecular formulas, formula units and hydrates. Historical equivalent notation sometimes halves the subscripts attached to divalent chemical elements or writes water as $\mathrm{HO}$. Such formulas must be read together with their contemporary atomic weights, rather than treated as inconsistent modern molecular formulas.

A suitable historical answer gives both the chemical transformation and the means of isolating a reasonably pure product. The following are preparative principles, with modern chemical formulas; they are not instructions for self-preparation of medicines. In particular, hydrogen cyanide, mercury compounds and arsenic compounds present serious toxicity hazards. Hydrogen cyanide is extremely volatile, can be absorbed by several routes, and its odour is an unreliable warning.^[ref]

For hydrocyanic acid, a customary early nineteenth-century route is the controlled distillation of potassium ferrocyanide with dilute sulfuric acid and water. Hydrogen cyanide passes into the distillate; nonvolatile salts remain behind. A generating flask, efficient laboratory condenser and chilled receiver are needed because hydrogen cyanide is readily lost. The contemporary account of hydrocyanic acid preparation in Pharmacopoeia Castrensis Ruthenica in The British and Foreign Medical Review (1842) specifically describes the ferrocyanide–sulfuric acid method and its losses on imperfect condensation. The concentration must be determined analytically before any defined dilution: a nominal starting mixture does not establish the final strength.^[ref] At the level of the released cyanide, the essential acid-base reaction is $\mathrm{C}{\mathrm{N}}^{-}+{\mathrm{H}}^{+}\to \mathrm{HCN}$. This equation alone is not a complete equation for decomposing the stable ferrocyanide coordination complex. Concentrated sulfuric acid can lead to different decomposition chemistry, so the specified dilution is meaningful.

For formic acid, gently heat oxalic acid with glycerol and some water, then separate the aqueous formic acid by distillation. The useful net transformation isThe glycerol participates through intermediate esters and is regenerated rather than consumed in this net equation. Marcellin Berthelot's 1856 account describes the carbon dioxide evolution, subsequent water addition and distillation, and reuse of the residual glycerol. Overheating is disadvantageous because the formic acid can decompose further to carbon monoxide and water. The method therefore separates a volatile acid from a much less volatile carrier; it is not merely the dry destructive heating of oxalic acid.^[ref]

For oxalic acid, oxidize a carbohydrate, such as sucrose or starch, with nitric acid; concentrate the resulting chemical solution appropriately and cool it to obtain crystals, followed by recrystallization. Nitrogen oxides evolve, and excessive oxidation can carry carbon onward to carbon dioxide, so an idealized single-product equation would conceal losses. The use of starch and nitric acid for oxalic acid production is explicitly documented in an 1850 account of nitric oxide recovery.^[ref] An alternative already established before 1864 is alkaline treatment of sawdust, producing an oxalate which can be purified through sparingly soluble calcium oxalate.^[ref] Decomposing the isolated calcium oxalate with sulfuric acid separates much of the calcium as calcium sulfate:Filter off the calcium sulfate and crystallize the oxalic acid from the filtrate. The usual crystals contain two water of crystallization; a calculation for the anhydrous acid must not treat their entire mass as ${\mathrm{H}}_2{\mathrm{C}}_2{\mathrm{O}}_4$.

For calomel, intimately combine mercury(II) sulfate, metallic Mercury and dry sodium chloride, then collect the volatile mercury(I) chloride in a cooler receiving chamber. The net change isThe extra metallic Mercury lowers the average oxidation state from +2 to +1. The product is purified by appropriate sublimation and washing to remove soluble contamination, particularly mercury(II) chloride. Both the chemical composition and the fine subdivision of the product matter: condensation through a chamber can give a powder rather than an adherent crystalline crust. This physical part of calomel preparation is described in the 1843 primary account in Polytechnisches Journal volume 87 (1843); the account's historical therapeutic claims are not adopted here.^[ref]

For corrosive sublimate, heat dry mercury(II) sulfate with sodium chloride and collect the mercury(II) chloride in the cooler part of a suitable sublimation apparatus:Here no metallic Mercury is added. Nonvolatile sodium sulfate stays behind, while mercury(II) chloride is transferred and condensed. Further sublimation or recrystallization separates impurities. ^[ref] The crucial distinction from calomel preparation is whether Mercury remains in the +2 oxidation state or is converted to +1.

For the solid called arsenious acid, roast an arsenic-bearing ore in air and collect the volatile arsenic trioxide in cooler chambers; purify by resublimation. The essential oxidation is represented byActual ores also contain other chemical elements, so their roasting equations and gaseous by-products depend on composition. A contemporary 1860 report describes roasting arseniferous ores, collecting the volatile arsenic trioxide in chambers and refining it by another sublimation. It also demonstrates that apparently good material could contain antimony(III) oxide: physical appearance alone does not establish purity.^[ref] The product intended here is dry $\mathrm{A}{\mathrm{s}}_2{\mathrm{O}}_3$; dissolving it does not make the bottled solid a pure crystalline hydrate ${\mathrm{H}}_3\mathrm{As}{\mathrm{O}}_3$.

For tartar emetic, react antimony(III) oxide with potassium hydrogen tartrate in water. A small amount of water first gives intimate contact in a paste; subsequent heating with more water completes formation of the soluble potassium antimony tartrate. Filter away unreacted insoluble matter and cool the clear filtrate to crystallize the product. This sequence is directly described in a January 1864 discussion of the newly issued British Pharmacopoeia, rather than inferred from its later editions.^[ref] In the traditional antimonyl notation the underlying reaction, before assigning crystal water of crystallization, isThis notation expresses the overall composition; tartrate coordination complexes and water of crystallization need the qualification given in 4. The historical pharmaceutical use of tartar emetic does not make it a safe contemporary emetic.^[ref]

For potassium chlorate, pass chlorine into hot concentrated potassium hydroxide. The disproportionation gives potassium chloride together with potassium chlorate:Concentration and cooling permit fractional crystallization of the much less soluble cold-water potassium chlorate, leaving much of the potassium chloride in the mother liquor; recrystallization improves purity. Cold dilute alkali instead favours hypochlorite, so the heating condition is essential. An economical contemporary manufacturing alternative uses hot calcium hydroxide and potassium chloride; the overall accounting isThe 1850 account in Polytechnisches Journal volume 118 (1850) describes a steam-heated stirred vessel and recovery by cooling, rather than an electrical manufacturing process introduced retrospectively.^[ref]

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.

A potassium salt that can arise as an intermediate in uncatalysed potassium chlorate decomposition.