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A historical arsenic-separation and recognition procedure associated with James Marsh. Volatile arsine carries arsenic away from a sample matrix and yields a deposit; stibine can interfere.

Keep an untouched portion, use clean apparatus and reagent blanks, separate the suspected arsenic from the organic material, and confirm it by independent chemical reactions. A coloured deposit alone would be inadequate evidence.

Record the container, seal and condition of the stomach contents before opening. Examine and describe the material, including any visible particles, without assuming that a white powder is arsenic trioxide. Retain an unaltered portion for a repeat examination. Because a solid poison may settle, examine representative liquid and solid portions separately rather than testing only the clear upper liquid. Label each portion and each subsequent extract so that a positive reaction can be traced back to its source.

A practicable historical preliminary separation is the Reinsch test. Warm a portion with hydrochloric acid and a clean strip of copper; a dark coating suggests deposition of a substance requiring further identification. Carry out a parallel blank with the same copper, chemical acid, water and apparatus. A coating may be caused by substances other than arsenic, and contaminated copper or reagents can create a false accusation. Wash and dry a coated strip, then heat it in a small tube: an arsenical deposit can give a sublimate of arsenic trioxide, whose crystals can be examined with a microscope. The deposit and sublimate, rather than their mere colour, are the material for confirmation.^[ref]

On a separate suitably prepared portion, the Marsh test provides another mode of separation. The original James Marsh apparatus collected a hydrogen mixture for deposition tests; a heated-tube implementation separates collection from the subsequent heating zone. Zinc and dilute chemical acid generate hydrogen; arsenic in a suitable chemical form is converted to volatile arsine, and heating the gas in a narrow tube can produce a metallic mirror. First run the generator with the actual reagents alone, until their freedom from arsenic has been demonstrated. Keep the sample out of the gas outlet, and distinguish chemical deposition from mechanical carry-over. The apparatus separates a volatile derivative from much of the organic matrix, which explains its analytical value. Arsine is extremely toxic: this is a description of historical analytical principles, not a procedure for an uncontained demonstration.^[ref]

A mirror is not uniquely arsenical: antimony can form stibine and give a misleading deposit. Recover or oxidize the material and use additional reactions, such as formation of yellow arsenic trisulfide under appropriate acidic conditions, together with the characteristic oxide sublimate. Separate aliquots, suitable controls and agreement between chemically distinct tests are more persuasive than repeatedly observing the same ambiguous stain. Organic material must be removed or treated by a controlled preparation that neither introduces nor loses arsenic; indiscriminate charring or heating can invalidate the examination.

Finally distinguish detection from interpretation. A demonstrated arsenical compound supports exposure, but the amount, distribution and circumstances determine its significance. A negative test on the stomach contents alone does not exclude poisoning after absorption or expulsion of the poison. Further organs or excretions could be examined if available, but no positive finding in such material is assumed here.

The historical Marsh test separates arsenic into a volatile hydride and then into a visible deposit, allowing it to be examined apart from much of the original organic matrix. It requires controls and confirmation because a dark deposit is not unique to arsenic. The test is associated with James Marsh; its primary account explicitly addresses mixtures containing animal and vegetable matter.^[ref]

Retain representative material and a control portion before destructive preparation. A complex organic sample can be clarified and, where needed, subjected to a validated wet oxidation that destroys interfering organic matter while retaining the arsenic in the analytical preparation. Avoid uncontrolled heating to dryness or conditions that volatilize an arsenic compound; successful mineralization cannot simply be assumed. The reagent sequence must leave the arsenic in a reducible form and must not leave enough oxidant to defeat the subsequent reduction. A recovery experiment with a known addition is a check on the entire preparation, not merely on the last colour reaction.

In the hydrogen-generating stage, arsenic-free zinc reacts with a suitable dilute acid. The sample's reducible arsenic is converted to arsine, which passes with the carrier gas out of the generating vessel. A representative net reduction balance for arsenic(III) isThis is a reaction balance, not a claim that the old phrase “nascent hydrogen” identifies one uniquely established microscopic mechanism.

The apparatus needs controlled reagent entry, an unobstructed gas path and a means of excluding droplets carried from the sample. In the later heated-tube form, the hydride decomposes at a hot section:Arsenic collects as a mirror on the cooler glass beyond it. Marsh's original flame method deposited material on a cold surface held in relation to the burning jet. The original arrangement and the heated-tube improvement should not be treated as identical apparatus. In either case the useful analytical separation is transfer of the arsenic away from the nonvolatile matrix, not just darkening of that matrix.

Run the complete reagent blank first: contaminated zinc or acid can otherwise make an arsenic-free sample appear positive. A positive known control checks that hydride production and collection work. Antimony can form stibine and a similar dark deposit, so mirror formation alone is not conclusive. Confirm with independent chemistry, for example controlled oxidation of the collected deposit followed by appropriate arsenic tests; the greater susceptibility of an arsenic mirror to suitable hypochlorite treatment supplies an additional historical distinction from an antimony deposit. No single visual resemblance should replace these discriminations.

A negative test is meaningful only relative to the validated preparation, detection limit and controls. Modern arsenic analysis uses instrumental methods with defined recovery and sensitivity; the historical demonstration is not itself a contemporary forensic certification. Arsine is acutely toxic, and the hydrogen-bearing gas stream introduces further apparatus hazards: this account explains the analytical chemistry, not a household procedure.^[ref]

Antimony is the brittle, silvery crystalline element $\mathrm{Sb}$, encountered especially in sulfide ores and in compounds of oxidation states $+3$ and $+5$. Its historical treatment as a metal is understandable from appearance and alloying behaviour; modern classifications commonly call it a metalloid. It is too brittle to behave like a readily drawn, ductile metal and is used in suitable alloys to alter properties such as hardness.

The important ore is stibnite, ${\mathrm{Sb}}_2{\mathrm{S}}_3$. A historical reduction can use iron to bind the sulfur:Another route roasts suitable sulfide material to an oxide and then reduces that oxide with carbon. For an ideal trioxide product,Real ore processing requires control of impurities and volatile losses, so these balances do not alone constitute a complete extraction flowsheet.^[ref]

Among its principal combinations, antimony(III) oxide is an amphoteric oxide. It dissolves under suitable acidic or alkaline conditions rather than fitting a universal rule that a metal oxide must be solely basic. Antimony(III) chloride, historically “butter of antimony”, hydrolyses on dilution and can deposit a white oxychloride-containing material. A useful simplified balance isAdded acid favours dissolution; a more extensively hydrolysed precipitate need not be pure $\mathrm{SbOCl}$. Pentavalent compounds include antimony(V) chloride and antimonate species; chloride-rich solutions and their hydrolysis require attention to the medium.

Antimony(III) sulfide can occur as the dark crystalline ore and as an orange precipitate obtained from a suitable solution with hydrogen sulfide:Its dissolution in suitable alkaline sulfide solutions forms thioantimony species, providing an analytical separation from some other sulfides. Acidification can reverse that operational separation. A volatile hydride, stibine, ${\mathrm{SbH}}_3$, can decompose to a dark antimony deposit and thus interfere with the Marsh test for arsenic.

Antimony potassium tartrate, “tartar emetic”, is a historically important complex salt, not merely an arbitrary mixture of an antimony salt and a potassium salt. It was used medicinally, but historical use is not proof of safety or a present indication; antimony-containing substances can cause serious poisoning. No dosage or treatment recommendation follows from describing them.^[ref]