Chemical element with atomic number 82 (Pb)
Lead () is a chemical element; it has symbol Pb (from Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cut, lead is a shiny gray with a hint of blue. It tarnishes to a dull gray color when exposed to air. Lead has the highest atomic number of any stable element and three of its isotopes are endpoints of major nuclear decay chains of heavier elements.
Lead is a relatively unreactive post-transition metal. Its weak metallic character is illustrated by its amphoteric nature; lead and lead oxides react with acids and bases, and it tends to form covalent bonds. Compounds of lead are usually found in the +2 oxidation state rather than the +4 state common with lighter members of the carbon group. Exceptions are mostly limited to organolead compounds. Like the lighter members of the group, lead tends to bond with itself; it can form chains and polyhedral structures.
Since lead is easily extracted from its ores, prehistoric people in the Near East were aware of it. Galena is a principal ore of lead which often bears silver. Interest in silver helped initiate widespread extraction and use of lead in ancient Rome. Lead production declined after the fall of Rome and did not reach comparable levels until the Industrial Revolution. Lead played a crucial role in the development of the printing press, as movable type could be relatively easily cast from lead alloys. In 2014, the annual global production of lead was about ten million tonnes, over half of which was from recycling. Lead's high density, low melting point, ductility and relative inertness to oxidation make it useful. These properties, combined with its relative abundance and low cost, resulted in its extensive use in construction, plumbing, batteries, bullets, shots, weights, solders, pewters, fusible alloys, lead paints, leaded gasoline, and radiation shielding.
Lead is a neurotoxin that accumulates in soft tissues and bones. It damages the nervous system and interferes with the function of biological enzymes, causing neurological disorders ranging from behavioral problems to brain damage, and also affects general health, cardiovascular, and renal systems. Lead's toxicity was first documented by ancient Greek and Roman writers, who noted some of the symptoms of lead poisoning, but became widely recognized in Europe in the late 19th century AD.
Physical properties.
Atomic.
A lead atom has 82 electrons, arranged in an electron configuration of [Xe]4f145d106s26p2. The sum of lead's first and second ionization energies—the total energy required to remove the two 6p electrons—is close to that of tin, lead's upper neighbor in the carbon group. This is unusual; ionization energies generally fall going down a group, as an element's outer electrons become more distant from the nucleus, and more shielded by smaller orbitals.
The sum of the first four ionization energies of lead exceeds that of tin, contrary to what periodic trends would predict. This is explained by relativistic effects, which become significant in heavier atoms, which contract s and p orbitals such that lead's 6s electrons have larger binding energies than its 5s electrons. A consequence is the so-called inert pair effect: the 6s electrons of lead become reluctant to participate in bonding, stabilising the +2 oxidation state and making the distance between nearest atoms in crystalline lead unusually long.
Lead's lighter carbon group congeners form stable or metastable allotropes with the tetrahedrally coordinated and covalently bonded diamond cubic structure. The energy levels of their outer s- and p-orbitals are close enough to allow mixing into four hybrid sp3 orbitals. In lead, the inert pair effect increases the separation between its s- and p-orbitals, and the gap cannot be overcome by the energy that would be released by extra bonds following hybridization. Rather than having a diamond cubic structure, lead forms metallic bonds in which only the p-electrons are delocalized and shared between the Pb2+ ions. Lead consequently has a face-centered cubic structure like the similarly sized divalent metals calcium and strontium.
Bulk.
Pure lead has a bright, shiny gray appearance with a hint of blue. It tarnishes on contact with moist air and takes on a dull appearance, the hue of which depends on the prevailing conditions. Characteristic properties of lead include high density, malleability, ductility, and high resistance to corrosion due to passivation.
Lead's close-packed face-centered cubic structure and high atomic weight result in a density of 11.34 g/cm3, which is greater than that of common metals such as iron (7.87 g/cm3), copper (8.93 g/cm3), and zinc (7.14 g/cm3). This density is the origin of the idiom "to go over like a lead balloon". Some rarer metals are denser: tungsten and gold are both at 19.3 g/cm3, and osmium—the densest metal known—has a density of 22.59 g/cm3, almost twice that of lead.
Lead is a very soft metal with a Mohs hardness of 1.5; it can be scratched with a fingernail. It is quite malleable and somewhat ductile. The bulk modulus of lead—a measure of its ease of compressibility—is 45.8 GPa. In comparison, that of aluminium is 75.2 GPa; copper 137.8 GPa; and mild steel 160–169 GPa. Lead's tensile strength, at 12–17 MPa, is low (that of aluminium is 6 times higher, copper 10 times, and mild steel 15 times higher); it can be strengthened by adding small amounts of copper or antimony.
The melting point of lead—at 327.5 °C (621.5 °F)—is very low compared to most metals. Its boiling point of 1749 °C (3180 °F) is the lowest among the carbon-group elements. The electrical resistivity of lead at 20 °C is 192 nanoohm-meters, almost an order of magnitude higher than those of other industrial metals (copper at ; gold ; and aluminium at ). Lead is a superconductor at temperatures lower than 7.19 K; this is the highest critical temperature of all type-I superconductors and the third highest of the elemental superconductors.
Isotopes.
Natural lead consists of four stable isotopes with mass numbers of 204, 206, 207, and 208, and traces of six short-lived radioisotopes with mass numbers 209–214 inclusive. The high number of isotopes is consistent with lead's atomic number being even. Lead has a magic number of protons (82), for which the nuclear shell model accurately predicts an especially stable nucleus. Lead-208 has 126 neutrons, another magic number, which may explain why lead-208 is extraordinarily stable.
With its high atomic number, lead is the heaviest element whose natural isotopes are regarded as stable; lead-208 is the heaviest stable nucleus. (This distinction formerly fell to bismuth, with an atomic number of 83, until its only primordial isotope, bismuth-209, was found in 2003 to decay very slowly.) The four stable isotopes of lead could theoretically undergo alpha decay to isotopes of mercury with a release of energy, but this has not been observed for any of them; their predicted half-lives range from 1035 to 10189 years (at least 1025 times the current age of the universe).
Three of the stable isotopes are found in three of the four major decay chains: lead-206, lead-207, and lead-208 are the final decay products of uranium-238, uranium-235, and thorium-232, respectively. These decay chains are called the uranium chain, the actinium chain, and the thorium chain. Their isotopic concentrations in a natural rock sample depends greatly on the presence of these three parent uranium and thorium isotopes. For example, the relative abundance of lead-208 can range from 52% in normal samples to 90% in thorium ores; for this reason, the standard atomic weight of lead is given to only one decimal place. As time passes, the ratio of lead-206 and lead-207 to lead-204 increases, since the former two are supplemented by radioactive decay of heavier elements while the latter is not; this allows for lead–lead dating. As uranium decays into lead, their relative amounts change; this is the basis for uranium–lead dating. Lead-207 exhibits nuclear magnetic resonance, a property that has been used to study its compounds in solution and solid state, including in the human body.
Apart from the stable isotopes, which make up almost all lead that exists naturally, there are trace quantities of a few radioactive isotopes. One of them is lead-210; although it has a half-life of only 22.2 years, small quantities occur in nature because lead-210 is produced by a long decay series that starts with uranium-238 (that has been present for billions of years on Earth). Lead-211, −212, and −214 are present in the decay chains of uranium-235, thorium-232, and uranium-238, respectively, so traces of all three of these lead isotopes are found naturally. Minute traces of lead-209 arise from the very rare cluster decay of radium-223, one of the daughter products of natural uranium-235, and the decay chain of neptunium-237, traces of which are produced by neutron capture in uranium ores. Lead-213 also occurs in the decay chain of neptunium-237. Lead-210 is particularly useful for helping to identify the ages of samples by measuring its ratio to lead-206 (both isotopes are present in a single decay chain).
In total, 43 lead isotopes have been synthesized, with mass numbers 178–220. Lead-205 is the most stable radioisotope, with a half-life of around 1.70×107 years. The second-most stable is lead-202, which has a half-life of about 52,500 years, longer than any of the natural trace radioisotopes.
Chemistry.
Bulk lead exposed to moist air forms a protective layer of varying composition. Lead(II) carbonate is a common constituent; the sulfate or chloride may also be present in urban or maritime settings. This layer makes bulk lead effectively chemically inert in the air. Finely powdered lead, as with many metals, is pyrophoric, and burns with a bluish-white flame.
Fluorine reacts with lead at room temperature, forming lead(II) fluoride. The reaction with chlorine is similar but requires heating, as the resulting chloride layer diminishes the reactivity of the elements. Molten lead reacts with the chalcogens to give lead(II) chalcogenides.
Lead metal resists sulfuric and phosphoric acid but not hydrochloric or nitric acid; the outcome depends on insolubility and subsequent passivation of the product salt. Organic acids, such as acetic acid, dissolve lead in the presence of oxygen. Concentrated alkalis dissolve lead and form plumbites.
Inorganic compounds.
Lead shows two main oxidation states: +4 and +2. The tetravalent state is common for the carbon group. The divalent state is rare for carbon and silicon, minor for germanium, important (but not prevailing) for tin, and is the more important of the two oxidation states for lead. This is attributable to relativistic effects, specifically the inert pair effect, which manifests itself when there is a large difference in electronegativity between lead and oxide, halide, or nitride anions, leading to a significant partial positive charge on lead. The result is a stronger contraction of the lead 6s orbital than is the case for the 6p orbital, making it rather inert in ionic compounds. The inert pair effect is less applicable to compounds in which lead forms covalent bonds with elements of similar electronegativity, such as carbon in organolead compounds. In these, the 6s and 6p orbitals remain similarly sized and sp3 hybridization is still energetically favorable. Lead, like carbon, is predominantly tetravalent in such compounds.
There is a relatively large difference in the electronegativity of lead(II) at 1.87 and lead(IV) at 2.33. This difference marks the reversal in the trend of increasing stability of the +4 oxidation state going down the carbon group; tin, by comparison, has values of 1.80 in the +2 oxidation state and 1.96 in the +4 state.
Lead(II).
Lead(II) compounds are characteristic of the inorganic chemistry of lead. Even strong oxidizing agents like fluorine and chlorine react with lead to give only PbF2 and PbCl2. Lead(II) ions are usually colorless in solution, and partially hydrolyze to form Pb(OH)+ and finally [Pb4(OH)4]4+ (in which the hydroxyl ions act as bridging ligands), but are not reducing agents as tin(II) ions are. Techniques for identifying the presence of the Pb2+ ion in water generally rely on the precipitation of lead(II) chloride using dilute hydrochloric acid. As the chloride salt is sparingly soluble in water, in very dilute solutions the precipitation of lead(II) sulfide is instead achieved by bubbling hydrogen sulfide through the solution.
Lead monoxide exists in two polymorphs, litharge α-PbO (red) and massicot β-PbO (yellow), the latter being stable only above around 488 °C. Litharge is the most commonly used inorganic compound of lead. There is no lead(II) hydroxide; increasing the pH of solutions of lead(II) salts leads to hydrolysis and condensation. Lead commonly reacts with heavier chalcogens. Lead sulfide