Part 4 - Nineteenth Century

About the same time Wollaston began separating palladium, John Dalton began the study of a new field of study on atomic weights. He began with the gases, and in 1804, turned to metals. This landmark thinking inspired Swedish chemist J. J. Berzelius to propose determining the atomic weight of all elements then known. By 1814 he published a tentative table, based on oxygen taken as 100. The table included numbers for palladium, platinum and rhodium. He also proposed the use of the now familiar chemical symbols. We acquired Pt for platinum, while his initial proposal for palladium was Pl, and was later revised twice, ending with the present Pd. A number of compounds of the platinum metals saw exploration. A rose colored salt formed from palladium with ammonia and chlorine was reported in 1813.

Wollaston continued to refine and market platinum group metals for various applications. He was most successful marketing platinum, but considerably less so with palladium, and without a market for it, his stocks of palladium continued to grow. It was a metal that was available before technology found uses for it. Wollaston did market the metal for use in analytical weights. Eventually he gave a considerable quantity of palladium to the Royal Society. Unfortunately, Wollaston’s supply of native platinum ended in 1820, when he ceased offering his products to industry.

Percival Norton Johnson, son and former apprentice of assayer John Johnson who had a close relationship with Wollaston, in 1817, formed a gold refining company and began refining gold, the beginnings of what became the Johnson Matthey Company. Johnson took up refining platinum when Wollaston abandoned his work. Brazilian gold, which had high palladium content, became a specialty largely because his refinery was the only one capable of refining the ore and separating the palladium. Like Wollaston, he had trouble finding an outlet for the large stores of palladium he began to collect. He marketed the metal for use in chemical balances, for rust free surgical instruments, use as lighthouse reflectors, and as a substitute for steel in some circumstances, such as pen tips.

1820s

In 1820 Humphrey Davy first observed the process of catalytic oxidation, describing it as a “perfectly new principal in combustion.” It was German Johann Wolfgang Döbereiner though, who carried on the experimentation to fully understand the process, finding that platinum group metals in a fine powder, had the power to unite oxygen and hydrogen even at low temperatures.

The 1820s also saw the discovery of platinum metals in Russia, though rumors had persisted from earlier. In 1825, the Imperial Russian Government declared native platinum to be a State Monopoly, and required a state license for any dealings in associated metals. All refining was to take place at the St. Petersburg Mint. One result of this was the growth of a robust smuggling enterprise, with the metal finding its way out of Russia through black market channels. Russian successes at separating platinum from gold, rendering it malleable and producing utensils from it were noteworthy. Russian scientist Peter Grigorievich Sobolevsky made important headway in his research given that Wollaston’s process had not yet been published.

1830s

The 1830s saw discoveries of a number of properties of this group of metals. Michael Faraday’s experiments in electrochemistry provided further scientific insight for the platinum group metals. Faraday often used platinum plates as electrodes because it was resistant to reaction with the other elements involved. He coined the terms we still use today: anode, cathode, electrolysis, and electrolyte. William Robert Grove, chemist and lawyer, added to the experimentation and quite notably, developed the first platinum based fuel cell. During 1832, English chemist and astronomer Sir John Herschel made a remarkable discovery with platinum concerning the effect of light on certain chemical reactions, a discovery that placed his name among the inventors of photography. Swedish chemist J. J. Berzelius experiments with and coins the term “catalysis”. Real progress in applications of catalysis in industry would wait many decades.

1840s

In 1840, a researcher named Alfred Smee published a landmark book entitled “Elements of Electrometallurgy” in which he described the processes of plating with both platinum and palladium through the use of a galvanic current. He called the process platinating or palladiating. For palladium plating, Smee used nitro-muriate of palladium as an electrolyte, and a palladium anode, though the process did pose some difficulties. Other researchers improved on the process through the decade. Another platinum group metal, ruthenium was discovered. During this period, the Russians, who had been using platinum for currency were now fighting an uphill battle using it. Coinage in platinum ceased, ending the sole commercial demand for the metal that had not yet developed other uses. Mining output from the Urals collapsed. George Matthey who began an apprenticeship with Percival Johnson as a teenager, took charge of the firm’s platinum laboratory at age 20.

1850s

In 1869, Graham had a number of medallions minted in what he believed to be an alloy of palladium and hydrogen, which he called hydrogenium

The 1850s began with a notable new partnership. George Matthey was successful in negotiating an arrangement with one of the Russian mine owners to be the sole platinum refiner and selling agent. One of palladium’s most important properties was discovered as a result of researches of Thomas Graham, London chemist. In 1854, he was investigating how red-hot platinum absorbed hydrogen and discovered it could do so for an indefinite period of time, and no other gases produced the remarkable effect. Turning to palladium, he found that it could absorb 5 or 6 hundred times its own volume in hydrogen. When exposed to coal gas, only the hydrogen penetrated the palladium. This decade also saw considerable improvements in the achievement of high temperatures for melting metals. In France, the use of coal gas and oxygen in blow pipes were investigated, and using crucibles of lime or magnesia, achieved some success with platinum. Using these principals, Frenchmen Deville and Debray devised a process to refine native platinum and filed patents in France and Britain in 1857. The British rights were immediately acquired by George Matthey.

1860s to 1900

The 1860s saw further progress in the commercial melting of platinum metals, though a problems with purity remained a concern. Separately in Germany, the firm Haraeus developed their own method for casting platinum. The growth of more available platinum metals fueled further search for applications. In 1867, an international metallurgical exhibition held in Paris was a huge success for the platinum products of Johnson Matthey, featuring over 15,000 ounces of platinum products including huge boilers. Scientific research of the 1860s and into the 1870s was influenced by the rise of German militarism and unification under Prussian dominance orchestrated by Otto von Bismarck with wars with Austria (1867), then France (1870-1871).

In 1888, rich copper nickel ore was discovered in Ontario, Canada containing some PGMs, but the successful extraction of these would wait years.

Continued from Part 3
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