Grantville Gazette Volume 25

by editor Paula Goodlett

  That said, given the difficulties of finding and processing the ore, I don't expect lithium to be in play in the 1630s.

  Sodium

  Sodium chloride is, of course, a classic food additive, and is also a deicing agent and a desiccant/preservative. The chemical industry uses it as a source of sodium (particularly sodium hydroxide and carbonate) and chlorine.

  Sodium hydroxide (lye, caustic soda) has been used as a strong base since medieval times (OED). In Gassage's method (1853), it was made by reaction of quicklime (calcium oxide) with a boiling solution of crude sodium carbonate. The modern industrial method is by the electrochemical chloralkali process. (EA). Sodium hydroxide is used by Lewis Bartolli in summer 1634 as a forensic reagent, to detect iron in gall inks. (Lewis has other weak and strong acids and alkalis at his disposal, but we don't know which.) Cooper, "Under the Tuscan Son" (Grantville Gazette 9).

  Sodium carbonate (soda ash) was derived down-time from seaweed, or salt-tolerant land plants. The plant material was dried and burnt, and then the ash was washed with water, and the resulting crude solution boiled dry to yield a purer ash. Because sodium carbonate was used as a flux in the glass industry, some of the plants so used were called glasswort. Spain exported soda ash (30% sodium carbonate) made from Salsola soda; it was illegal to export the seed.

  The modern American source is trona, which is a mixture of sodium carbonate and sodium bicarbonate. Trona itself is similar to ancient Egyptian natron (the inspiration for the "Na" used to symbolize the element sodium).

  Sodium carbonate can also be synthesized, and several of the earliest industrial chemical processes were intended to produce it (EB11, Alkali Manufacture). The LeBlanc process (1790) featured a double replacement reaction; sodium chloride reacted with sulfuric acid to make sodium sulfate and hydrochloric acid. The sodium sulfate was then "fluxed" with calcium carbonate and coal.

  The LeBlanc process was eclipsed by the ammonia-soda process (1838), especially as improved by Solvay (1872). Ammonia, water and carbon dioxide react in situ to make ammonium bicarbonate, and that reacts with sodium chloride to make sodium bicarbonate and ammonium chloride. The bicarbonate, when heated, releases the carbonate and carbon dioxide.

  Sodium bicarbonate (baking soda) can be synthesized by adding carbon dioxide to sodium carbonate. Another route is by interrupting the Solvay process of producing sodium carbonate. Sodium bicarbonate was made in 1631-32 by Dr. Phil in Offord, "The Doctor Gribbleflotz Chronicles, Part 1: Calling Dr. Phil," Grantville Gazette 6. Dr. Phil used the Solvay technique (Offord, private communication).

  Sodium nitrate is found in large deposits in Chile, and can be converted to potassium nitrate by reacting it with potassium chloride. Glauberite (sodium calcium nitrate) is found in Stassfurt (EB11).

  Glauber's salt is sodium sulfate and was first prepared (as sal mirabilis) by Johann Glauber in 1658. He reacted sodium chloride with sulfuric acid.

  Sodium fluoride is made by treating sodium hydroxide or sodium carbonate with HF.

  Natural cryolite (sodium aluminum fluoride) is mined in Greenland, in summer 1633, by an expedition sponsored by Louis De Geer. Mackey, "Land of Ice and Sun" (Grantville Gazette 11). The cryolite is of value in making soda (sodium carbonate) by the "cryolite soda" process, as a flux in smelting aluminum from aluminum oxide, and as an aluminum ore in its own right. By early 1636, Dr. Phil's HDG Enterprizes has made synthetic cryolite in small quantities. Offord, "Doctor Phil's Family" (Grantville Gazette 15). Most likely, this was by reacting sodium hydroxide, aluminum hydroxide, and HF.

  Sodium metal is a johnny-come-lately. It was first made in 1807 by electrolysis of sodium hydroxide. Then, for a period, it was made by igniting charcoal with sodium hydroxide. The current production method is by electrolysis of molten sodium chloride together with calcium chloride or sodium carbonate.

  The metal is used as a reducing and dehydrating agent, and in sodium vapor lamps (EA). It can also be used in preparation of the organic chemical reagent sodium borohydride.

  I expect sodium metal to be the first of the group 1 or 2 metals to be produced post-RoF. However, problems (see EB11/Sodium) should be expected in attempting to reduce so reactive an element.

  Potassium

  Potassium nitrate (saltpeter) is formed by bacterial action on human and animal waste. It is one of the three main ingredients of gunpowder.

  Potassium chloride's principal use is as a source of potassium ions for plant growth. It's also used to make potassium carbonate. It's found naturally as sylvinite (potassium and sodium chloride) or carnallite (potassium and magnesium chloride). The latter is found at Stassfurt (Emsley 336).

  Potassium chlorate has been used, by 1634, as a primer for the French "Cardinal" musket. Greg Ferrara, the USE's R&D boss, had told Mike Stearns that "the production process would be way too complicated," but that was an oversight on his part. Flint, 1634: The Baltic War, Chapter 55.

  Potassium hydroxide (caustic potash) is made by down-timers by reacting calcium hydroxide (slaked lime) with potassium carbonate (EB11). The reaction is driven by the precipitation of the insoluble calcium carbonate. The modern production method (I don't know if it's known in Grantville) is by electrolysis of potassium chloride solutions.

  Potassium carbonate was derived down-time from hardwood trees. The wood was burnt, and the ash washed with water and then boiled dry to yield the impure salt, potash. This could be baked in a kiln to make a purer form, pearlash. A modern method of making it is by electrolysis of potassium chloride in an aqueous solution, yielding potassium hydroxide, which in turn is carbonated.

  Potassium bicarbonate is useful in baking and, interestingly, as a fire suppression agent.

  Alum is not a single compound but rather a series of related compounds that are all "double" sulfates, that is, sulfates of two different cations, an alkali metal (or ammonium) and a trivalent metal. Potassium aluminum sulfate occurs in nature in the mineral alunite, from which it can be obtained by treatment with sulfuric acid. In the late twentieth century, the two most important alums were potassium aluminum sulfate and ammonium aluminum sulfate All of the alums can be made by mixing and heating solutions of the appropriate single sulfates. Alums are used as mordants, that is, to fix dyes to fabric.

  Potassium metal isn't used much, because its uses are similar to those of the cheaper metal, sodium. (EA).

  Other Group 1 Metals

  Rubidium, cesium and francium. Ignored.

  Group 2 Metals

  Beryllium

  Beryllium metal is alloyed with copper (EA) and nickel (Emsley 58), improving their conductivity and elasticity. Beryllium oxide is used in ceramics.

  The principal ore is beryl (beryllium aluminum silicate), and European sources exist. (EB11/Beryl). The modern production method involves treatment with, successively, sodium fluoride, caustic soda and HCl or HF, and then electrolytic reduction of the chloride or magnesium reduction of the fluoride (EA).

  The beryllium content of beryl is rather low (Simons 13) and I can't help thinking it's more trouble than it's worth.

  Calcium

  Calcium oxide (quick lime) is produced down-time by heating calcium carbonate (from limestone) sufficiently to decompose it into calcium oxide and carbon dioxide. It is much more important than calcium metal (Table 2-3 above; Emsley 87).

  Calcium hydroxide (slaked lime) has also been known since ancient times, and was made by reacting calcium oxide with water.

  Calcium sulfate is, in hydrated form, the mineral gypsum. It is used in the manufacture of plaster of Paris and Portland cement.

  Calcium hypochlorite. In December, 1633, Nicki Jo tells Scaglia and Rubens that Essen is producing this bleach and a disinfectant. Mackey, "Ounces of Prevention" (Grantville Gazette 5). It's doing so by the processes described in Wagner, A Handbook of Chemical Technology (1872) (Mackey, private communication). Wagner makes calcium hypochlorite by reacting chlorine gas with slaked lime (calcium hydroxide). That reaction is described in EB11/Alkal
i Manufacture.

  Calcium carbide is made by reducing lime with coke in an electric furnace at 2000oC. It is an "acetylene generator"; add water, and it decomposes into acetylene and lime. This reaction explains the flame of the miner's safety lamp. Carbide lamps are used in January 1635 by the miners in Huston, "Twenty-Eight Men" (Grantville Gazette 10). They have clearly been made since the RoF since they were retrofitted onto the up-time hard hats.

  Calcium carbonate is the principal mineral of chalk, limestone and marble, and is also found in shells.

  Calcium metal is used as a reducing and drying agent. Its reducing power is such that it can react with water to generate hydrogen. It's produced by electrolysis of the fused chloride or fluoride, or reduction of lime with aluminum and heat. (EA).

  Plainly, several calcium compounds are going to be available even in 1631. Calcium metal can be made electrolytically in Grantville, which has cheap electricity, at least once we have graphite to serve as the anode. The question is when will the demand be sufficient to warrant the startup costs. My guess is that this will be affected by the demand for metals which can be reduced by calcium but not (at least easily) by carbon—e.g., sodium and magnesium. Outside Grantville, production of calcium metal will be dependent on the availability of aluminum.

  Magnesium

  Magnesium has a variety of uses. Pure magnesium powder is used in pyrotechnics and incendiaries. Magnesium is also necessary to make Grignard reagents, which are important organic chemical intermediates. The bulk metal can also be used to protect less active metals from corrosion. Magnesium-steel alloys have a high strength-to-weight ratio.

  There are several ores (see table 2-3), and magnesium can also be found in seawater and salt well brines.

  The secret to extracting magnesium from seawater (0.13% magnesium) is to add a calcium salt, which, by a double replacement, causes production of an insoluble magnesium salt. The latter can then be converted into the chloride.

  Magnesium metal is preferably made by electrolytic reduction of the fused chloride, and CW215 suggests that it be a mixture of magnesium, calcium, and sodium chlorides (which avoids a separation step). The alternative is chemical reduction of the oxide with carbon or ferrosilicon ,at high temperature, but it's inefficient. EB11 teaches that carboreduction doesn't work, but CW215 suggests heating with coke at 2000oC followed by rapid quenching.

  Epsom salts (crude magnesium sulfate) were discovered by Henry Wicker in 1618 (Emsley 245).

  Strontium

  Ignored.

  Barium

  Barium is found principally as barite (barium sulfate) or witherite (barium carbonate). Barite is associated with lead and silver ore veins (EB11/Barytes), and it can be found near Stuttgart (HCA).

  It has been known since 1602 that barite phosphoresces if heated. Barium sulfate is undoubtedly known to Grantville's doctors because of its use in X-ray studies of the digestive system. Lithopore (mixture of barium sulfate and zinc sulfide) is a white pigment. Both the sulfate and the carbonate are used in fluxes. Barium peroxide was used in 1818 to prepare hydrogen peroxide.

  Barium proper, in vapor form, is used to remove oxygen, nitrogen and carbon dioxide from vacuum tubes. Manufacturing barium is by reduction of barium oxide (derived from the sulfate or carbonate) with aluminum.

  In conclusion, barium is an element of mild interest. Barite itself can be exploited early on, but use of the metal must await the production of aluminum (and vacuum tubes).

  Radium

  Ignored.

  Group 3 Metals

  Scandium, yttrium and lutetium. Ignored.

  Group 4 Metals

  Titanium

  Titanium dioxide occurs in nature as the minerals rutile, rookite and anatase. There are hints that Portuguese entrepreneurs are considering the mining of the Keralese beach deposits in Cooper, "Gajam Raanni," (Grantville Gazette 25).

  Titanium was first used as a structural metal in 1952 (NACE 1978); it has the highest strength-weight ratio of the metals (making it attractive for aircraft), and good corrosion resistance. Some of the early methods of extracting titanium include fusion with potassium bisulfate or with potassium carbonate, or by the reaction of titanium fluoride with steam. (EB11/Titanium). However, EA says that it was not possible to mass produce titanium until the development of the Kroll process (1937), which it nonetheless characterizes as "relatively slow and costly." The requirements for the Kroll process include chlorine (to form titanium tetrachloride), metallic magnesium or sodium, and some kind of inert atmosphere (typically argon or helium, and very definitely not nitrogen).

  In view of the discouraging text, not to mention the difficulties of satisfying the prerequisites for the Kroll process, I think that titanium isn't likely to be exploited, in elemental form, in the 1630s.

  Of course, that doesn't mean we can't make use of titanium dioxide directly; it's a fine white pigment.

  Zirconium

  The principal ore of zirconium is zircon (zirconium silicate), which pokes its toe into seventeenth century international commerce as a Ceylonese gemstone. EB11 gives instructions for the preparation of zirconia (zirconium oxide); you need potassium fluoride, hydrofluoric acid, and ammonia. Zirconia is good for high-temperature ceramics.

  We could probably make zirconia in 1636, but we aren't like to have a need for it for many years later. The metal (which has good corrosion resistance) is unlikely to be of interest in the up-timers' lifetimes.

  Hafnium

  Ignored.

  Group 5 Metals

  Vanadium

  Vanadium is the most important metal of this group. The metal is alloyed with steel and titanium; Runkle listed it as an important ingredient for tool steel and stainless steel.

  Vanadium was first discovered in the slag from a Swedish iron smelter; the iron ore came from Taberg. The ore descloizite (lead-zinc vanadate) is found at, among other sites, Eisen-Kappel near Klagenfurt in Carinthia, associated with lead ores (EB11). There are other ores which are oxides or sulfides. There are relatively few mines. (Simons 224).

  Considering not only what the encyclopedias say about vanadium extraction, but also other sources, I get the impression that the process is on the difficult side. While the encyclopedias mention alternative methods, it seems that the principal large-scale process is reducing the oxide with calcium (see above) in the presence of calcium chloride or iodide at a high temperature, and possibly in an inert gas (argon) atmosphere. (Emsley, 485; Simons, 224; Patnaik 964). EA mistakenly says that vanadium oxide can be reduced with carbon (Emsley).

  The only hope I see for "first decade" production of vanadium-steel alloys is if we can make those alloys without first extracting vanadium. Emsley says that "ferrovanadium," which is what is added to steel, can be made from vanadium oxide by heating with ferrosilicon.

  Niobium

  Niobium (EB11/Columbium) is used as an anti-corrosive alloying element in steel. It was produced, at the end of the twentieth century, at a rate of 25000 tonnes annually, of which over 85% came from Brazil (Emsley 284). Its principal ore is columbite, a complex oxide. The closest source to the USE is probably Rabenstein, Bavaria (EB11/Columbite), but I don't know if it's an economic one.

  Tantalum

  Tantalum is of minor importance; even in 2000, demand was around 1000 tonnes annually. At one time, lamp filaments were made out of Tantalum, but such were superseded by Tungsten. Nowadays, it's important mostly because of its superb corrosion resistance, which is comparable to that of glass (rembar.com), and as a melting point-enhancing alloying element. It is usually found with niobium.

  Group 6 Metals

  Chromium

  Chromium is needed to make stainless (>10% chromium) steel, and other alloys (nichrome, stellite). It can also be used to plate other metals. The principal ore of chromium is chromite (ferrous chromate). There are chromite prospectors in Kemi, Finland by 1633 (1633 Chap. 26) and in Maryland perhaps by 1634. (Mackey, "Trip to Paris," Grantville Gazette 9). However, as of July
1634, Lolly Aossi is not aware of any chromium having come on the market yet. Runkle, "Sunday Driver" (Grantville Gazette 13).

  Of course, the chromium has to be extracted. It can be recovered by several methods, one of which successively requires soda ash, coke and aluminum, and the other, direct reduction with carbon or silicon in an electric arc furnace (EA), and there are additional variations disclosed by EB11. My guess is that the electric arc furnace process would be favored in Grantville, which has plentiful cheap electricity. Essen has also obtained cryolite (see "Aluminum") and therefore might favor the first method.

  EA/Steel says that virtually all stainless are at least 11.5% chromium, and that AISI 302, with excellent corrosion resistance, is 0.15% carbon, 18% chromium, 8% nickel.

  Chromic oxide is used as a green pigment, and it's an intermediate in the soda ash-coke process of producing chromium. Sodium chromate, sodium and ammonium dichromate, and chromic acid are strong oxidizing agents. Lead chromate (the mineral crocoisite) is the pignment "chrome yellow." Chromic acid is obtained by dissolving chromic oxide in water, and EB11/Bichromates and chromates explains how to make many of its salts.

  The earliest I imagine chromium metal could be available is 1635, but 1636 is perhaps more likely. Once we have chromic oxide, we can make the chromates and dichromates.

  Molybdenum

  Molybdenum is used as a catalyst and an alloying element (it hardens and toughens steel). The main ore is molybdenite (molybdenum sulfide) , which looks quite a bit like graphite, and like it was used in "lead" pencils (Sarkar, 504). Chemists didn't distinguish molybdenum from graphite until 1779. It's therefore conceivable that a pre-RoF reference to a "drawing lead" is actually to molybdenite, but I think that unlikely, as the principal European deposits are in Norway and Norway was not very developed in the early seventeenth century.