Questions for the student of elementary chemistry - Journal of

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The Chemistry Student QUESTIONS FOR THE STUDENT OF ELEMENTARY CHEMISTRY

The first picture here reproduced is from the Currus Triumphalis Antimonii (Triumphal Chariot of Antimony) of the fictitious Benedictine monk of Erfurt, Basil Valentine, published in Latin with the commentary of Theodore Kerckringius, Amsterdam, 1685. The work was first published in German early in the seventeenth century by Johann Tholde who

claimed to have discovered i t in an ancient manuscript but probably wrote it himself. It is one of the earliest of chemical monographs, and contains clear and adequate directions for the preparation, from the natural sulfide, of antimony metal, of the oxide, chloride, oxychloride, oxysulfide, and of various other compounds of antimony. The second picture is reproduced from an Italian book, Faramaceutica Antimoniale overo Trionfo dell' Antimonio, by Carlo Lanallotti, Modona, 1683. The book summarizes the writings relative to antimony of Basil Valentine, Paracelsus, Penotus, Quercetanus, Milius, Sennert, Beguinus, Angela Sala, and many others. It shows that the chemists of the seventeenth century had not only a first-class manipulative skill but an amazing amount of accurate qualitative knowledge of the chemistry of antimony. 1141

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THETwo TITLEPAGBSOF KERCK~~INGIUS' COMMENTARY

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Both books were written, as their titles indicate, because their authors believed strongly in the medicinal value of antimony preparations. The use of these medicines had previously led to such abuses that the French Parliament, acting on the recommendation of the Medical Faculty of Paris, had forbidden their use in 1566. Paumier, a chemist and physician of Caen, had been expelled from practice in 1607 because he persisted in using them. The legislation against them was repealed in 1624. Early in the seventeenth century Sala insisted upon the precautions which are necessary when using compounds of antimony. "Whoever loves his health," said he, "must take care with these medicaments. Unlike arsenic which is naturally poisonous, antimony may acquire poisonous properties by combining with other substances-just as mercury, which is not a poison by itself, becomes a poison in the state of sublimate." The Dutch publishers of the seventeenth century had the pleasant habit of issuing their books with two title pages. The first or engraved title page generally carried a picture of considerable artistic merit and gave only the bald title of the book, while the second or printed title page really fulfilled the functions which were proper to it. The Commentary of Kerc-

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THE CHEMISTRY STUDENT

kringius on Basil Valentine is supplied with a very beautiful engraved title page by Romijn de Hooghe, dated 1674, representing the triumphal chariot of antimony. The Italian book contains two folding plates, one of which pictures the triumph of antimony as being similar to that of a Roman Emperor returning from his conquests in a chariot drawn by Nubian lions. The affair appears to he taking place with full benefit of clergy. The Emperor walks, his conquered kings preceding him, while Time and Health ride in the chariot, with Antimony, surrounded by the utensils of chemistry, on top of it in the place of greatest honor. Many of Basil Valentine's directions for the preparation of antimony compounds are satisfactory laboratory directions for the student of today. He can carry them out, with slight modification, with apparatus which he can find in the highschool laboratory. The processes, three centuries old, are a challenge to him. Can he write formulas for the reactions which are involved in the

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experiments described by our author? Can he tell why certain steps are required in the procedure? See what you can do with the following directions of Basil Valentine.' (Remember that "Antimony" means the mineral stibnite, Sb&, and that "Regulus of Antimony," little king of antimony, means the metal.) 1. Take best Hungarian Antimony, or any kind you can get, pulverize i t as finely as possible, spread thinly on an earthenware dish (round or square) provided with a low margin; place the dish on a calcinatory furnace over a coal fire, which should a t first be moderate. As s w n as YOU see smoke rise from the Antimony, .. stir it about with an iron spoon, and continue doing so till there is no more smoke, and the Antimony sticks together in the shape of small globules. Remove i t from the fire, pulverize again into a fine powder, place i t on the tire, and calcine as before, till there is no more smoke. This calcination must be repeatednot only till the Antimony gives out no more smoke, but does not conglomerate into globules, and has the appearance of pure white ashes. Then has the calcination of Antinomy heen successfully completed.

[What are the reddish colored, fusible globules? Why is it necessary to break them up in order to accomplish the successful preparation of antimony oxide? What would happen if the heat were too strong?] 2. Place this calcined Antimony in a mcihle, such as goldsmiths use for melting gold and silver, and set i t over a violent fire, either lighted in a wind furnace or increased by means of the bellows, till the Antimony becomes liquid like pure water. T o test whether the Antimony has acquired its proper glassy transparency, dip in it an oblong piece of cold iron, and examine carefully the Antimony which clings t o it. If i t he dear, pure, and transparent, i t is alright, and has attained its due maturity. The tyro, or beginner, should know (these remarks are addressed to beginners who are students of the Spagyric Art) that glass, whether prepared from metals, minerals, or any other substance, must be subjected to heat, till i t has attained t o maturity, and exhibits a clear and pellucid transparency.. . .When Antimony has become vitrified in the way described, heat a flat, broad, copper dish over the tire, pour into it the Antimony in as clear and thin a state as possible, and you will have pure, yellow, pellucid glass of Antimony. This preparation of what I call the glass of Antimony is the simplest, best, and most efficacious with which I am acquainted. 3. Common glass of Antimony is pulverized; six grains or more are ahsolved in warm wine overnight: in the morning the wine is drunk without the sediment, and purges, both by laxation and vomiting, on account of the poisonous crudeness which still remains in the glass of Antimony.

[Knowing that wine contains a certain amount of potassium hydrogen tartrate, what soluble compound of antimony would you expect to be formed? Is the author correct in ascribing the potency of his medicine to the "poisonous crudeness which still remains in the glass of Antimony?" If a sample of the same wine were allowed t o stand over night in a cup of metallic antimony, would the resulting medicine be weaker or stronger than that which is described?] 1 The quoted passages, unless otherwise noted, are from "The Triumphal Chariot of Antimony" (an English translation by Arthur Edward Waite of Kerckringius' book of 1685). London, 1893.

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APPARATUS OF KERCKRINGIUS FOR THE PURIFICATION OP ANTIMONY TRICELORIDS TO BASILVALENTINE ACCORDING 4. Take one part each of finely pulverized Antimony and pulverized salt-armoniac [ammonium chloride], so called hecause it comes from Armenia: mix these together. place in a retort, and distil together. On the product of this distillation pour hat distilled (common) rain water, removing thereby every salt and acrid taste [washing thoroughly]. Then the Antimony will he of a pure, brilliant, and feathery white.

[Write reactions.]

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5. There remains another extraction by means of a certain caustic water, which experience teaches ought to be carried out in this fashion. Take vitriol [sulfuric acid] and common salt [and antimony sulfide], equal parts of each. Take the water distilled from these per latus. When this is urged strongly by the fire, it yields a substance similar to butter or olive oil.'

[These directions are n o t especially clear. T h e a u t h o r evidently means that a n t i m o n y sulfide, sodium chloride, a n d sulfuric acid a r e to be distilled together. T h e reagents being moist, the acid probably not being anhydrous, t h e product is a watery liquid-a solution of antimony trichloride i n aqueous hydrochloric acid. W h e n t h i s is distilled i n t h e apparatus of Kerckringius, fractional condensation occurs a n d t h e trichloride collects i n t h e first receiver, the aqueous portion i n t h e second. W r i t e t h e reactions.]

6. Pulverize pure Hungarian Antimony, and an equal quantity of thrice-purified saltpeter; burn this composition all together in a new glazed pot, which is free from grease, over a circulatory fire, but not all a t once. (This operation the ancients called detonation.) Then pulverize the hard matter which remains in the pot: pour over it moderately hot ordinary water, and when the powder has settled a t the bottom, add New translation from the Latin

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more water, till all the saltpeter is extracted. Dry the substance, and again add to it its own weight of saltpeter; burn again, and repeat this operation three times.

[Write reactions.] 7. Take equal parts of the best Hungarian Antimouy and crude tartar [potassium hydrogen tartrate], and half the quantity of saltpeter; pound together, melt over a wind fire, pour into a copper dish, allow to cool, and you will find the Regulus. The Regulus is thrice, or oftener, purified with tartar and saltpeter till it becomes oi a hrilliant silvery white.

[What reactions would o&ur if a mixture of antimony sulfide and pw tassium hydrogen tartrate were heated? How does it happen that the mixture of potassium nitrate and potassium hydrogen tartrate acts upon antimony sulfide in a manner so different from either of these substances alone? Write the reactions.] 8. Pound together one pound of Antimony, half a pound of common salt, and five pounds of broken bricks; place in a retort and distil a yellow ail, when all the spirits will pass away. Pour into a fresh vessel, and remove its oiliness [by washing with water]; there remains a powder, which, spread on a stoneina humid placc, and you will have a humid balm which is of great efficacy against foul wounds.

[What is the purpose of the powdered brick? Does it take part in the reaction? Write equations.] 9. Sulfur of Antimony may also he prepared in the following manner: Pulverize the Antimony, and digest for two hours,,or longer, in strong lye made of the ashes of beechwood. Strain, add vinegar, and the sulfur will he of a red color, and sink t o the bottom; pour off the liquid, and dry the powdebgently.

[The reddish brown powder is the material which the alchemists called kermes. What is the source of the odor produced during the boiling' How does antimony sulfide react with boiling aqueous potassium carbonate? What is the effect of adding dilute acetic acid? What would be the effect of hydrochloric acid on the product?] 10. Take two parts of Hungarian Antimony, and one part of steel; melt with four parts of burnt tartar [potassium carbonate] in an iron basin, such as those in which goldsmiths refine gold. Cool, take out the Regulus, remove all impurities and scoriae, pulverize finely, add to it, after ascertaining its weight, three times as much burnt tartar; melt, and pour into a basin as before. Repeat a third time, and the Rcgulus becomes highly refined and brilliant. If you have performed the fusion properlywhich is the point of greatest importance--you will have a beautiful star of a brilliant white. The Star is as distinct as if a draftsman had traced it with a pair of compasses.

[The star which so fascinated the alchemists is caused by the crystallization of the antimony button. What is accomplished by submitting the first crude regulus to a second and third treatment with potassium carbonate? From a given w?ight of antimony sulfide, which method, this or the one described earlier, would give the better yield of metallic antimony? Why? Which would yield the purer product?]