Past exam of the medicine course of the University of Oxford / 1867 / First examination / Chemistry (No. IV.)

Original volume: Examination papers for the Degree of Bachelor of Medicine by the University of Oxford (1864–1867). Original scanned volume, PDF page 83. Oxford, December 1867.

Original questions are transcribed from the public-domain edition. Credit: Wellcome Collection; original supplied by Royal College of Physicians, London. Source and public-domain rights statement.

The explanations retain the historical meanings of the names while using modern chemical formulas and atomic weights. Historical analytical methods are distinguished from present water quality assessment.

What is meant by a combustible substance ?

A combustible substance can sustain a sufficiently rapid, heat-producing chemical reaction with a suitable oxidizing agent. In ordinary air this usually means combination with molecular oxygen, producing enough heat to maintain the reaction after ignition. A visible flame is not essential: carbon can glow as it undergoes combustion.

Combustibility depends on the surroundings and experimental conditions. A cold block of wax does not ignite merely because it meets air: heating must first provide combustible vapour and overcome the kinetic barrier to reaction. Finely divided iron burns much more readily than a massive bar because more surface is exposed per unit mass. Nor is oxygen universally required: molecular hydrogen can undergo combustion in chlorine. The expression “supports combustion” identifies the surrounding reactant in a particular experiment; it does not establish an absolute division between two kinds of chemical substance.

Give an account of the physical and chemical changes which constitute the burning of a candle.

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 equationReal 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.

How is bleaching-powder made ? What are its chief properties ?

Bleaching powder is made by passing chlorine over slaked lime, exposing a large surface of the powder to the gas. The contemporary name “chlorinated lime” is more informative than treating it as pure calcium chloride. The 1867 British Pharmacopoeia (1867) describes this manufacture and a dull-white, partly water-soluble powder with bleaching and disinfecting properties.^[ref]

An idealized overall chemical equation isThe chlorine undergoes disproportionation: one part becomes chloride, with oxidation state $-1$, and another becomes hypochlorite, with oxidation state $+1$. Commercial bleaching powder contains residual calcium hydroxide, water and chlorine-bearing solid phases; the chemical equation is a useful composition balance, not a claim that the powder is one pure molecular substance or simply a fully characterized mechanical mixture. The old formula ${\mathrm{CaOCl}}_2$ is an abbreviated representation, not the formula of pure calcium hypochlorite, ${\mathrm{Ca}(\mathrm{OCl})}_2$.

Its chief properties follow from the hypochlorite chemistry. The aqueous extract is alkaline and oxidizing. The chemical equilibriumproduces hypochlorous acid on lowering the pH. Oxidation of coloured organic compounds can destroy the chromophores responsible for their colour. This is irreversible chemical alteration of a dye, rather than merely washing it away. The historical description that bleaching works through “nascent oxygen” is not a necessary modern mechanism: hypochlorous acid and related reactive chlorine species themselves react with substrates.

With sufficient hydrochloric acid, the hypochlorite and chloride can generate chlorine:This explains acid-induced gas evolution and why acidification is not an innocuous way to use a bleaching material. Exposure, moisture and heating can reduce the stored oxidizing strength. Its useful strength is measured as available chlorine, rather than inferred from the powder's total mass or its smell; inert material and residual lime do not provide the same bleaching capacity.

Write equations expressing the changes which take place when chlorate of potash, nitrate of ammonia, and carbonate of lime, are decomposed by heat ; also when zinc, magnesia, and alumina, are dissolved in hydrochloric acid.

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.

How is the atomic theory related to the laws of definite and of multiple proportions ?

Atomic theory explains fixed composition by fixed numbers of chemical atoms, and multiple proportions by different small whole-number combinations of the same chemical atoms. The two laws are empirical regularities which the theory explains; they are not themselves direct observations of individual chemical atoms.

For the law of definite proportions, suppose a pure chemical compound has composition ${\mathrm{A}}_x{\mathrm{B}}_y$. If the atomic masses are $m_A$ and $m_B$, every formula unit contains masses $x{m}_A$ and $y{m}_B$. Enlarging the sample multiplies both by the same number, soThe mass ratio is therefore independent of sample size or preparation route, provided the same pure stoichiometric chemical compound is obtained. Ordinary water supplies an example: its hydrogen-to-oxygen mass ratio is approximately $1:8$.

For the law of multiple proportions, compare ${\mathrm{A}}_x{\mathrm{B}}_y$ and ${\mathrm{A}}_u{\mathrm{B}}_v$. At a fixed mass of A, the masses of B are in the ratioThis is a ratio of integers, and is often a ratio of small integers for simple chemical compounds. With carbon monoxide and carbon dioxide, about $12$ mass units of carbon combine with about $16$ and $32$ of oxygen: the oxygen masses are in the ratio $1:2$. The chemical formulas explain why adding a second oxygen chemical atom doubles the oxygen contribution without changing the carbon contribution.

The laws alone do not uniquely determine the correct chemical formulas or the atomic weights; independent information is needed to distinguish, for example, one formula unit from a multiple of it. Modern qualifications include variations in isotopic composition and non-stoichiometric compounds. These refine the simple nineteenth-century formulation without removing its usefulness for pure compounds of fixed composition.

What are the relative specific gravities of carbonic acid, carbonic oxide, nitrous oxide, air, ammonia, olefiant gas, and the vapours of alcohol and ether ?

Take dry air as unity, and compare each gas at the same temperature and pressure. In the ideal gas approximation, $\rho =pM/(RT)$, so the relative density isHere $M$ is molar mass. The following values use modern approximate molar masses; rounding and historical atomic weight conventions can shift the last figures.

“Olefiant gas” is confirmed as a historical synonym of Ethylene in the NIST Chemistry WebBook, SRD 69. In this gas list, “carbonic acid” means carbon dioxide, not an isolated vapour of aqueous ${\mathrm{H}}_2{\mathrm{CO}}_3$. “Alcohol” and “ether” refer to ethanol and diethyl ether, rather than their entire modern chemical classes.^[ref]

The order is therefore Ammonia, then carbon monoxide and Ethylene nearly tied, then air, then carbon dioxide and nitrous oxide nearly tied, then ethanol vapour, then diethyl ether vapour. Nearly equal molar masses do not imply equal chemical behaviour.

If instead molecular hydrogen is chosen as unity, divide each molar mass by about $2.016\mathrm{g}\mathrm{mo}{\mathrm{l}}^{-1}$ and state that convention. In the older nominal ${\mathrm{H}}_2=2$ approximation, the corresponding values are about $22,14,22,14.5,8.5,14,23,37$ in the source order. These are a different reference scale, not different substances.

The vapour comparisons are not comparisons of the liquid densities. Pure ethanol and diethyl ether must be considered at conditions where they remain gaseous, or by a low-pressure gas approximation. Their liquids can be lighter than water while their vapours are heavier than air.

Name some fluids that are heavier and some that are lighter than water.

Examples heavier than water are Mercury, glycerol and concentrated sulfuric acid; examples lighter than water are ethanol and diethyl ether. “Heavier” here means greater mass for the same volume, rather than greater total mass in arbitrarily sized samples.

Representative room-temperature relative densities, with water as unity, are

These are illustrative values, not exact constants independent of temperature or composition. Dilution changes the density of sulfuric acid, glycerol and ethanol solutions.^[ref][ref]

A distinction from simply observing a floating layer is essential: ethanol is miscible with water, so it mixes rather than remaining as a permanent upper layer. Diethyl ether has limited water solubility and can form an upper layer. More broadly, gases are also fluids, but the natural comparison intended here is between liquids; air at ordinary conditions is much less dense than liquid water.

What is steel? Give a short account of the processes by which it is obtained from an ore of iron.

Steel is an iron-based alloy with controlled carbon content and impurities; its manufacture requires extracting iron from an ore and then adjusting the composition. In a modern plain-carbon classification, steel generally contains less than about $2\%$ carbon by mass, whereas pig iron is more carbon-rich. The historical practical contrast was with low-carbon wrought iron and readily cast but relatively brittle cast iron. Hardening by quenching is characteristic of suitable carbon-rich steels, but not every grade hardens in the same way.

Begin, for example, with an iron oxide ore. Preparation removes some earthy matter and, where appropriate, roasting expels moisture or converts a carbonate-bearing ore to oxide. A blast furnace receives the ore, coke and a flux such as limestone. The hot air blast sustains combustion of coke, generating heat and the carbon monoxide needed for much of the oxide reduction. Representative overall balances areCalcination of limestone provides calcium oxide. Combination with acidic gangue, represented by silica, gives a liquid slag:Actual slag is a multicomponent melt, rather than necessarily pure calcium silicate. The descending iron picks up carbon and other impurities and collects as molten pig iron. This first extraction product is not already finished steel.

Two important routes available in 1867 proceed from this stage. In the older indirect route, refining and puddling oxidize much of the carbon and remove slag-associated impurities to obtain wrought iron. Bars packed with charcoal are then heated for a prolonged period in the cementation process. Carbon enters the bars, giving blister steel; forging and welding can make shear steel, while melting suitable stock in covered crucibles produces more uniform crucible steel. The bar can acquire carbon through gas-mediated surface reactions and diffusion; the process should not be imagined as intact charcoal grains travelling through the iron.

In the Bessemer process, an air blast passes through molten pig iron in a converter. Oxidation of silicon, manganese and carbon supplies heat, while lowering the carbon content. Composition can be corrected by adding a controlled carbon- and manganese-bearing material such as spiegeleisen. Henry Bessemer's 1856 patent describes the central idea of maintaining the conversion by oxidizing constituents of the molten metal, without fuel for reheating during that stage.^[ref]

The early acidic converter demanded suitable feed: it did not solve removal of phosphorus from every ore. Later basic converter practice must not be silently imported into a December 1867 account. Final casting, working and heat treatment determine the steel microstructure and properties as well as composition. The useful manufacturing chain is therefore ore → extracted carbon-rich iron → controlled composition → worked and appropriately heat-treated steel.

How would you examine a sample of water suspected of sewage contamination ?

Combine investigation of the source with several independent analyses; a clear appearance or a single negative chemical test cannot exclude sewage pollution. No sample results are supplied, so the answer is an examination scheme rather than a finding about an actual water sample.

Record where and when the water was collected, recent rainfall, proximity of drains and cesspits, and possible routes from sewage to the supply. Compare with a credible uncontaminated sample from the same geological setting. Use clean, suitably closed vessels and examine promptly; contamination introduced during sampling and chemical changes during storage can both mislead. Separate portions are needed when one analysis alters the sample for another.

For an 1867 investigation, inspect colour, turbidity and sediment, and examine concentrated sediment by microscopy for suspicious organic debris. These observations can motivate further work but cannot identify all disease-causing agents. Determine residue after evaporating a measured volume; carefully heating that residue may reveal charring or a volatile fraction. Loss on ignition is not a specific measure of sewage: mineral constituents can also change on heating, and some organic material can be lost during evaporation itself.

Test a separate aliquot for chloride, for example by silver nitrate precipitation, and compare its quantity with local background. Elevated chloride can accompany sewage but also comes from natural salts. Examine Ammonia or ammonium and oxidized nitrogen, nitrite and nitrate. Organic nitrogen can be converted during decomposition and nitrification, so an old contamination may have little free Ammonia. Conversely, a nitrogen signal alone does not establish its origin.

An oxidant-consumption experiment with a known amount of potassium permanganate, under controlled reaction time, temperature and acidity, supplies another comparison. Residual oxidant is measured against a reagent blank. A large consumption indicates oxidizable material, but reducing inorganic constituents also consume oxidant, while some organic materials react incompletely. It is therefore an operational test, not a direct count of sewage organisms.

A method actually reported in June–July 1867 first distils off free Ammonia, then uses alkaline permanganate to generate further Ammonia from some organic nitrogen. A boiling flask, condenser and successive receiving vessels separate the fractions, whose Ammonia can be compared by colour with standards using Nessler's reagent. The later fraction became known as albuminoid ammonia. It is neither proof of the presence of albumen specifically nor complete conversion of every organic nitrogen compound. Contemporary discussion already disputed how different substances behaved in the preliminary distillation.^[ref]

A present-day assessment adds validated microbiological water testing, including a specific Escherichia coli test using culture or an accepted equivalent, together with quality control and a sanitary survey. Escherichia coli is an indicator of faecal contamination, not a label for all sewage-derived pathogens. The Australian drinking water guideline specifies none detected in a $100\mathrm{mL}$ sample and notes that the indicator does not reliably represent all enteric viruses or protozoa.^[ref]

The justified conclusion comes from the combined evidence and the detection limits. Chemical indicators can support a sewage-contamination hypothesis, but chemical clarity or a negative result in one aliquot is not a certificate of microbiological safety. This modern distinction should not be attributed to an examiner as a fully developed 1867 laboratory protocol.

Describe iodine. Whence is it derived ?

Iodine is a dark, lustrous crystalline halogen which gives a violet vapour; historically, an important source was the ash of iodine-rich seaweeds. Elemental iodine commonly occurs as diatomic ${\mathrm{I}}_2$. It melts at about $114{}^{\circ }\mathrm{C}$ and boils at about $184{}^{\circ }\mathrm{C}$ at ordinary atmospheric pressure. It also undergoes sublimation below its melting point, depositing crystals again on a cooler surface.^[ref]

Iodine is sparingly soluble in water, giving a brownish solution, and dissolves more freely in ethanol and in an aqueous iodide solution. In the latter case the chemical equilibriumforms triiodide. Iodine with starch, under suitable conditions, gives a sensitive dark-blue colour; this is a useful recognition test, but oxidants that liberate iodine from added iodide must be distinguished from iodine initially present. Reaction with reactive metals gives iodides; in such compounds the iodine usually has oxidation state $-1$.

For the historical seaweed route, collect and burn iodine-accumulating seaweeds to produce kelp ash, then extract the soluble salts with water. Crystallization removes much of the common salt content, leaving an iodide-enriched mother liquor. Oxidation releases iodine, which can be distilled or sublimed and collected on a cool surface. One representative net chemical equation for liberation from iodide isThe manganese dioxide is the oxidizing agent; the seaweed does not contain a supply of ready-made violet iodine crystals. This describes the chemical principle of a historical extraction, rather than prescribing one unique factory recipe.

Iodine also occurs in natural brines and in iodate-bearing deposits associated with nitrate ores. Modern industrial supply relies heavily on brines and iodate ores; it should not be equated with the seaweed source emphasized in nineteenth-century teaching.^[ref]

In what forms does carbon appear ?

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]

How may a liquid be tested for hydrocyanic acid, and the quantity present be estimated ?

Confirm hydrogen cyanide by chemical tests on a suitable separated fraction, then estimate its amount with a defined quantitative assay. Here “hydrocyanic acid” means $\mathrm{HCN}$ in water, also historically called prussic acid. Smelling or tasting is not an analytical test: hydrogen cyanide is acutely poisonous, and its characteristic odour is not reliably perceived.^[ref]

A coloured or complex liquid can mask the tests or contain interfering ions. Historically, controlled distillation separated volatile hydrogen cyanide from many nonvolatile constituents; a receiving solution captures the analyte. In a modern analytical apparatus, the closed transfer system includes a condenser and an alkaline gas absorber. The receiver converts volatile hydrogen cyanide into less volatile cyanide:The measured fraction must be defined: free hydrogen cyanide in the original liquid is not automatically identical to “total cyanide” released from complexes by a more aggressive preparation. A blank, a known positive control and recovery checks help distinguish a negative sample from failed separation or reagent failure.^[ref]

For the historical iron test, make a separate test portion alkaline, introduce fresh iron(II) salt together with an iron(III) source, and finally acidify as specified by the historical procedure. Cyanide first forms ferrocyanide with iron(II); iron(III) then gives the characteristic Prussian blue precipitate. Idealized balances explaining the recognition chemistry areReal Prussian blue can be hydrated and nonstoichiometric; the second chemical equation is a useful idealization. The acid stage also removes obscuring iron hydroxide precipitates. These steps explain the old mixed iron-salt test, rather than assuming that cyanide simply reacts directly with any iron salt to give blue material.^[ref]

A second aliquot can be examined with silver nitrate. Silver cyanide is white, but whiteness alone is not specific because silver chloride and other precipitates can interfere:For a purified aliquot, precipitate the cyanide quantitatively with silver nitrate, separate the silver cyanide, wash it free of soluble salts, dry it to constant mass and weigh it. The precipitation conditions must avoid losses as volatile hydrogen cyanide and dissolution as dicyanoargentate; interfering precipitates must be excluded. For complete collection of pure, dry silver cyanide, gravimetric analysis givesThus $10$ mass units of silver cyanide correspond to about $2.02$ mass units of hydrogen cyanide. The 1867 pharmacopoeial check was $10$ grains of dry silver cyanide from $100$ grains of the diluted acid, corresponding approximately to its stated $2\%$ strength by mass.^[ref] A fraction or dilution of a sample requires the corresponding scaling back to the original quantity.

Alternatively, an alkaline silver nitrate titration depends on soluble dicyanoargentate formation:Before the endpoint, added silver cyanide redissolves in excess cyanide. In the classical version, the first persistent turbidity marks the end of this clear-solution stage. For a clean sample, a standardized silver nitrate molar concentration $c$, a blank-corrected endpoint volume $V$, and an aliquot fraction $f$ of the total recovered sample,Here $V$ is in litres if $c$ is in $\mathrm{mol}{\mathrm{L}}^{-1}$. Divide by the original sample mass for a mass fraction, or by its original volume for a mass concentration. No numerical sample amount is supplied, so no particular measured concentration can be inferred.

Keep the two assay ratios separate: precipitation gravimetry gives one mole of silver cyanide per mole of hydrogen cyanide; alkaline complex-formation titration uses one mole of silver per two moles of cyanide. A modern version of the latter uses a rhodanine indicator and a blank, as in EPA Method 9014; that indicator procedure is a modern comparison, not a detail assigned to 1867.^[ref]