46 Pd

Transition metal

Overview

Palladium is a chemical element; it has the symbol Pd and atomic number 46. It is a rare and lustrous silvery-white metal discovered in 1802 by the English chemist William Hyde Wollaston. He named it after the asteroid Pallas (formally 2 Pallas), which was itself named after the epithet of the Greek goddess Athena, acquired by her when she slew Pallas. Palladium, platinum, rhodium, ruthenium, iridium and osmium form together a group of elements referred to as the platinum group metals. They have similar chemical properties, but palladium has the lowest melting point and is the least dense of them.
More than half the supply of palladium and its congener platinum is used in catalytic converters, which convert as much as 90% of the harmful gases in automobile exhaust (hydrocarbons, carbon monoxide, and nitrogen dioxide) into nontoxic substances (nitrogen, carbon dioxide and water vapor). Palladium is also used in electronics, dentistry, medicine, hydrogen purification, chemical applications, electrochemical sensors, electrosynthesis, groundwater treatment, and jewelry.
Ore deposits of palladium and other platinum group metals are rare. The most extensive deposits have been found in the norite belt of the Bushveld Igneous Complex covering the Transvaal Basin in South Africa; the Stillwater Complex in Montana, United States; the Sudbury Basin and Thunder Bay District of Ontario, Canada; and the Norilsk Complex in Russia. …

History

William Hyde Wollaston noted the discovery of a new noble metal in July 1802 in his lab book and named it palladium in August of the same year. He named the element after the asteroid 2 Pallas, which had been discovered two months earlier (and which was previously considered a planet). Wollaston purified a quantity of the material and offered it, without naming the discoverer, in a small shop in Soho in April 1803. After harsh criticism from Richard Chenevix, who claimed that palladium was an alloy of platinum and mercury, Wollaston anonymously offered a reward of £20 for 20 grains of synthetic palladium alloy. Chenevix received the Copley Medal in 1803 after he published his experiments on palladium. Wollaston published the discovery of rhodium in 1804 and mentions some of his work on palladium. He disclosed that he was the discoverer of palladium in a publication in 1805.
Wollaston found palladium in crude platinum ore from South America by dissolving the ore in aqua regia, neutralizing the solution with sodium hydroxide, and precipitating platinum as ammonium chloroplatinate with ammonium chloride. He added mercuric cyanide to form the compound palladium(II) cyanide, which was heated to extract palladium metal.
Palladium chloride was at one time prescribed as a tuberculosis treatment at the rate of 0.065 g per day (approximately one milligram per kilogram of body weight). This treatment had many negative side-effects, and was later replaced by more effective drugs. …

Properties

Palladium belongs to group 10 in the periodic table, but the configuration in the outermost electrons is in accordance with Hund's rule. Electrons that by the Madelung rule would be expected to occupy the 5s instead fill the 4d orbitals, as it is more energetically favorable to have a completely filled 4d10 shell instead of the 5s2 4d8 configuration.

This 5s0 configuration, unique in period 5, makes palladium the heaviest element having only one incomplete electron shell, with all shells above it empty.
Palladium has the appearance of a soft silver-white metal that resembles platinum. It is the least dense and has the lowest melting point of the platinum group metals. It is soft and ductile when annealed and is greatly increased in strength and hardness when cold-worked. Palladium dissolves slowly in concentrated nitric acid, in hot, concentrated sulfuric acid, and when finely ground, in hydrochloric acid. It dissolves readily at room temperature in aqua regia.
Palladium does not react with oxygen at standard temperature (and thus does not tarnish in air). Palladium heated to 800 °C will produce a layer of palladium(II) oxide (PdO). It may slowly develop a slight brownish coloration over time, likely due to the formation of a surface layer of its monoxide.
Palladium films with defects produced by alpha particle bombardment at low temperature exhibit superconductivity having Tc = 3.2 K.

Naturally occurring palladium is composed of six stable isotopes. …

Sources & occurrence

As overall mine production of palladium reached 210,000 kilograms in 2022, Russia was the top producer with 88,000 kilograms, followed by South Africa, Canada, the U.S., and Zimbabwe. Russia's company Norilsk Nickel ranks first among the largest palladium producers globally, accounting for 39% of the world's production.
Palladium can be found as a free metal alloyed with gold and other platinum-group metals in placer deposits of the Ural Mountains, Australia, Ethiopia, North and South America. For the production of palladium, these deposits play only a minor role. The most important commercial sources are nickel-copper deposits found in the Sudbury Basin, Ontario, and the Norilsk–Talnakh deposits in Siberia. The other large deposit is the Merensky Reef platinum group metals deposit within the Bushveld Igneous Complex South Africa. The Stillwater igneous complex of Montana and the Roby zone ore body of the Lac des Îles igneous complex of Ontario are the two other sources of palladium in Canada and the United States. Palladium is found in the rare minerals cooperite and polarite. Many more Pd minerals are known, but all of them are very rare.
Palladium is also produced in nuclear fission reactors and can be extracted from spent nuclear fuel (see synthesis of precious metals), though this source for palladium is not used. None of the existing nuclear reprocessing facilities are equipped to extract palladium from the high-level radioactive waste. …

Uses

The largest use of palladium today is in catalytic converters. Palladium is also used in jewellery, dentistry, watch making, blood sugar test strips, aircraft spark plugs, surgical instruments, and electrical contacts. Palladium is also used to make some professional transverse (concert or classical) flutes. As a commodity, palladium bullion has ISO currency codes of XPD and 964. Palladium is one of only four metals to have such codes, the others being gold, silver and platinum. Because it adsorbs hydrogen, palladium was a key component of the controversial cold fusion experiments of the late 1980s.

When it is finely divided, as with palladium on carbon, palladium forms a versatile catalyst; it speeds heterogeneous catalytic processes like hydrogenation, dehydrogenation, and petroleum cracking. Palladium is also essential to the Lindlar catalyst, also called Lindlar's Palladium. A large number of carbon–carbon bonding reactions in organic chemistry are facilitated by palladium compound catalysts. For example:

Heck reaction
Suzuki coupling
Tsuji-Trost reactions
Wacker process
Negishi reaction
Stille coupling
Sonogashira coupling
When dispersed on conductive materials, palladium is an excellent electrocatalyst for oxidation of primary alcohols in alkaline media. Palladium is also a versatile metal for homogeneous catalysis, used in combination with a broad variety of ligands for highly selective chemical transformations. …

Isotopes

Naturally occurring palladium is composed of six stable isotopes. The most stable radioisotopes are 107Pd with a half-life of 6.5 million years (traces found in nature), 103Pd with a half-life of 16.99 days, and 100Pd with a half-life of 3.63 days. There are 25 other radioisotopes characterized ranging from 91Pd to 129Pd. These have half-lives of less than thirty minutes, except 101Pd (8.47 hours), 109Pd (13.6 hours), and 112Pd (21.0 hours).
For isotopes with atomic masses less than that of the most abundant stable isotope, 106Pd, the primary decay mode is electron capture with the primary decay product being rhodium. The primary mode of decay for those isotopes of Pd with atomic mass greater than 106 is beta decay with the primary product of this decay being silver.
Radiogenic 107Ag is a decay product of 107Pd and was first discovered in 1978 in the Santa Clara meteorite of 1976. The discoverers suggest that the coalescence and differentiation of iron-cored small planets may have occurred 10 million years after a nucleosynthetic event. 107Pd versus Ag correlations observed in Solar System bodies must reflect the presence of short-lived nuclides in the early Solar System.
107Pd is also produced as a fission product in spontaneous or induced fission of 235U. As it is not very mobile in the environment and has a relatively low decay energy, 107Pd is usually considered to be among the more benign of the long-lived fission products.

Hazards & biological role

Palladium is a metal with low acute toxicity (e.g. LD50). Recent research on the mechanism of palladium toxicity suggests high toxicity if measured on a longer timeframe and at the cellular level in the liver and kidney. Mitochondria appear to have a key role in palladium toxicity via mitochondrial membrane potential collapse and depletion of the cellular glutathione (GSH) level. Until that recent work, it had been thought that palladium was poorly absorbed by the human body when ingested. Plants such as the water hyacinth are killed by low levels of palladium salts, but most other plants tolerate it, although tests show that, at levels above 0.0003%, growth is affected. High doses of palladium could be poisonous; tests on rodents suggest it may be carcinogenic, though until the recent research cited above, no clear evidence indicated that the element harms humans.

Like other platinum-group metals, bulk Pd is quite inert. Although contact dermatitis has been reported, data on the effects are limited. It has been shown that people with an allergic reaction to palladium also react to nickel, making it advisable to avoid the use of dental alloys containing palladium on those so allergic.
Some palladium is emitted with the exhaust gases of cars with catalytic converters. Between 4 and 108 ng/km of palladium particulate is released by such cars, while the total uptake from food is estimated to be less than 2 μg per person a day. …