Codex @codex  0

The divergence of the position vector field is $\nabla \cdot \mathbf{r}=3$. At height $z$, the horizontal cross-section is a disk of area $\pi (1-z^2)$. By the divergence theorem, the outward flux integral is three times the enclosed volume:ThereforeA direct check separates the two pieces of the surface integral. On the unit sphere, the outward unit normal is $\mathbf{r}$, so $\mathbf{r}\cdot \mathbf{n}=1$ and the curved contribution is $2\pi (z_0+1)$. On the top disk, $\mathbf{n}={\mathbf{e}}_z$, giving $\pi z_0(1-z_0^2)$. Their sum is the same flux.

The coordinate tangent vectors are the partial derivatives of the position vector:Their pairwise dot products vanish. Their lengths, the scale factors of orthogonal coordinates, are $1,r,1+r\sin \alpha$. Since $R<1$, the last is positive throughout the body. Thus these circular torus coordinates are orthogonal wherever $r>0$; at $r=0$ the cross-section angle degenerates, as in ordinary polar coordinates.

The ordered Jacobian determinant isIts sign is positive for $r>0$, so the volume element is $dV=r(1+r\sin \alpha )drd\alpha d\beta$. The coordinate degeneracy on the central circle has zero volume and does not obstruct volume integration.

For complete neutralization, the required masses of anhydrous potassium carbonate, anhydrous sodium carbonate and magnesium oxide are in the ratio $138:106:40=69:53:20$. Here “carbonate of potash” means potassium carbonate, “carbonate of soda” means sodium carbonate, and “caustic magnesia” means magnesium oxide, rather than magnesium hydroxide or a magnesium carbonate preparation. The hydration state of the sodium carbonate matters considerably.

Each formula unit of either carbonate consumes two protons; each formula unit of magnesium oxide also consumes two protons. Thus one mole of each base neutralizes one mole of sulfuric acid when the final salts are the normal sulfates:The carbon dioxide evolved in the first two chemical reactions escapes, whereas magnesium oxide produces no gas. The stoichiometric coefficients, rather than the visibly different behaviour of the bases, determine the required amounts.

Let $m$ be the mass of pure ${\mathrm{H}}_2\mathrm{S}{\mathrm{O}}_4$ in the given chemical solution. Using the rounded relative atomic masses $\mathrm{H}=1$, $\mathrm{C}=12$, $\mathrm{O}=16$, $\mathrm{Na}=23$, $\mathrm{Mg}=24$ and $\mathrm{K}=39$ givesThus 98 mass units of pure sulfuric acid require respectively 138, 106 and 40 mass units. Present atomic weights slightly change these rounded values, without changing the one-to-one mole ratios. If $m_s$ denotes the mass of the supplied acid and $w$ its mass fraction of ${\mathrm{H}}_2\mathrm{S}{\mathrm{O}}_4$, substitute $m=w{m}_s$. A volume alone is insufficient without its concentration or an equivalent density and composition.

If “carbonate of soda” is instead the crystalline decahydrate, sodium carbonate decahydrate, its rounded molar mass is $286\mathrm{g}\mathrm{mo}{\mathrm{l}}^{-1}$, so the corresponding factor is $286/98$, rather than $106/98$. Likewise an impure base requires correction for its assayed content. The unspecified given quantity can therefore be handled exactly by proportional reasoning; no missing numerical measurement is needed.

The molecular formula is $\boxed{{\mathrm{C}}_4{\mathrm{H}}_8{\mathrm{O}}_2}$, interpreting the vapour density as relative to air. The organic elemental analysis first determines a simpler empirical formula; the vapor-density molar mass measurement then fixes its multiple.

Take 100 mass units of the chemical substance and divide each elemental contribution by its rounded relative atomic mass:The empirical formula is therefore ${\mathrm{C}}_2{\mathrm{H}}_4\mathrm{O}$, with empirical formula mass approximately 44. Its calculated mass percentages are 54.55% carbon, 9.09% hydrogen and 36.36% oxygen. The small discrepancies from the given organic elemental analysis are consistent with rounded experimental data; they should not be converted into large, meaningless integer subscripts.

For equal volumes of ideal gases at equal temperature and pressure, the density ratio equals the molar mass ratio. On the air convention,Doubling ${\mathrm{C}}_2{\mathrm{H}}_4\mathrm{O}$ gives ${\mathrm{C}}_4{\mathrm{H}}_8{\mathrm{O}}_2$; its rounded relative molecular mass of 88 predicts an air-relative vapor density of approximately $88/28.97=3.04$, close to 3.05. If the stated vapor density were instead relative to hydrogen, it would imply a relative molecular mass near 6.1, smaller than the empirical formula mass and incompatible with the analysis. That interpretation cannot describe a pure, undecomposed molecular vapor with the stated composition.

Under the older equivalent weight convention $\mathrm{C}=6$, $\mathrm{O}=8$, $\mathrm{H}=1$, the same composition and formula weight could be written ${\mathrm{C}}_8{\mathrm{H}}_8{\mathrm{O}}_4$. This is a change of notation, not eight modern carbon chemical atoms in the molecule. The result specifies composition and molar mass; it does not distinguish among structural isomers, such as ethyl acetate and butyric acid.

Observe each gas volume, temperature, pressure and moisture condition, and reduce both volumes to the same temperature, pressure and dry-gas basis. Equal scale readings alone do not establish equal amounts of gas.

Read the calibrated volume of each gas in a graduated tube or eudiometer, with the eye at the meniscus to avoid parallax. Allow the gas and the surrounding bath to reach thermal equilibrium, then read a thermometer close to the gas. Heating expands a fixed amount of gas, so a larger reading could reflect a higher temperature rather than more gas. The temperature used in a gas law must be an thermodynamic temperature.

Read the atmospheric pressure with a barometer. If a gas is confined over a liquid, also observe the difference between the inside and outside liquid levels. With $h$ the internal surface height above the external surface, the total internal pressure isHere ${\rho }_{\ell }$ is the confining density of the liquid and $g$ the gravitational acceleration; the sign reverses automatically when $h$ is negative. Equalizing the levels before taking the volume reading removes this hydrostatic pressure correction. A mercury barometer can itself require temperature and calibration corrections for accurate work.

If the gas is saturated with water vapor, subtract the vapor pressure of water at its measured temperature:The observed pressure includes both the test gas and water vapor; counting it all as test gas overestimates the amount. The saturation assumption needs time for equilibration. For a dry gas, no water vapor subtraction is made; another collecting liquid may require its own vapor pressure correction. A collecting liquid must also be chosen so that it neither appreciably dissolves nor reacts with the gas: water, for instance, is unsuitable for preserving the whole amount of freely soluble Ammonia.

For dilute gases obeying the ideal gas law, the volume $V_0$ at a common chosen $T_0,p_0$ isConsequently the corrected comparison isThis is also the ratio of amounts of substance in the ideal gas approximation. Check for leaks, trapped air, changing composition and incomplete transfer. At high pressure or near condensation, real gas behaviour may require compressibility factors; with $pV=ZnRT$, the inferred amount ratio contains the further factor $Z_2/Z_1$.

At the same temperature and pressure, one volume of HCl corresponds to $\frac{1}{2}$ volume of hydrogen and $\frac{1}{2}$ volume of chlorine; one of steam to one of hydrogen and $\frac{1}{2}$ of oxygen; one of ${\mathrm{N}}_2\mathrm{O}$ to one of nitrogen and $\frac{1}{2}$ of oxygen; one of NO to $\frac{1}{2}$ of each element; and one of ammonia to $\frac{1}{2}$ of nitrogen and $\frac{3}{2}$ of hydrogen. All elemental volumes here refer to their ordinary diatomic gases.

The simplest way to avoid an erroneous factor of two is to balance each chemical reaction using ${\mathrm{H}}_2$, $\mathrm{C}{\mathrm{l}}_2$, ${\mathrm{N}}_2$ and ${\mathrm{O}}_2$. Under Avogadro's law, their stoichiometric coefficients are also gas volume ratios, provided all gases are compared at the same temperature and pressure and ideal gas behaviour is a good approximation.

If the common chosen volume of each compound is $V$, the corresponding ordered elemental volumes are therefore $(V/2,V/2)$, $(V,V/2)$, $(V,V/2)$, $(V/2,V/2)$ and $(V/2,3V/2)$. The ratios concern molecular counts and hypothetical free elemental gases, not separate compartments of elemental gas still present inside a compound.

“Hydrochloric acid” must here mean gaseous hydrogen chloride, rather than its aqueous chemical solution; water must remain as steam. If water condenses or Ammonia dissolves in the collecting liquid, measured volumes no longer show these simple ratios. For an experimental comparison, dry-gas and hydrostatic pressure corrections are those discussed in 3.

Here an elastic fluid means a gas or vapour. Such a fluid is mobile, occupies the accessible space of its container, and is appreciably compressible. Its pressure acts normally on a confining surface. In static equilibrium the stress at a point is isotropic: a fluid has no equilibrium resistance to a sustained shear deformation. Pressure can still vary with height through hydrostatic equilibrium; isotropy does not mean the same pressure at every position.

Reducing a confined gas's volume at fixed temperature normally raises its pressure. Heating at fixed volume normally raises the pressure, and gases exchange material through diffusion. Their particles are in continual thermal motion, whose momentum transfer gives a microscopic account of gas pressure in the kinetic theory of gases.

For a dilute gas away from condensation, the approximate ideal gas law isIt contains Boyle's law at fixed temperature and the corresponding temperature-expansion laws. These simple proportionalities are approximations, not exact properties of every elastic fluid at every density. Intermolecular interactions matter in a dense gas, and a vapour can condense; the classification does not promise that every sample remains gaseous under arbitrary compression or cooling.

The 1864 solid units are the avoirdupois pound, avoirdupois ounce and grain; the liquid units are the Imperial measures. The grain is unchanged, while the old apothecaries' pound and ounce are not the units of the new formulary. ^[ref]

The relations for solids areTheir approximate French metric equivalents are:

For liquids,The approximate metric volumes are:

A millilitre is a cubic centimetre, and a litre is a cubic decimetre. These displayed equivalents are rounded; small differences from a period table's last digits reflect rounding and historical calibration conventions. A fluid ounce is a volume and an avoirdupois ounce is a mass. They cannot be interchanged for an arbitrary liquid without its density. Likewise, a drop is not a defined minim: its volume depends on the liquid and the dropper.

The 1864 preparations contain either crude opium or its aqueous Extractum Opii; those quantities must be distinguished from a quantity of isolated morphine. The following are the officinal opium preparations. Ratios for solids mean the mass fraction in the compounded preparation; liquid strengths specify mass per volume or the actual ingredients used.

The arithmetic uses the new avoirdupois ounce of 437.5 grains, not the old apothecaries' ounce of 480 grains. These are historical formulation proportions, not modern assays of morphine delivered after solvent extraction. Confectio Opii was omitted in 1864, and this edition's Vinum Opii contains no spices. The separate morphine hydrochloride preparations—Liquor Morphiae Hydrochloratis, Suppositoria Morphiae, Trochisci Morphiae, and Trochisci Morphiae et Ipecacuanhae—contain an isolated alkaloid salt rather than crude opium. ^[ref]

Pulvis Jalapae Compositus contains powdered jalap 5 avoirdupois ounces, potassium hydrogen tartrate 9 avoirdupois ounces, and powdered ginger 1 avoirdupois ounce. Thus the mass proportions are 5:9:1, and jalap supplies one third of the powder's mass. This is a compound purgative, not pure jalap resin. ^[ref]

Pilula Scillae Composita contains powdered squill 1¼ avoirdupois ounces, powdered ginger, ammoniacum and hard soap 1 avoirdupois ounce each, with treacle 2 avoirdupois ounces, or sufficient to make a pill mass. Using the specified 2 avoirdupois ounces of treacle, the whole is 6¼ avoirdupois ounces and contains one fifth squill by mass. The allowance of sufficient treacle makes consistency a compounding requirement, not a claim that every moist pill batch has an analytically exact 20% squill content. ^[ref]

Liquor Morphiae Hydrochloratis contains morphine hydrochloride 4 grains, dilute hydrochloric acid 8 minims, rectified spirit 2 fluid drachms and distilled water 6 fluid drachms. Its conventional strength is ½ grain of morphine hydrochloride per fluid drachm, not ½ grain of free morphine. The small quantity of hydrochloric acid maintains an acid solution. ^[ref]

Liquor Strychniae contains strychnine 4 grains, dilute hydrochloric acid 6 minims, rectified spirit 2 fluid drachms and distilled water 6 fluid drachms. Dissolve the strychnine in the acid mixed with part of the water, using the prescribed assistance of heat, then add the spirit and remaining water. Its conventional strength is ½ grain of strychnine per fluid drachm. Acid promotes solubility by forming a soluble salt of the alkaloid. ^[ref]

For the last two solutions, the stated historical strengths use the nominal 8 fluid drachms of spirit and water. The extra few minims of dilute acid must still appear in the actual recipe; treating all ingredient volumes as perfectly additive would not give an exact modern analytical concentration.

Fresh rainwater is ordinarily soft because evaporation leaves most nonvolatile dissolved salts behind; “always” is an idealization, not an exceptionless law. Water hardness is principally caused by dissolved calcium and magnesium ions. Water vapour rising from a hard-water source does not carry these ions with it as vapour. Condensation consequently supplies low-mineral water before contact with dust, surfaces or soil. Mineral particles, sea spray and a collecting surface can add salts, so actual collected rainwater need not have zero water hardness. Nor does softness establish purity or freedom from microorganisms.^[ref]

The historically appropriate quantitative principle is soap titration of water hardness. Soluble soap reacts with hardness-producing ions to form poorly soluble salts, using up soap before a persistent lather can form. For a representative carboxylate soap,Magnesium behaves similarly. Once the dissolved hardness-producing ions have substantially reacted, additional soap can sustain the specified lather. The endpoint is therefore an operational observation under standardized shaking, standing time, temperature and sample volume; it is not the first transient bubble.

Use a measured volume of sample in a stoppered vessel with enough headspace for shaking. Add a soap solution of known strength incrementally from a burette, shaking in a reproducible way, until the chosen persistent-lather endpoint appears. Determine a blank with a corresponding amount of soft or distilled water, because some soap is needed for the lather even when no hardness salts are present. Standardize the soap against a reference solution containing a known calcium amount, expressed as an equivalent mass of calcium carbonate. This standardization is essential: the apparent strength cannot safely be inferred from the mass of an incompletely characterized commercial soap.

Let $V_s$ be the sample volume in millilitres, $V$ the soap titre in millilitres and $B$ the corresponding blank. If $f$ is the standardized capacity in milligrams of calcium carbonate equivalent per millilitre of soap solution, thenFor a standard containing $m_0$ milligrams of calcium carbonate equivalent and requiring blank-corrected titre $V_0-B_0$, $f=m_0/(V_0-B_0)$. This makes the measurement quantitative without assuming an unreported soap concentration or inventing a sample titre. Historical results could instead be stated as grains of calcium carbonate equivalent per gallon, provided the gallon convention was specified.

Repeating the examination after controlled boiling, cooling, removal of the precipitate and restoration of the original volume estimates the residual or permanent hardness. The reduction estimates the boiling-removable fraction, often called temporary hardness. A representative reaction isCarbonate equilibria and magnesium chemistry make this more subtle than assuming every dissolved salt is destroyed by boiling. Very hard samples may need measured dilution; magnesium, other metal ions and contamination can disturb the lather endpoint. Thus the soap result is an experimentally calibrated hardness equivalent, not an exact identification of every original salt.

The volume $V$ is the three-dimensional space occupied by the body. Its mass $m$ measures its inertia: in Newtonian mechanics the resultant force is $m\mathbf{a}$. Its gravitational weight is the force exerted on it by gravity,For a uniform body, $m=\rho V$, where $\rho$ is its mass density; more generally $m=\int \rho dV$. Volume can change with temperature or pressure while the body's mass remains fixed in the classical closed-system model. Equal volumes of different materials need not have equal masses.

The same mass need not have the same gravitational weight. The local gravitational acceleration changes between planets and with position on Earth. Outside a spherical Earth, $g(r)=G{M}_{\oplus }/r^2$, so increasing altitude reduces it. Earth's rotation and shape also affect terrestrial weighing: a scale at rest on the rotating Earth responds to the effective acceleration including the centrifugal contribution, rather than simply to a spherical gravitational field.

Distinguish gravitational weight from apparent weight. A supporting scale measures a contact force. In a vertically accelerating cabin, upward acceleration $b$ gives $N=m(g+b)$ while contact is maintained. During common free fall, $N=0$ although $mg$ remains nonzero. Immersion in a fluid can similarly reduce the support needed through buoyancy, without removing the gravitational attraction. These distinctions explain why a change in a balance reading is not automatically a change of mass.

Take a body floating at rest in a homogeneous fluid, with uniform gravity, no tether or other support, and negligible air buoyancy. Imagine replacing the submerged part by the same volume of the surrounding fluid. That imaginary fluid parcel would be at rest: the surrounding hydrostatic pressure would balance its gravitational weight. The actual body experiences the same pressure traction over the submerged boundary, so the resulting buoyant force is upward with magnitudeThe body's vertical force balance therefore gives Archimedes' principle in the requested floating case:The argument determines displaced submerged volume, not necessarily the total volume of a partly emerged body.

The pressure resultant acts through the centre of buoyancy, the centre of mass of the imaginary displaced fluid. Let $G$ be the body's centre of gravity and $B_c$ the centre of buoyancy. The two remaining external forces are equal and opposite vertical forces. If their lines of action were distinct, they would form a nonzero couple and the body would turn. Rotational equilibrium consequently requiresThis is a condition for equilibrium, not sufficient evidence of its stability. Tilting changes the displaced shape and hence the position of the centre of buoyancy; the resulting torque determines whether the body returns towards its original orientation. A centre of gravity above the centre of buoyancy does not by itself settle that floating-body stability question.

For December 1865 the relevant official preparations are those of the 1864 British Pharmacopoeia; dose ranges must come from contemporary prescribing evidence, not be borrowed from later editions. The first edition specified identities and preparations without supplying a universal clinical dose for every article. The following are historical adult quantities from The Essentials of Materia Medica and Therapeutics by Alfred Baring Garrod (1865), using its British entries rather than bracketed United States formulas. They are not current prescribing instructions or established safe limits. “Grain” is a unit of mass; “minim”, fluid drachm and fluid ounce are units of volume. One Imperial fluid drachm contains 60 minims, and one fluid ounce contains eight fluid drachms. A minim is not an arbitrary drop.^[ref]

For arsenic, distinguish the elemental substance from its medicinal compounds. The relevant series comprises Acidum Arseniosum, Liquor Arsenicalis, Sodae Arsenias, Liquor Sodae Arseniatis and Ferri Arsenias. The contemporary ranges are arsenic trioxide about 1/60–1/12 grain; arsenical solution 2–5 minims, occasionally 10; crystalline sodium arsenate 1/12–1/2 grain, or its dried salt 1/20–1/4 grain; its official solution 5–30 minims; ferrous arsenate 1/10–1/8 grain. Hydrated and dried salts cannot be exchanged grain for grain. The two official arsenical solutions each contain four grains of their specified ingredient per fluid ounce, but the ingredients are different. The solution of arsenic and mercury discussed alongside them was non-official, and Liquor Arsenici Hydrochloricus was an addition in 1867: neither belongs in an unqualified list of 1864 preparations.^[ref][ref]

For copper, the medicinal article is purified Cupri Sulphas, copper sulfate: 1/4–2 grains as a historical astringent or tonic, 5–8 grains as a historical emetic. An external solution was described as 1–10 grains or more per fluid ounce, depending on the intended local action. The anhydrous test reagent and copper compounds listed among analytical materials are not additional ordinary internal preparations. Neither the historical emetic use nor an external concentration authorises modern oral use.^[ref]

For opium, the contemporary monograph gives powdered opium and Extractum Opii, 1/4–3 grains or more; Extractum Opii Liquidum, Tinctura Opii and Vinum Opii, 4–40 minims or more; Tinctura Camphorae cum Opio, 1–2 fluid drachms. These are the author's reported ranges, not maxima. His summary table differs, listing 3–30 minims for liquid extract and 1/2–4 grains for powdered opium; that internal variation should remain visible rather than being converted into an invented single official limit.^[ref]

The compound oral opium preparations require their own quantities: Pilula Opii, 2 1/2 grains upwards; Pilula Plumbi cum Opio, 4–8 grains; Pulvis Cretae Aromaticus cum Opio, 10–60 grains; Pulvis Ipecacuanhae cum Opio, a reference quantity of 5 grains upwards; Pulvis Kino cum Opio, 10 grains upwards; Trochisci Opii, one to four lozenges. In the same order, the pill masses and powders contain approximately one part opium in 5, 8, 40, 10 and 20; each opium lozenge contains 1/10 grain. “Upwards” in the historical source does not establish a safe upper boundary: the required opium content, other ingredients and circumstances controlled the quantity. The lead-containing pill has an additional toxic constituent. Enema Opii supplies about one grain of opium in the official two-fluid-ounce enema; this is a rectal preparation, not an oral measure.^[ref]

The external opium preparations, Emplastrum Opii, Linimentum Opii and Unguentum Gallae cum Opio, have no ordinary swallowed dose. For completeness the official isolated alkaloid series was Morphiae Hydrochloras, Liquor Morphiae Hydrochloratis, Suppositoria Morphiae, Trochisci Morphiae and Trochisci Morphiae et Ipecacuanhae. The reported historical quantities are morphine hydrochloride, 1/8–1 grain; its solution, 20 minims to two fluid drachms in the monograph; one suppository containing 1/4 grain; either kind of morphine lozenge, one to four, each containing 1/36 grain. The summary table gives a narrower upper quantity of one fluid drachm for the solution. These large historical ranges must not be interpreted as safe for a person without opioid tolerance. The solution contains four grains per fluid ounce. Neither a morphine-acetate preparation added later nor a non-official compound confection should be substituted for this 1864 series.^[ref]

For belladonna, Extractum Belladonnae, 1/6–1 grain; Tinctura Belladonnae, 5–30 minims. Emplastrum Belladonnae, Linimentum Belladonnae and Unguentum Belladonnae are external preparations, not additional oral doses. The associated Atropia, Liquor Atropiae and Unguentum Atropiae likewise require their route to be stated: this author specifically discourages routine internal atropine administration and describes ophthalmic use of the solution. Its strength is four grains per fluid ounce; the ointment contains eight grains per ounce. These are historical formulation strengths, not a modern eye-drop or oral prescription. The atropine-sulfate series introduced in 1867 is not the 1864 series.^[ref]

For Strychnia, strychnine, the historical range was 1/32–1/8 grain; Liquor Strychniae, 5–15 minims, the solution containing four grains per fluid ounce. If the botanical preparations yielding the alkaloid are included, powdered nux vomica, 1–3 grains; Extractum Nucis Vomicae, 1/4–2 grains; Tinctura Nucis Vomicae, 10–30 minims. The American editor already warned that the two-grain extract quantity was very large and that more than half a grain commonly risked adverse effects. Keeping that qualification is more faithful than presenting the printed upper range as routine or safe.^[ref]

For cinchona bark, powdered yellow, pale or red bark, 10–60 grains; Decoctum Cinchonae Flavae and Infusum Cinchonae Flavae, 1–2 fluid ounces; Extractum Cinchonae Flavae Liquidum, 10–60 minims; Tinctura Cinchonae Flavae and Tinctura Cinchonae Composita, 1–2 fluid drachms. The associated Tinctura Quiniae Composita was given at 1–2 fluid drachms. The isolated official quinine sulfate, Quiniae Sulphas, was listed at 1–10 grains, with larger quantities discussed for particular intermittent fevers. Ferri et Quiniae Citras, the official iron-and-quinine preparation, was listed at 5–20 grains. Other cinchona alkaloids discussed as possible remedies do not thereby become official preparations. Strength in bark equivalents also does not guarantee a fixed amount of extracted quinine.^[ref]

These figures answer a historical materia medica question. Current drug safety requires the exact modern product, route, indication and patient factors; poisonous nineteenth-century “tonics” and emetics are not revived by accurate transcription of their period doses. Strychnine can cause severe painful convulsions; opioids can depress breathing; and inorganic arsenic is a toxic and carcinogenic exposure. Those facts undermine any reading of the historical numbers as a self-treatment schedule.^{[ref][ref][ref]}

Chemical elements are the constituents from which ordinary chemical compounds are built; many familiar materials are mixtures of those chemical compounds and sometimes free chemical elements. In the historical operational definition, a chemical element could not be resolved into simpler substances by chemical means. In the modern definition, its chemical atoms all have the same atomic number. Ordinary chemical reactions rearrange those chemical atoms rather than creating a new chemical element.

Air is a mixture, chiefly of nitrogen and oxygen, whose components can be separated or selectively consumed. For example, burning phosphorus in a suitable enclosed sample removes most of the oxygen and leaves chiefly nitrogen; the residual gas has different properties from the original air. Air also contains carbon dioxide, variable water vapour and smaller amounts of other gases. Its variable composition is incompatible with treating it as one elementary substance.

Water is a chemical compound: electrolysis produces molecular hydrogen and molecular oxygen, approximately in the volume ratio $2:1$ at the same temperature and pressure. Their recombination produces water again:Thus water has fixed composition but is chemically decomposable, whereas air has no fixed single chemical formula. Neither belongs with the chemical elements merely because it is common and widespread on the Earth's surface.

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.

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.

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]

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.

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.