Purified coal gas is mainly molecular hydrogen, methane and carbon monoxide, with smaller quantities of other hydrocarbons and diluent gases. It is made by heating coal in retorts with little or no admitted air, not by completely burning the coal.
The hot products include permanent gases, condensable organic vapours and water vapour, leaving coke in the retort. Cooling removes much of the coal tar and condenses water, which captures Ammonia as ammoniacal liquor. Further washing and purification remove much of the remaining Ammonia, hydrogen sulfide and other objectionable constituents before the gas is distributed. A crude retort product and purified household coal gas therefore have different compositions.
Molecular hydrogen is commonly the largest component by volume. Methane is another major combustible constituent, while carbon monoxide contributes fuel value and serious toxicity. Ethylene and other unsaturated hydrocarbons, together with vapours such as benzene, contribute strongly to the luminous flame. Their thermal breakdown can produce incandescent soot, explaining why a small fraction of heavier hydrocarbons can disproportionately affect lighting quality. Smaller or variable quantities of carbon dioxide and molecular nitrogen dilute the combustible mixture. Molecular oxygen is not an intended major constituent; air ingress can change the mixture.
There is no single balanced chemical equation for making coal gas: coal is a complex feed and produces many products simultaneously. Nor is one exact percentage composition universal; it depends on the coal, retort temperature, operating conditions and purification. The main distinction is between the light combustible gases, the smaller illuminating hydrocarbon fraction, and contaminants or diluents. Modern natural gas, usually rich in methane, should not be used as a synonym for historical coal gas.
The conventional nineteenth-century answer is diamond, graphite and so-called amorphous carbon. These exhibit strikingly different physical properties while sharing the same chemical element, carbon.
Diamond is a crystalline, usually transparent form, very hard and ordinarily an electrical insulator. Its three-dimensional covalent bond network joins each carbon chemical atom to four neighbours. Graphite is a dark, soft, crystalline form with layered bonding; easy shear between layers makes it useful for marking and lubrication. Its electronic structure permits much greater electrical conductivity than that of ordinary diamond.
The historical “amorphous” class includes charcoal, coke, lampblack and soot, as well as carbon-rich materials such as gas-retort carbon. Such names describe preparation and texture as well as structure: restricted-air heating of wood gives charcoal, destructive distillation of coal gives coke, and incomplete combustion of a carbon-bearing fuel produces soot. Modern structural examination shows that these materials can contain small, imperfect graphitic regions. They are not necessarily one distinct pure allotrope. Coal itself is a chemically complex, impure carbon-rich material, rather than a pure form of the chemical element.
A common chemical connection is that pure samples of these carbon forms can yield carbon dioxide upon complete combustion in excess oxygen:
Their different hardness, appearance and electrical conductivity arise from structure and impurities, rather than from being different chemical elements. This is the explanatory role of allotropy.
Modern lists also include fullerenes, carbon nanotubes and graphene. These are useful present-day extensions, not discoveries to credit to the 1867 candidate.[ref]
The wick supplies liquid wax by capillary action; wax vapour reacts with atmospheric oxygen, releasing the heat that keeps the supply going. The wick is a delivery system, rather than the principal fuel.
First, an external flame warms the wick and adjacent wax. Melting produces a small liquid reservoir, and capillary action draws it into the spaces between the wick fibres. Near the hot tip, evaporation and some pyrolysis supply gaseous fuel. Melting and evaporation are physical changes; pyrolysis and combustion change the chemical substances present. Once established, the candle flame transfers enough heat back to the wax to maintain this sequence.[ref]
The candle flame is a diffusion flame. Its relatively dark inner region contains newly supplied fuel with limited access to oxygen. In the yellow luminous region, incomplete conversion of the hydrocarbons produces small soot particles, which become incandescent. Farther out, mixing supplies enough oxygen to consume most of the remaining fuel, carbon monoxide and soot. Thus the yellow light is largely thermal emission from hot particles, rather than a yellow gas.[ref]
For a representative alkane component of paraffin wax, complete combustion has the chemical equation
Real candle materials are mixtures, and some, such as fatty materials, already contain oxygen; the displayed chemical equation is an illustrative wax model. The principal products of complete combustion are carbon dioxide and water vapour. Convection carries the hot gases upward and brings fresh air into the flame. A cold collector can reveal condensed water; collecting the gases and passing them into limewater gives a calcium carbonate cloudiness from carbon dioxide.
Removing the oxygen supply, cooling the reaction zone, or cutting off wax delivery extinguishes the flame. The smoking wick immediately afterwards can still emit combustible vapour; without sufficient heat at the mixing zone, that vapour need not sustain a flame.
Distinguish diseases caused by inhaled air pollutants from infections transmitted through air. The principal impurity groups are gases and vapours, suspended particles and biological material; detection must identify the particular group and, where possible, measure its concentration.
The nineteenth-century phrase “impure air” mixed several different mechanisms. Irritant smoke and dust can damage the respiratory system; toxic gases can poison without causing an infection; crowded, poorly ventilated rooms can increase exposure to infectious material. The historical miasma theory treated foul emanations much more broadly as generators of disease. In particular, the smell of sewage does not itself establish the cause of typhoid fever, cholera or malaria.
For the first part, important real consequences include the following:
For the second part, ordinary outdoor air already contains nitrogen, oxygen, a small amount of carbon dioxide, and variable water vapour. Their presence alone is not evidence of pollution. In a smoky industrial town, soot, mineral dust, products of fuel combustion and sulfur dioxide would be particularly relevant. In occupied rooms, expired carbon dioxide, water vapour and suspended biological material increase unless removed. Decomposing wastes may contribute Ammonia, hydrogen sulfide and other volatile products. The actual mixture depends on sources, ventilation and weather.
For the third part, begin with a defined sampling site and time, record occupancy or industrial activity, and compare with a suitable reference. A volume of air, not simply an unrecorded sniff or a discoloured paper, is the basis of quantitative comparison. Methods available by 1867 include:
The chemical equations underlying two of these qualitative tests are
Here the precipitates are barium carbonate and lead sulfide. For the baryta absorption method, in an ideal, fully captured sample with no interfering acid gases, the difference between blank and sample acid requirements satisfies
where is the amount concentration of titratable acid equivalents and the volumes refer to titration of the entire corresponding absorbent portions; any aliquot requires its scale factor. The factor two follows from the two acid equivalents neutralized per mole of barium hydroxide. This calculation assumes that the barium carbonate precipitate is excluded from the residual-base determination; dissolving it again with the titrant would invalidate the inference.
Odour, visible smoke and room stuffiness are useful prompts to investigate, but no single smell, carbon dioxide value, microscopic field or chemical colour test establishes that air is free of harmful impurities. Specify which material was measured and which uncertainty remains.