Grantville Gazette Volume 25

by editor Paula Goodlett

  Zinc oxide was produced in thirteenth century Persia (Emsley 502). It's a normal intermediate in the reduction of zinc ore to zinc, but it is preferably produced by oxidizing zinc vapors (EB11/Zinc). It's a possible substitute for titanium dioxide as a white pigment.

  The alchemists' "white vitriol" is zinc sulfate heptahydrate, and it appears to have been known by the late sixteenth century (Beckmann, 81).. It's produced by reacting zinc with sulfuric acid. It's now used in making rayon, and in zinc plating.

  Zinc chloride is mentioned as a wart remedy by Clark, "The Secret Book of Zink" (Grantville Gazette 2). It's used to preserve and fireproof wood, and for other purposes (EA). It can be made by reaction of the metal with chlorine gas or with HCl (EB11).

  The main impediment to exploitation of zinc and its standard salts is one of communication; the up-timers have to accurately convey what it is that they are seeking. Zinc and its compounds should be available in limited quantities in 1633, but it will probably be a struggle to keep up with demand until 1635 or so.

  Cadmium

  The situation of cadmium is a peculiar one, in that the down-timers may have encountered one of its compounds, without knowing that it contained a new element, and it's uncertain whether the up-timers will be able to enlighten them.

  The principal cadmium ore is greenockite (cadmium sulfide). Emsley (77) asserts that it was mined in Classical Greece and used as a yellow pigment. This is plausible—it is found, in association with calamine, at Laurion—but it has been challenged by other authorities (Eastaugh, 176).

  Cadmium sulfide entered the historical record in the early nineteenth century, when Stromeyer, the inspector of pharmacies, investigated a complaint by Hannover druggists that the zinc oxide they made by heating calamine sometimes was yellow rather than white. (Emsley 76). The calamine trade is centuries old, and I can't help but wonder whether this yellow adulterant is known to the seventeenth-century apothecaries. If so, they may question the up-time chemists about it, and Stromeyer's discovery may be anticipated by several centuries.

  In any event, the up-timers certainly know that the element cadmium exists, and that it's associated with flue dust from zinc ore processing.

  Cadmium plating has been used to protect steel from salt water, and cadmium is used in Nicad batteries. Cadmium sulfide is used as a pigment, semiconductor, and photoelectric cell component.

  That said, I don't expect cadmium to come into the chemical marketplace in the NTL 1630s.

  Mercury

  Mercury, as a pure element, is known to the down-timers. It is obtained from cinnabar (mercuric sulfide). The mineral itself can be powdered to produce the pigment vermillion.

  Mercury, although used by down-timers as a treatment for syphilis, is poisonous, which comes as an unpleasant surprise to potion maker Guba Ivashka Kalachnikov. Huff and Goodlett, "Butterflies in the Kremlin, Part Four" (Grantville Gazette 11) and is mentioned by Dr. Abrabanel in "Venus and Mercury" (Lee Grantville Gazette 24).

  Heating the metal in air yields mercuric oxide, and then dissolving the oxide in nitric acid provides the nitrate (mercurous nitrate if dilute acid, mercuric if strong).

  Mercurous chloride (calomel) occurs in nature, and was used in medicine (as laxative and diuretic) before RoF. It can be produced by heating mercury in chlorine, or reducing mercuric chloride, or reacting mercurous sulfate and sodium chloride.

  Mercuric chloride (corrosive sublimate) is another alchemical favorite, and can be obtained by heating mercuric sulfate with sodium chloride, or mercurous sulfate with HCl, or by simply chlorinating mercury or calomel. (EB11). The twelfth century Indian method was "heating mercury, salt, brick dust and alum for 3 days in a closed earthenware pot, and then adding water to dissolve out the corrosive sublimate before crystallizing it" (Emsley 255).

  Fulminate of mercury is used to make percussion caps. It is very dangerous stuff. Flint, 1633, Chapter 28. By September 1633 it is available in the USE, manufactured in pounds per week quantities, by workers receiving "hazardous duty" pay. Offord and Boatright, "The Dr. Gribbleflotz Chronicles, Part 2: Dr. Phil's Amazing Essence Of Fire Tablets" (Grantville Gazette 10) and Offord "A Change of Hart" (Grantville Gazette 25).

  In April 1632, Jan de Vries, one of De Geer's lieutenants, mentions plans to make mercury fulminate by "trial and error." Mackey, "The Essen Steel Chronicles, Part 2: Louis de Geer" (Grantville Gazette 8). By 1634, the Bernese are experimenting with it. Evans, "Thunder in the Mountains" (Grantville Gazette 12). And the French did the same, until Glauber gave them a better solution (see potassium chlorate). Flint, 1634: The Baltic War, Chapter 27.

  With the exception of the dangerous fulminate, mercury and its "standard" salts should be readily available, in limited quantities, even in 1631-32.

  Group 13 Metals

  Aluminum

  Aluminum is a precious metal, post-RoF, at least until we start producing it again. Massey, "Ultralight" (Grantville Gazette 9); Bergstralh, "One Man's Junk" (Grantville Gazette 4); Schillawski and Rigby, "Recycling" (Grantville Gazette 6). Anneke has a brand-new aluminum slide rule; made from a recycled strip. Carroll, "Stepping Up" (Grantville Gazette 14). Dr. Phil is driving people a little crazy with his quest for aluminum. Offord and Boatright, "Dr. Phil's Aeolian Transformers" (Grantville Gazette 6); DeMarce "Songs and Ballads" (Grantville Gazette 14); Cooper, "Stretching Out, Part Three: Maria's Mission" (Grantville Gazette 14).

  Cooper, "Aluminum: Will O' the Wisp?" (Grantville Gazette 8) explains where to find aluminum ores, how to extract alumina, how to refine it to obtain elemental aluminum, and finally how to use it. To mass produce it, we need bauxite as the ore, cryolite as a flux, and lots of cheap electricity. There are older methods which involve use of sodium or potassium as reducing agents. Right now, I am guessing "new" aluminum will be available in 1635. That's earlier than I said in my article, because I wasn't expecting cryolite to be mined as early as 1633. In Mackey, "Land of Ice and Sun" (Grantville Gazette 11), de Erauso brings back over 80 tons.

  Aluminum sulfate occurs in nature as keramohalite, but is more likely to be obtained by treating an aluminum-rich kaolin or china clay with sulfuric acid (EB11/Aluminium).

  Aluminum oxide (alumina) is an intermediate in the processing of bauxite into aluminum It is also the chemical composition of corundum, rubies and sapphires. .

  This is probably as good a place as any to mention the thermite reaction. Thermite is a mixture of aluminum powder and a metal oxide, usually iron oxide. When heated to the ignition temperature, the aluminum reacts with the iron oxide to form aluminum oxide. This is an extremely exothermic reaction, so it creates intense heat. Erwin O'Keefe demonstrates thermite welding to Dr. Phillip Gribbleflotz in Offord and Boatright, "The Dr. Gribbleflotz Chronicles, Part 2: Dr. Phil's Amazing Essence Of Fire Tablets"(Grantville Gazette 7), and Dr. Phil's Candles of the Essence of Light are apparently fabricated from thermite powder. Thermite reactions are more than just a curiosity, or a useful welding technique; they underlie the method used to extract a number of metals from their ores.

  Aluminum hydroxide is found in nature as the mineral gibbsite, in the ore bauxite. It is also produced by the Bayer process (1887) from alumina in bauxite. See Cooper, "Aluminum: Will O' The Wisp?" (Grantville Gazette 8).

  Gallium

  A byproduct of aluminum refining, hence unlikely to be exploited in the 1630s. It's used in high temperature thermometers because of its large liquid range. It is also a useful alloy. Gallium arsenide is a semiconductor.

  Other Group 13 Metals

  Indium, Thallium. Ignored

  Group 14 Metals/Metalloids

  Germanium

  Germanium is associated with silver, copper and zinc ores. (EA). In its heyday, germanium, suitably "doped," was a major semiconductor material. (You needed to provide it in extremely pure form, of course.) Nowadays, it has been superseded by other semiconductors, and its main use is in glass for infrared devices.

  For germanium to be of interest post-Ro
F, we would have to have advanced to the point of needing semiconductors, but not be able to make silicon in the necessary purity (Wikipedia).

  Tin

  Tin is obtained by heating cassiterite (tin oxide) with coke. Tin was used in the ancient world; the tin was alloyed with copper to make bronze. There is also tin foil, which was used pre-RoF as a reflective backing for glass mirrors.

  Tin is an old commodity, but the up-timers will teach the old dog some new tricks. These will include new alloys (e.g., Babbitt metal), tin plating of steel (the tin can be transferred to the steel surface by the chloride or sulfate, or deposited electrolytically), and the use of molten tin as the "float" in the Pilkington float glass process.

  Some tin compounds are already known to the down-timers. Stannous chloride was discovered in 1630, by Cornelius Drebbel, to be useful as a mordant. Satterlund, "Dyes and Mordants" (Grantville Gazette 5). Stannic chloride (spiritus fumans) was made by Libavius in 1605, by reaction with mercuric chloride (Levity).

  Other tin compounds should be fairly easy to make by instructions given in EB11, assuming the reagent is available.

  Lead

  Lead is also a metal of antiquity. Its principal ore is galena (lead sulfide), but cerussite (lead carbonate) and anglesite (lead sulfate) are also of interest. We will want to use lead, which is corrosion resistant, in sulfuric acid processing, and in making storage batteries.

  Lead oxide (litharge) is known to the down-timers. But the up-timers will reveal to them that it can be used to make lead-alkali (flint) glass.

  They are also familiar with lead acetate (sugar of lead), which is obtained by reacting lead oxide with vinegar.

  Lead nitrate (calx plumb dulcis) was known to Libavius (EB11).

  Lead chromate is a useful yellow pigment, known since the early nineteenth century (Eastaugh 99).

  The availability of lead compounds is going to be "anion-limited"; we need HCl to make the chloride, and chromate to make chrome yellow.

  Group 15 Metals/Metalloids

  The elements of this group are all known to down-timers (although not qua elements) and hence can be exploited fairly rapidly.

  Bismuth

  The down-timers have encountered bismuth (which occurs naturally in elemental form), although it's often confused with lead, tin, and antimony. It can be mined in Schneeburg, Saxony and Joachimsthal, Bohemia (EB11).

  The metal's most interesting use is perhaps as an alloying element in the low-melting Wood's metal. (EA). Unidentified bismuth compounds have been used to treat syphilis. Bismuth oxychloride might be used by the "new" cosmetics industry to impart an iridescent look.

  Arsenic

  Arsenic is known to the down-timers in the form of the naturally occurring realgar (disulfide)and orpiment (trisulfide), and the synthesized "white arsenic" (trioxide). The alchemists have probably made the metal itself, too, by reduction with carbon.

  The most common mineral is arsenopyrite (iron sulfide + iron arsenide, and arsenic is usually obtained as a byproduct of copper, gold, silver, lead, nickel or cobalt mining.

  Realgar and orpiment were in pre-RoF use as pigments (and white arsenic as the infamous "inheritance powder").

  The reaction of arsenic with concentrated nitric acid produces arsenic acid. Several arsenate salts (copper, calcium, lead) were used in decades past as insecticides.

  Arsphenamine, an organo-arsenic compound, was introduced in 1909 as a treatment for syphilis. Its formula appears in the Merck Index.

  The most interesting use of elemental arsenic is probably in the hardening of lead shot (EB11/Lead).

  Antimony

  Antimony is found in nature as white antimony (oxide) and black antimony (trisulfide; stibnite; kohl). The down-timers have isolated the pure element and quite a few antimony compounds. The Triumphal Chariot of Antimony, 1604 (attributed to Basil Valentine but actually written by Johann Tholde) apparently refers to antimony trichloride ("butter of antimony"), antimony nitrate ("fixed antimony") and antimony oxysulfide ("glass of antimony"). Oswald Croll's Basilica Chymica (1604) discussed antimony trichloride and antimony oxychloride ("powder of algaroth"). (Emsley II, 201). Beguin's Elements of Chemistry (1615) describes the reaction of stibnite with mercuric chloride to make antimony trichloride (Salzberg 151). The Chaldeans used lead antimonate, and there is reason to believe that Greek fire included antimony sulfide.

  Antimony metal is used to harden lead. Antimony oxide is used as a flame retardant.

  Predictions

  Table 2-4 suggests a chronology for when the metals are available, whether as cations of salts, or in elemental form. This is a summary (and gross simplification) of the analysis earlier in the article. If you are interested in a particular chemical, read the detailed analysis. In general, the metal will first be available as a cation of a naturally occurring salt, and only later (sometimes much later) as the metal itself. How soon will depend on both the demand for the metal and the ease of extraction.

  This table is not canon! If enough effort is devoted, early enough, chemicals can be produced earlier than what I forecast.

  Some of the elemental metals (e.g., potassium) are listed relatively late because I don't expect them to be in great demand. If you want to write a story whose character has an earlier need for potassium, that's fine with me and the Grantville Gazette Editorial Board.

  Production of elemental metals is dependent on access to the ores. For the purpose of this article, I ignore which countries control that access. For control issues, see Cooper, "Mineral Mastery: Discovery and Control of Ore Deposits After the Baltic War" (Grantville Gazette 23).

  And I assume a minimum of problems in getting access. Please note that it can take years to get an expedition approved by a government (especially Spain), and without bureaucratic blessing, you can find your mother lode and have it taken away from you immediately. And it can take more years to find the deposit, especially if you have to hack your way through jungle or fend off unfriendly natives.

  Production of metals can also be dependent on technology, e.g., an electric furnace or electrochemical cells. I have assumed that these are available, on a laboratory scale, by 1633.

  There are also "connections" between chemicals. For example, some elements are found as byproducts of mining for other elements. Others are extracted using another element (e.g., aluminum, sodium) as a reducing agent. That increases the demand for the reducing agent, but means that if there are problems obtaining it, the chronology gets thrown off.

  Next Part . . . Organic Chemistry!

  Binding the Land With Steel

  Written by Kevin H. Evans

  It came to pass in the days of Gustav Adolphus, messengers came forth from another time, and the people all did clamor, "Our children are starving and we are cold."

  And behold, the messengers did create Granges and Factories, and plenty from there came forth. And the people again did cry out, "The bounty does not come forth from the messengers to feed our children."

  Wherefore, the messengers were sent to create roads of iron. And thereafter, rails did span the land, and there was abundance for all.

  Maybe this is how European historians will record it hundreds of years after our time frame. It will appear that the up-timers waved their magical wands, and the railroads were created. These abilities would be terrific, but the reality of creating a working railroad from scratch is much different.

  Construction of a railroad, especially a railroad where almost all the work is done by hand, is an enormous undertaking. Such construction may be one of the largest projects that the down-time population has ever seen. The construction of the mighty Roman roads and cities, or the great cathedrals of Europe come close in the amount of manpower and effort required. Of all works that people create, railroads are among the largest.

  Even a short line railroad typically includes a right-of-way, or path, that is some fifty feet wide and many hundreds of miles in length. The facilities required include stations, track maintenan
ce facilities, the actual track, and large numbers of vehicles that are used to transport people and commodities over the route. The crews that build these railroads are really large. In the late 1800s the crew that built the transcontinental railroad from Omaha, Nebraska to San Francisco was composed of over twenty thousand men. Construction required a little over five years, even with such large crews. The record for the amount of track laid in one day was only ten miles. Food, shelter, sanitation, and supply were major concerns.

  While we will use the railroads constructed in North America as our source, we will primarily talk about the new timeline. Constructing a railroad falls into roughly ten major areas of concern, or tasks. These responsibilities will be divided over three crews.

  In order of process, these tasks are: setting the standards, obtaining the right-of-way, financing, surveying the route, creating the road bed, laying down the ties, setting the rails, attaching the rails to the ties, ballasting the track, and all of the support services needed to keep everybody working.

  The three crews actually involved in the construction are the survey crew, the grading crew, and the track-laying crew.

  The first couple of the tasks mentioned have either been covered elsewhere, or are too complicated to go into for this article. The tasks of setting the standards and route selection have been covered by Iver P Cooper and Carsten Edelberger in Grantville Gazette, Volume Seven. In these articles, careful attention has been paid to just exactly what we need as standards, and where we need to build the railroads.

  Obtaining the right-of-way has also been covered. We should note that in the 1632 universe, railroads are very new ideas. Nobles and landowners, farmers and local residents, city dwellers and itinerant workers will all be alternately frightened, concerned, fascinated, or misinformed on the real value of railroad. So before anything is done on building, securing the land to build on will be paramount.