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Calcium
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| Calcium | ||||||||||||||||||||||||||||||||||||||||||||||||||||||||
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| Appearance | dull gray, silver; with a pale yellow tint[1] | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Standard atomic weight Ar°(Ca) | ||||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Calcium in the periodic table | ||||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Atomic number (Z) | 20 | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Group | group 2 (alkaline earth metals) | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Period | period 4 | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Block | s-block | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Electron configuration | [Ar] 4s2 | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Electrons per shell | 2, 8, 8, 2 | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Physical properties | ||||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Phase at STP | solid | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Melting point | 1115 K (842 °C, 1548 °F) | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Boiling point | 1757 K (1484 °C, 2703 °F) | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Density (at 20° C) | 1.526 g/cm3 [4] | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| when liquid (at m.p.) | 1.378 g/cm3 | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Heat of fusion | 8.54 kJ/mol | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Heat of vaporisation | 154.7 kJ/mol | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Molar heat capacity | 25.929 J/(mol·K) | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
Vapour pressure
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| Atomic properties | ||||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Oxidation states | common: +2 +1[5] | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Electronegativity | Pauling scale: 1.00 | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Ionisation energies |
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| Atomic radius | empirical: 197 pm | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Covalent radius | 176±10 pm | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Van der Waals radius | 231 pm | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Other properties | ||||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Natural occurrence | primordial | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Crystal structure | face-centred cubic (fcc) (cF4) | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Lattice constant | a = 558.8 pm (at 20 °C)[4] | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Thermal expansion | 22.27×10−6/K (at 20 °C)[4] | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Thermal conductivity | 201 W/(m⋅K) | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Electrical resistivity | 33.6 nΩ⋅m (at 20 °C) | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Magnetic ordering | diamagnetic | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Molar magnetic susceptibility | +40.0×10−6 cm3/mol[6] | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Young's modulus | 20 GPa | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Shear modulus | 7.4 GPa | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Bulk modulus | 17 GPa | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Speed of sound thin rod | 3810 m/s (at 20 °C) | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Poisson ratio | 0.31 | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Mohs hardness | 1.75 | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Brinell hardness | 170–416 MPa | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| CAS Number | 7440-70-2 | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| History | ||||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Naming | from the Latin word for lime, calx | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Discovery and first isolation | Humphry Davy (1808) | |||||||||||||||||||||||||||||||||||||||||||||||||||||||
| Isotopes of calcium | ||||||||||||||||||||||||||||||||||||||||||||||||||||||||
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Calcium is a chemical element; it has symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to its heavier homologues strontium and barium. It is the fifth most abundant element in Earth's crust, and the third most abundant metal, after iron and aluminium. The most common calcium compound on Earth is calcium carbonate, found in limestone and the fossils of early sea life; gypsum, anhydrite, fluorite, and apatite are also sources of calcium. The name comes from Latin calx "lime", which was obtained from heating limestone.
Some calcium compounds were known to the ancients, though their chemistry was unknown until the seventeenth century. Pure calcium was isolated in 1808 via electrolysis of its oxide by Humphry Davy, who named the element. Calcium compounds are widely used in many industries: in foods and pharmaceuticals for calcium supplementation, in the paper industry as bleaches, as components in cement and electrical insulators, and in the manufacture of soaps. On the other hand, the metal in pure form has few applications due to its high reactivity; still, in small quantities it is often used as an alloying component in steelmaking, and sometimes, as a calcium–lead alloy, in making automotive batteries.
Calcium is the most abundant metal and the fifth-most abundant element in the human body.[8] As electrolytes, calcium ions (Ca2+) play a vital role in the physiological and biochemical processes of organisms and cells: in signal transduction pathways where they act as a second messenger; in neurotransmitter release from neurons; in contraction of all muscle cell types; as cofactors in many enzymes; and in fertilization.[8] Calcium ions outside cells are important for maintaining the potential difference across excitable cell membranes, protein synthesis, and bone formation.[8][9]
Characteristics
[edit]Classification
[edit]
Calcium is a very ductile silvery metal (sometimes described as pale yellow) whose properties are very similar to the heavier elements in its group, strontium, barium, and radium. A calcium atom has 20 electrons, with electron configuration [Ar]4s2. Like the other elements in group 2 of the periodic table, calcium has two valence electrons in the outermost s-orbital, which are very easily lost in chemical reactions to form a dipositive ion with the stable electron configuration of a noble gas, in this case argon.[10]
Hence, calcium is almost always divalent in its compounds, which are usually ionic. Hypothetical univalent salts of calcium would be stable with respect to their elements, but not to disproportionation to the divalent salts and calcium metal, because the enthalpy of formation of MX2 is much higher than those of the hypothetical MX. This occurs because of the much greater lattice energy afforded by the more highly charged Ca2+ cation compared to the hypothetical Ca+ cation.[10]
Calcium, strontium, barium, and radium are always considered to be alkaline earth metals; the lighter beryllium and magnesium, also in group 2 of the periodic table, are often included as well. Nevertheless, beryllium and magnesium differ significantly from the other members of the group in their physical and chemical behavior: they behave more like aluminium and zinc respectively and have some of the weaker metallic character of the post-transition metals, which is why the traditional definition of the term "alkaline earth metal" excludes them.[11]
Physical properties
[edit]Calcium metal melts at 842 °C and boils at 1494 °C; these values are higher than those for magnesium and strontium, the neighbouring group 2 metals. It crystallises in the face-centered cubic arrangement like strontium and barium; above 443 °C (716 K), it changes to body-centered cubic.[4][12] Its density of 1.526 g/cm3 (at 20 °C)[4] is the lowest in its group.[10]
Calcium is harder than lead but can be cut with a knife with effort. While calcium is a poorer conductor of electricity than copper or aluminium by volume, it is a better conductor by mass than both due to its very low density.[13] While calcium is infeasible as a conductor for most terrestrial applications as it reacts quickly with atmospheric oxygen, its use as such in space has been considered.[13]
Chemical properties
[edit]
The chemistry of calcium is that of a typical heavy alkaline earth metal. For example, calcium spontaneously reacts with water more quickly than magnesium but less quickly than strontium to produce calcium hydroxide and hydrogen gas. It also reacts with the oxygen and nitrogen in air to form a mixture of calcium oxide and calcium nitride.[14] When finely divided, it spontaneously burns in air to produce the nitride. Bulk calcium is less reactive: it quickly forms a hydration coating in moist air, but below 30% relative humidity it may be stored indefinitely at room temperature.[15]
Besides the simple oxide CaO, calcium peroxide, CaO2, can be made by direct oxidation of calcium metal under a high pressure of oxygen, and there is some evidence for a yellow superoxide Ca(O2)2.[16]Calcium hydroxide, Ca(OH)2, is a strong base, though not as strong as the hydroxides of strontium, barium or the alkali metals.[17] All four dihalides of calcium are known.[18] Calcium carbonate (CaCO3) and calcium sulfate (CaSO4) are particularly abundant minerals.[19] Like strontium and barium, as well as the alkali metals and the divalent lanthanides europium and ytterbium, calcium metal dissolves directly in liquid ammonia to give a dark blue solution.[20]
Due to the large size of the calcium ion (Ca2+), high coordination numbers are common, up to 24 in some intermetallic compounds such as CaZn13.[21] Calcium is readily complexed by oxygen chelates such as EDTA and polyphosphates, which are useful in analytic chemistry and removing calcium ions from hard water. In the absence of steric hindrance, smaller group 2 cations tend to form stronger complexes, but when large polydentate macrocycles are involved the trend is reversed.[19]
Organocalcium compounds
[edit]In contrast to organomagnesium compounds, organocalcium compounds are not similarly useful, with one major exception, calcium carbide, CaC2. This material, which has historic significance, is prepared by heating calcium oxide with carbon. According to X-ray crystallography, calcium carbide can be described as Ca2+ derivative of acetylide, C22-, although it is not a salt. Several million tons of calcium carbide are produced annually. Hydrolysis gives acetylene, which is used in welding and a chemical precursor. Reaction with nitrogen gas converts calcium carbide to calcium cyanamide.[22]
A dominant theme in molecular organocalcium chemistry is the large radius of calcium, which often leads to high coordination numbers. For example, dimethylcalcium appears to be a 3-dimensional polymer,[23] whereas dimethylmagnesium is a linear polymer with tetrahedral Mg centers. Bulky ligands are often required to disfavor polymeric species. For example, calcium dicyclopentadienyl, Ca(C5H5)2 has a polymeric structure and thus is nonvolatile and insoluble in solvents. Replacing the C5H5 ligand with the bulkier C5(CH3)5 (pentamethylcyclopentadienyl) gives a soluble complex that sublimes and forms well-defined adducts with ethers.[19] Organocalcium compounds tend to be more similar to organoytterbium compounds due to the similar ionic radii of Yb2+ (102 pm) and Ca2+ (100 pm).[24]
Organocalcium compounds have been well investigated. Some such complexes exhibit catalytic properties,[25] although none have been commercialized.
Isotopes
[edit]Natural calcium is a mixture of five stable isotopes—40Ca, 42Ca, 43Ca, 44Ca, and 46Ca—and 48Ca, whose half-life of 4.3 × 1019 years is so long that it can be considered stable for all practical purposes. Calcium is the first (lightest) element to have six naturally occurring isotopes.[14]
By far the most common isotope is 40Ca, which makes up 96.941% of natural calcium. It is produced in the silicon-burning process from fusion of alpha particles and is the heaviest stable nuclide with equal proton and neutron numbers; its occurrence is also supplemented slowly by the decay of primordial 40K. Adding another alpha particle leads to unstable 44Ti, which decays via two successive electron captures to stable 44Ca; this makes up 2.806% of natural calcium and is the second-most common isotope.[26][27]
The other four natural isotopes, 42, 43, 46, 48Ca, are significantly rarer, each comprising less than 1% of natural calcium. The four lighter isotopes are mainly products of oxygen-burning and silicon-burning, leaving the two heavier ones to be produced via neutron capture. 46Ca is mostly produced in a "hot" s-process, as its formation requires a rather high neutron flux to allow short-lived 45Ca to capture a neutron. 48Ca is produced by electron capture in the r-process in type Ia supernovae, where high neutron excess and low enough entropy ensures its survival.[26][27]
46Ca and 48Ca are the first "classically stable" nuclides with a 6-neutron or 8-neutron excess respectively. Though extremely neutron-rich for such a light element, 48Ca is very stable because it is a doubly magic nucleus, with 20 protons and 28 neutrons arranged in closed shells. Its beta decay to 48Sc is very hindered by the gross mismatch of nuclear spin: 48Ca has zero nuclear spin, being even–even, while 48Sc has spin 6+, so the decay is forbidden by conservation of angular momentum. While two excited states of 48Sc are available for decay as well, they are also forbidden due to their high spins. As a result, when 48Ca does decay, it does so by double beta decay to 48Ti instead, being the lightest nuclide known to undergo double beta decay.[28][29]
46Ca can also theoretically double-beta-decay to 46Ti, but this has never been observed. The most common isotope 40Ca is also doubly magic and could undergo double electron capture to 40Ar, but this has likewise never been observed. Calcium is the only element with two primordial doubly magic isotopes. The experimental lower limits for the half-lives of 40Ca and 46Ca are 5.9 × 1021 years and 2.8 × 1015 years respectively.[28]
Excluding 48Ca, the longest lived radioisotope of calcium is 41Ca. It decays by electron capture to stable 41K with a half-life of about 105 years. Its existence in the early Solar System as an extinct radionuclide has been inferred from excesses of 41K. Traces of 41Ca also still exist today, as it is a cosmogenic nuclide, continuously produced through neutron activation of natural 40Ca.[27]
Many other calcium radioisotopes are known, ranging from 35Ca to 60Ca. They are all much shorter-lived than 41Ca; the most stable are 45Ca (half-life 163 days) and 47Ca (half-life 4.54 days). Isotopes lighter than 42Ca usually undergo beta plus decay to isotopes of potassium, and those heavier than 44Ca usually undergo beta minus decay to scandium; though near the nuclear drip lines, proton emission and neutron emission begin to be significant decay modes as well.[28]
Like other elements, a variety of processes alter the relative abundance of calcium isotopes.[30] The best studied of these processes is the mass-dependent fractionation of calcium isotopes that accompanies the precipitation of calcium minerals such as calcite, aragonite and apatite from solution. Lighter isotopes are preferentially incorporated into these minerals, leaving the surrounding solution enriched in heavier isotopes at a magnitude of roughly 0.025% per atomic mass unit (amu) at room temperature. Mass-dependent differences in calcium isotope composition are conventionally expressed by the ratio of two isotopes (usually 44Ca/40Ca) in a sample compared to the same ratio in a standard reference material. 44Ca/40Ca varies by about 1–2‰ among organisms on Earth.[31]
History
[edit]
Calcium compounds were known for millennia, though their chemical makeup was not understood until the 17th century.[32] Lime as a building material[33] and as plaster for statues was used as far back as around 7000 BC.[34] The first dated lime kiln dates back to 2500 BC and was found in Khafajah, Mesopotamia.[35][36]
About the same time, dehydrated gypsum (CaSO4·2H2O) was being used in the Great Pyramid of Giza. This material would later be used for the plaster in the tomb of Tutankhamun. The ancient Romans instead used lime mortars made by heating limestone (CaCO3). The name "calcium" itself derives from the Latin word calx "lime".[32]
Vitruvius noted that the lime that resulted was lighter than the original limestone, attributing this to the boiling of the water. In 1755, Joseph Black proved that this was due to the loss of carbon dioxide, which as a gas had not been recognised by the ancient Romans.[37]
In 1789, Antoine Lavoisier suspected that lime might be an oxide of an element. In his table of the elements, Lavoisier listed five "salifiable earths" (i.e., ores that could be made to react with acids to produce salts (salis = salt, in Latin): chaux (calcium oxide), magnésie (magnesia, magnesium oxide), baryte (barium sulfate), alumine (alumina, aluminium oxide), and silice (silica, silicon dioxide)). About these "elements", Lavoisier reasoned:
We are probably only acquainted as yet with a part of the metallic substances existing in nature, as all those which have a stronger affinity to oxygen than carbon possesses, are incapable, hitherto, of being reduced to a metallic state, and consequently, being only presented to our observation under the form of oxyds, are confounded with earths. It is extremely probable that barytes, which we have just now arranged with earths, is in this situation; for in many experiments it exhibits properties nearly approaching to those of metallic bodies. It is even possible that all the substances we call earths may be only metallic oxyds, irreducible by any hitherto known process.[38]
Calcium, along with its congeners magnesium, strontium, and barium, was first isolated by Humphry Davy in 1808. Following the work of Jöns Jakob Berzelius and Magnus Martin of Pontin on electrolysis, Davy isolated calcium and magnesium by putting a mixture of the respective metal oxides with mercury(II) oxide on a platinum plate which was used as the anode, the cathode being a platinum wire partially submerged into mercury. Electrolysis then gave calcium–mercury and magnesium–mercury amalgams, and distilling off the mercury gave the metal.[32][39] However, pure calcium cannot be prepared in bulk by this method and a workable commercial process for its production was not found until over a century later.[37]
Occurrence and production
[edit]At 3%, calcium is the fifth most abundant element in the Earth's crust, and the third most abundant metal behind aluminium and iron.[40] It is also the fourth most abundant element in the lunar highlands.[15] Sedimentary calcium carbonate deposits pervade the Earth's surface as fossilised remains of past marine life; they occur in two forms, the rhombohedral calcite (more common) and the orthorhombic aragonite (forming in more temperate seas). Minerals of the first type include limestone, dolomite, marble, chalk, and Iceland spar; aragonite beds make up the Bahamas, the Florida Keys, and the Red Sea basins. Corals, sea shells, and pearls are mostly made up of calcium carbonate. Among the other important minerals of calcium are gypsum (CaSO4·2H2O), anhydrite (CaSO4), fluorite (CaF2), and apatite ([Ca5(PO4)3X], X = OH, Cl, or F)[32]
The major producers of calcium are China (about 10000 to 12000 tonnes per year), Russia (about 6000 to 8000 tonnes per year), and the United States (about 2000 to 4000 tonnes per year). Canada and France are among the minor producers. In 2005, about 24000 tonnes of calcium were produced; about half of the world's extracted calcium is used by the United States, with about 80% of the output used each year.[13]
In Russia and China, Davy's method of electrolysis is still used, but is instead applied to molten calcium chloride.[13] Since calcium is less reactive than strontium or barium, the oxide–nitride coating that results in air is stable and lathe machining and other standard metallurgical techniques are suitable for calcium.[41]
In the U.S. and Canada, calcium is instead produced by reducing lime with aluminium at high temperatures.[13] In this process, powdered high-calcium lime and powdered aluminum are mixed and compacted into briquettes for a high degree of contact, which are then placed in a sealed retort which has been evacuated and heated to ~1200°C.[13] The briquettes release calcium vapor into the vacuum for about 8 hours, which then condenses in the cooled ends of the retorts to form 24-34 kg pieces of calcium metal, as well as some residue of calcium aluminate.[13] High-purity calcium can be obtained by distilling low-purity calcium at high temperatures.[13]
Geochemical cycling
[edit]Calcium cycling provides a link between tectonics, climate, and the carbon cycle. In the simplest terms, mountain-building exposes calcium-bearing rocks such as basalt and granodiorite to chemical weathering and releases Ca2+ into surface water. These ions are transported to the ocean where they react with dissolved CO2 to form limestone (CaCO3), which in turn settles to the sea floor where it is incorporated into new rocks. Dissolved CO2, along with carbonate and bicarbonate ions, are termed "dissolved inorganic carbon" (DIC).[42]
The actual reaction is more complicated and involves the bicarbonate ion (HCO−
3) that forms when CO2 reacts with water at seawater pH:
- Ca2+ + 2 HCO−3 → CaCO3↓ + CO2 + H2O
At seawater pH, most of the dissolved CO2 is immediately converted back into HCO−
3. The reaction results in a net transport of one molecule of CO2 from the ocean/atmosphere into the lithosphere.[43] The result is that each Ca2+ ion released by chemical weathering ultimately removes one CO2 molecule from the surficial system (atmosphere, ocean, soil and living organisms), storing it in carbonate rocks where it is likely to stay for hundreds of millions of years. The weathering of calcium from rocks thus scrubs CO2 from the ocean and air, exerting a strong long-term effect on climate.[42][44]
Applications
[edit]The largest use of metallic calcium is in steelmaking, due to its strong chemical affinity for chalcogens oxygen and sulfur. Its oxides and sulfides, once formed, give liquid lime aluminate and sulfide inclusions in steel which float out; on treatment, these inclusions disperse throughout the steel and become small and spherical, improving castability, cleanliness and general mechanical properties. Calcium is also used in maintenance-free automotive batteries, in which the use of 0.1% calcium–lead alloys instead of the usual antimony–lead alloys leads to lower water loss and lower self-discharging.[45]
Due to the risk of expansion and cracking, aluminium is sometimes also incorporated into these alloys. These lead–calcium alloys are also used in casting, replacing lead–antimony alloys.[45] Calcium is also used to strengthen aluminium alloys used for bearings, for the control of graphitic carbon in cast iron, and to remove bismuth impurities from lead.[41] Calcium metal is found in some drain cleaners, where it functions to generate heat and calcium hydroxide that saponifies the fats and liquefies the proteins (for example, those in hair) that block drains.[46]
Besides metallurgy, the reactivity of calcium is exploited to remove nitrogen from high-purity argon gas and as a getter for oxygen and nitrogen. It is also used as a reducing agent in the production of chromium, zirconium, thorium, vanadium and uranium. It can also be used to store hydrogen gas, as it reacts with hydrogen to form solid calcium hydride, from which the hydrogen can easily be re-extracted.[41]
Calcium isotope fractionation during mineral formation has led to several applications of calcium isotopes. In particular, the 1997 observation by Skulan and DePaolo[47] that calcium minerals are isotopically lighter than the solutions from which the minerals precipitate is the basis of analogous applications in medicine and in paleoceanography. In animals with skeletons mineralised with calcium, the calcium isotopic composition of soft tissues reflects the relative rate of formation and dissolution of skeletal mineral.[48]
In humans, changes in the calcium isotopic composition of urine have been shown to be related to changes in bone mineral balance. When the rate of bone formation exceeds the rate of bone resorption, the 44Ca/40Ca ratio in soft tissue rises and vice versa. Because of this relationship, calcium isotopic measurements of urine or blood may be useful in the early detection of metabolic bone diseases like osteoporosis.[48]
A similar system exists in seawater, where 44Ca/40Ca tends to rise when the rate of removal of Ca2+ by mineral precipitation exceeds the input of new calcium into the ocean. In 1997, Skulan and DePaolo presented the first evidence of change in seawater 44Ca/40Ca over geologic time, along with a theoretical explanation of these changes. More recent papers have confirmed this observation, demonstrating that seawater Ca2+ concentration is not constant, and that the ocean is never in a "steady state" with respect to calcium input and output. This has important climatological implications, as the marine calcium cycle is closely tied to the carbon cycle.[49][50]
Many calcium compounds are used in food, as pharmaceuticals, and in medicine, among others. For example, calcium and phosphorus are supplemented in foods through the addition of calcium lactate, calcium diphosphate, and tricalcium phosphate. The last is also used as a polishing agent in toothpaste and in antacids. Calcium lactobionate is a white powder that is used as a suspending agent for pharmaceuticals. In baking, calcium phosphate is used as a leavening agent. Calcium sulfite is used as a bleach in papermaking and as a disinfectant, calcium silicate is used as a reinforcing agent in rubber, and calcium acetate is a component of liming rosin and is used to make metallic soaps and synthetic resins.[45]
Calcium supplement is on the World Health Organization's List of Essential Medicines.[51]
Food sources
[edit]Foods rich in calcium include dairy products such as milk, yogurt, and cheese, as well as sardines, salmon, soy products, kale, and fortified breakfast cereals.[9]
Because of concerns for long-term adverse side effects, including calcification of arteries and kidney stones, both the U.S. Institute of Medicine (IOM) and the European Food Safety Authority (EFSA) set tolerable upper intake levels (ULs) for combined dietary and supplemental calcium. From the IOM, people of ages 9–18 years are not to exceed 3 g/day combined intake; for ages 19–50, not to exceed 2.5 g/day; for ages 51 and older, not to exceed 2 g/day.[52] EFSA set the UL for all adults at 2.5 g/day, but decided the information for children and adolescents was not sufficient to determine ULs.[53]
Biological and pathological role
[edit]| Age | Calcium (mg/day) |
|---|---|
| 1–3 years | 700 |
| 4–8 years | 1000 |
| 9–18 years | 1300 |
| 19–50 years | 1000 |
| >51 years | 1000 |
| Pregnancy | 1000 |
| Lactation | 1000 |

Function
[edit]Calcium is an essential element needed in large quantities.[8][9] The Ca2+ ion acts as an electrolyte and is vital to the health of the muscular, circulatory, and digestive systems; is indispensable to the building of bone in the form of hydroxyapatite; and supports synthesis and function of blood cells. For example, it regulates the contraction of muscles, nerve conduction, and the clotting of blood. As a result, intra- and extracellular calcium levels are tightly regulated by the body. Calcium can play this role because the Ca2+ ion forms stable coordination complexes with many organic compounds, especially proteins; it also forms compounds with a wide range of solubilities, enabling the formation of the skeleton.[8] [56]
Binding
[edit]Calcium ions may be complexed by proteins through binding the carboxyl groups of glutamic acid or aspartic acid residues; through interacting with phosphorylated serine, tyrosine, or threonine residues; or by being chelated by γ-carboxylated amino acid residues. Trypsin, a digestive enzyme, uses the first method; osteocalcin, a bone matrix protein, uses the third.[57]
Some other bone matrix proteins such as osteopontin and bone sialoprotein use both the first and the second. Direct activation of enzymes by binding calcium is common; some other enzymes are activated by noncovalent association with direct calcium-binding enzymes. Calcium also binds to the phospholipid layer of the cell membrane, anchoring proteins associated with the cell surface.[57]
Solubility
[edit]As an example of the wide range of solubility of calcium compounds, monocalcium phosphate is very soluble in water, 85% of extracellular calcium is as dicalcium phosphate with a solubility of 2.00 mM, and the hydroxyapatite of bones in an organic matrix is tricalcium phosphate with a solubility of 1000 μM.[57]
Nutrition
[edit]Calcium is a common constituent of multivitamin dietary supplements,[8] but the composition of calcium complexes in supplements may affect its bioavailability which varies by solubility of the salt involved: calcium citrate, malate, and lactate are highly bioavailable, while the oxalate is less. Other calcium preparations include calcium carbonate, calcium citrate malate, and calcium gluconate.[8] The intestine absorbs about one-third of calcium eaten as the free ion, and plasma calcium level is then regulated by the kidneys.[8]
Hormonal regulation of bone formation and serum levels
[edit]Parathyroid hormone and vitamin D promote the formation of bone by allowing and enhancing the deposition of calcium ions there, allowing rapid bone turnover without affecting bone mass or mineral content.[8] When plasma calcium levels fall, cell surface receptors are activated and the secretion of parathyroid hormone occurs; it then proceeds to stimulate the entry of calcium into the plasma pool by taking it from targeted kidney, gut, and bone cells, with the bone-forming action of parathyroid hormone being antagonised by calcitonin, whose secretion increases with increasing plasma calcium levels.[57]
Abnormal serum levels
[edit]Excess intake of calcium may cause hypercalcemia. However, because calcium is absorbed rather inefficiently by the intestines, high serum calcium is more likely caused by excessive secretion of parathyroid hormone (PTH) or possibly by excessive intake of vitamin D, both of which facilitate calcium absorption. All these conditions result in excess calcium salts being deposited in the heart, blood vessels, or kidneys. Symptoms include anorexia, nausea, vomiting, memory loss, confusion, muscle weakness, increased urination, dehydration, and metabolic bone disease.[57]
Chronic hypercalcaemia typically leads to calcification of soft tissue and its serious consequences: for example, calcification can cause loss of elasticity of vascular walls and disruption of laminar blood flow—and thence to plaque rupture and thrombosis. Conversely, inadequate calcium or vitamin D intakes may result in hypocalcemia, often caused also by inadequate secretion of parathyroid hormone or defective PTH receptors in cells. Symptoms include neuromuscular excitability, which potentially causes tetany and disruption of conductivity in cardiac tissue.[57]
Bone disease
[edit]As calcium is required for bone development, many bone diseases can be traced to the organic matrix or the hydroxyapatite in molecular structure or organization of bone. Osteoporosis is a reduction in mineral content of bone per unit volume, and can be treated by supplementation of calcium, vitamin D, and bisphosphonates.[8][9] Inadequate amounts of calcium, vitamin D, or phosphates can lead to softening of bones, called osteomalacia.[57]
Safety
[edit]Metallic calcium
[edit]| Hazards | |
|---|---|
| GHS labelling:[58] | |
| Danger | |
| H261 | |
| P231+P232 | |
| NFPA 704 (fire diamond) | |
Because calcium reacts exothermically with water and acids, calcium metal coming into contact with bodily moisture results in severe corrosive irritation.[59] When swallowed, calcium metal has the same effect on the mouth, oesophagus, and stomach, and can be fatal.[46] However, long-term exposure is not known to have distinct adverse effects.[59]
References
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Calcium
View on GrokipediaCharacteristics
Classification
Calcium is a chemical element with atomic number 20, positioned in group 2 and period 4 of the periodic table, classifying it as an alkaline earth metal.[8] Its ground-state electron configuration is [Ar] 4s², with the two valence electrons occupying the 4s orbital, which contributes to its characteristic chemical behavior within the group.[8] Alkaline earth metals like calcium are highly reactive, owing to their tendency to lose both valence electrons and form stable divalent cations (M²⁺), resulting in a +2 oxidation state in most compounds./08:_Chemistry_of_the_Main_Group_Elements/8.05:_Group_2_The_Alkaline_Earth_Metals/8.5.02:_Alkaline_Earth_Metals'_Chemical_Properties) This reactivity is enhanced by their low electronegativity; calcium specifically has an electronegativity of 1.00 on the Pauling scale, making it prone to ionic bonding with nonmetals.80142-5) Compared to other group 2 elements, calcium's atomic radius of 197 pm is intermediate, larger than magnesium (160 pm) but smaller than strontium (215 pm), illustrating the trend of increasing size down the group due to additional electron shells.[9] Its ionization energies reflect this position: the first is 589.8 kJ/mol and the second is 1145 kJ/mol, values higher than magnesium's (738 kJ/mol first, 1451 kJ/mol second) but lower than strontium's (549 kJ/mol first, 1064 kJ/mol second), consistent with decreasing ionization energy as atomic size increases.[10]Physical properties
Calcium is a soft, silvery-white metal that rapidly tarnishes in air to form a grayish-white oxide layer.[11] This malleable and ductile nature allows it to be easily shaped or drawn into wires, characteristic of its position among the alkaline earth metals.[1] The density of elemental calcium is 1.55 g/cm³ at 20 °C.[11] It has a melting point of 842 °C (1115 K) and a boiling point of 1484 °C (1757 K).[11] Calcium exhibits a face-centered cubic (FCC) crystal structure with a lattice constant of 558.8 pm at 20 °C.[12] Elemental calcium demonstrates good thermal conductivity of 201 W/(m·K) and electrical resistivity of 34 nΩ·m at 20 °C, reflecting its metallic bonding and free electron behavior.[13] These properties contribute to its utility in applications requiring heat dissipation or electrical conduction, though its reactivity limits direct use.Chemical properties
Calcium is a highly reactive alkaline earth metal that tarnishes rapidly in air, forming a gray-white coating of calcium oxide (CaO) and calcium nitride (Ca₃N₂) due to its affinity for oxygen and nitrogen. Finely divided calcium is pyrophoric and ignites spontaneously in air, burning with an intense white flame.[11] It reacts vigorously with water at room temperature, liberating hydrogen gas and forming calcium hydroxide (Ca(OH)₂), as represented by the equation: This exothermic reaction demonstrates calcium's strong reducing properties.[14][5][15] The predominant oxidation state of calcium is +2, resulting from the facile loss of its two 4s valence electrons, enabled by relatively low successive ionization energies (first: 589.8 kJ/mol; second: 1145.3 kJ/mol). This electron configuration promotes ionic bonding in calcium compounds, where the Ca²⁺ cation electrostatically interacts with anions, favoring the formation of ionic lattices over covalent structures. Calcium's position in the reactivity series places it above magnesium but below sodium, underscoring its ability to displace hydrogen from dilute acids, yielding hydrogen gas and soluble calcium salts.[11][1][16] Calcium readily forms compounds such as oxides (e.g., CaO), halides (e.g., CaCl₂), and sulfates (e.g., CaSO₄), with solubility trends governed by lattice energy and hydration effects. Most calcium salts exhibit good solubility in water, but notable exceptions include calcium carbonate (CaCO₃), which is insoluble (K_{sp} = 2.8 \times 10^{-9}), and calcium sulfate dihydrate (CaSO₄·2H₂O, gypsum), which has limited solubility (K_{sp} = 2.4 \times 10^{-5} at 25°C).[14][17] The standard reduction potential for the Ca²⁺/Ca half-cell is -2.87 V versus the standard hydrogen electrode, indicating calcium's potent reducing capability and thermodynamic tendency to oxidize.[18]Isotopes
Calcium has 25 known isotopes, with mass numbers ranging from 34 to 58.[19] Six of these isotopes are stable and occur naturally on Earth, while the remainder are radioactive with half-lives spanning from microseconds to over 100,000 years. The stable isotopes dominate the natural composition of calcium, with variations in abundance reflecting both primordial nucleosynthesis and minor cosmogenic production. The stable isotopes of calcium, along with their approximate natural abundances in terrestrial materials, are listed below:| Isotope | Natural Abundance (%) |
|---|---|
| ⁴⁰Ca | 96.941 |
| ⁴²Ca | 0.647 |
| ⁴³Ca | 0.135 |
| ⁴⁴Ca | 2.086 |
| ⁴⁶Ca | 0.004 |
| ⁴⁸Ca | 0.187 |
History
Discovery and isolation
Lime, or calcium oxide (CaO), has been utilized as a compound since prehistoric times, with evidence of its use in construction dating back to approximately 4000 BCE in ancient Egypt, where it served as a binding mortar and plaster in the building of early pyramids, such as those at Meidum around 2600 BCE.[24][25] This early recognition of lime's properties as a reactive material for mortar highlights its role in foundational civil engineering, though the elemental nature of calcium remained unrecognized for millennia.[26] Efforts to isolate calcium as a pure element began in the early 19th century amid advances in electrochemistry. In 1803, Swedish chemists Jöns Jacob Berzelius and Magnus Martin Pontin conducted electrolysis of lime dissolved in mercury, producing a calcium-mercury amalgam but failing to obtain the pure metal due to the amalgam's stability.[27][6] Inspired by their work, British chemist Humphry Davy pursued similar experiments at the Royal Institution in London.[28] Davy successfully isolated metallic calcium in 1808 through electrolysis of a mixture of moist lime (CaO) and mercuric oxide (HgO), using a mercury cathode to form a calcium amalgam, which he then heated in a retort to distill away the mercury and yield impure calcium metal.[8][1] This breakthrough, announced in a series of lectures to the Royal Society, marked the first production of calcium in its elemental form and demonstrated the power of electrolysis for decomposing refractory oxides, a technique Davy had previously applied to potassium and sodium.[29] The resulting calcium appeared as a soft, silvery-white solid that rapidly tarnished in air, confirming its reactivity and placement among the alkaline earth metals.[28]Etymology and early recognition
The term "calcium" originates from the Latin word calx, meaning lime or limestone, reflecting the element's long association with calcium oxide (CaO), commonly known as quicklime.[1] This nomenclature was proposed by British chemist Humphry Davy in 1808, following his electrolytic isolation of the metal from a mixture of lime and mercuric oxide, to denote the new element distinct from earlier uses of "calx" for calcined substances like ashes.[8] Prior to this, in alchemical and early chemical traditions, calcium compounds were referred to as "calcareous earth" or "earth of lime," encompassing materials such as limestone and chalk that were manipulated in processes like calcination to produce lime for various applications.[30] Human recognition of calcium-based materials dates back millennia, with evidence of their use in construction predating the element's identification. Gypsum (CaSO₄·2H₂O), a hydrated calcium sulfate, was employed as plaster in Neolithic settlements, notably at Çatalhöyük in modern-day Turkey around 7500 BCE, where it was mixed with lime for wall coatings and decorative purposes.[31] By the Roman era, quicklime played a pivotal role in durable concrete formulations; for instance, the Pantheon's massive dome, completed in 126 CE under Emperor Hadrian, utilized pozzolanic concrete incorporating quicklime, volcanic ash, and aggregates, enabling self-healing properties through hot-mixing techniques that formed lime clasts for crack repair.[32] In the pre-modern scientific framework, calcium was understood as an elemental "earth" rather than a metal. French chemist Antoine Lavoisier, in his 1789 treatise Traité Élémentaire de Chimie, classified "terre calcaire" (calcareous earth) among the simple substances, listing it alongside other earths like magnesia and baryta based on their resistance to decomposition and role in forming salts.[33] Swedish chemist Jöns Jacob Berzelius, who assisted Davy in early experiments, further refined the terminology in 1810 by adopting and promoting "calcium" in chemical nomenclature, aligning it with emerging conventions for metallic elements derived from earths.[34] This progression from alchemical "earth of lime" to a recognized element underscored calcium's foundational role in both practical arts and systematic chemistry.Occurrence and production
Natural occurrence
Calcium is produced primarily through stellar nucleosynthesis in massive stars and is relatively abundant in the universe compared to heavier elements. Its cosmic distribution reflects contributions from Big Bang nucleosynthesis for lighter elements and subsequent stellar processes for heavier ones like calcium.[35] On Earth, calcium ranks as the fifth most abundant element in the crust, comprising approximately 3.6% by mass.[36] In the oceans, it is present at a concentration of about 0.4 g/L primarily as Ca²⁺ ions, dissolved from continental weathering and contributing to marine chemistry.[37] Calcium occurs naturally in a variety of minerals, with calcite (CaCO₃) being the most prevalent, accounting for roughly 4% of the Earth's crust and forming extensive limestone deposits. Other significant minerals include dolomite (CaMg(CO₃)₂), which is common in sedimentary rocks; gypsum (CaSO₄·2H₂O), found in evaporite deposits; and fluorite (CaF₂), a key source of fluorine.[38] In the biosphere, calcium is highly concentrated in the exoskeletons, shells, and bones of organisms, where it forms structural components like calcium carbonate in marine shells and hydroxyapatite in vertebrate bones. Marine organisms, such as mollusks, corals, and plankton, extract calcium from seawater to build these structures, facilitating its distribution across ecosystems.[39] Within the solar system, calcium is a major component of chondritic meteorites, representing primitive solar material with typical CaO contents around 1–2%, and lunar rocks, particularly anorthosites in the highlands, where CaO levels can reach up to 10–15%.[40]Industrial production
The primary industrial method for producing elemental calcium is the aluminothermic reduction of calcium oxide (CaO), a process conducted under vacuum at approximately 1200°C. In this reaction, aluminum serves as the reducing agent, following the equation: This yields calcium metal that can be further processed for higher purity.[41] An alternative method, electrolysis of molten calcium chloride (CaCl₂), has been employed since the 1890s and remains in use for producing calcium of about 99% purity. The process involves electrolyzing the molten salt with a sacrificial anode, where calcium deposits at the cathode and chlorine gas is evolved at the anode.[42] Global annual production of calcium metal is approximately 10,000 tons as of 2023, with the majority originating from China and Russia.[43] Following initial production, calcium is purified by vacuum distillation to achieve 99.9% purity, removing volatile impurities and residual oxides.[44] The raw material for these processes is typically derived from the calcination of limestone (CaCO₃), which decomposes to form CaO and releases CO₂ as a byproduct: CaCO₃ → CaO + CO₂.[41]Geochemical cycling
Calcium plays a central role in the carbonate-silicate cycle, a fundamental geochemical process that regulates Earth's long-term carbon budget and climate stability. During chemical weathering of calcium-rich silicate rocks, such as plagioclase feldspars, carbonic acid derived from atmospheric CO₂ reacts with minerals to release Ca²⁺ ions into solution, which are then transported to the oceans via rivers. In marine settings, these ions combine with bicarbonate (HCO₃⁻) to form calcium carbonate (CaCO₃), primarily through biogenic precipitation by organisms like coccolithophores and foraminifera. This precipitation effectively sequesters carbon, with global riverine inputs delivering approximately 0.65 Gt of Ca per year to the oceans from both riverine and minor hydrothermal sources.[45] The reverse process occurs through volcanic and metamorphic degassing, releasing CO₂ and enabling renewed weathering. In the oceanic realm, the calcium cycle involves biological uptake, sedimentation, and physical mixing. Calcifying plankton incorporate Ca²⁺ into CaCO₃ structures, which sink as particulate matter and accumulate as sediments, forming vast limestone deposits over geological time. A significant portion—over 80%—of produced CaCO₃ dissolves in the water column or upper sediments due to increasing pressure and decreasing pH with depth, but the net burial flux balances inputs at roughly 0.6 Gt Ca per year. Upwelling circulates dissolved calcium back to surface waters, sustaining productivity in nutrient-limited regions. The average residence time of calcium in seawater is approximately 1 million years, reflecting its conservative behavior and well-mixed distribution throughout the global ocean.[46][47] Volcanic processes contribute to calcium inputs primarily through the formation and subsequent weathering of basaltic rocks at mid-ocean ridges and arcs, where CaO constitutes about 10-12% of basalt composition. The flux from these sources, including hydrothermal alteration, is estimated at around 0.1 Gt Ca per year, providing a steady supply that supports the cycle's continuity. On land, the biosphere influences local calcium dynamics: plants absorb Ca²⁺ from soils for structural roles in cell walls, while herbivores and decomposers recycle it through excretion and decay, with minimal net loss over short timescales but significant fractionation observable in isotopic signatures.[48] Human activities have introduced perturbations to this ancient cycle, notably through intensified mining of limestone and the production of Portland cement, which consumes over 4 Gt of CaCO₃ annually and releases about 1 Gt of CO₂ per year via calcination (CaCO₃ → CaO + CO₂). This process accelerates calcium mobilization and atmospheric CO₂ enrichment, bypassing natural weathering rates and enhancing the reverse flux in the carbonate-silicate cycle, with potential long-term implications for ocean alkalinity and calcification.[47]Calcium compounds
Inorganic compounds
Calcium oxide (CaO), commonly known as quicklime, is a white, caustic, alkaline solid produced primarily by the calcination of limestone or other calcium carbonate sources. The reaction involves heating calcium carbonate to temperatures exceeding 900°C, yielding calcium oxide and carbon dioxide gas:. [49][50]
Quicklime exhibits high reactivity with water, undergoing a strongly exothermic hydration to form calcium hydroxide (slaked lime):
. [49]
It has a melting point of 2,613°C and is widely used as a key ingredient in Portland cement production due to its binding properties upon hydration. [49] Calcium carbonate (CaCO₃) occurs naturally in several polymorphic forms, including the stable calcite (rhombohedral structure) and the metastable aragonite (orthorhombic structure), both of which are principal components of limestone, marble, and seashells. [51]
It is sparingly soluble in water, with a solubility product constant (Ksp) of approximately 3.7 × 10⁻⁹ at 25°C, which governs its precipitation in aqueous environments and contributes to its role in geological formations like stalactites. [52]
Calcium carbonate decomposes thermally above 840°C to form calcium oxide and carbon dioxide, mirroring the preparation of quicklime. [51] Among the calcium halides, calcium chloride (CaCl₂) is highly hygroscopic and deliquescent, readily absorbing moisture from the air to form hydrates such as the dihydrate (CaCl₂·2H₂O). [53][54]
It is typically prepared by reacting calcium carbonate with hydrochloric acid:
. [53][55]
Anhydrous calcium chloride has a melting point of 772°C and is soluble in water to the extent of about 74 g/100 mL at 20°C, making it useful in de-icing applications due to its exothermic dissolution. [53][56]
In contrast, calcium fluoride (CaF₂), known as fluorite or fluorspar, is nearly insoluble in water (Ksp ≈ 3.9 × 10⁻¹¹ at 25°C) and adopts a cubic fluorite crystal structure. [57][58]
It occurs naturally as a mineral and has a high melting point of 1,418°C, contributing to its use in optics and metallurgy for its transparency to infrared radiation. [57][59] Calcium sulfate exists predominantly as the dihydrate (CaSO₄·2H₂O), or gypsum, a soft, white mineral with a Mohs hardness of 2, commonly found in sedimentary deposits. [60][61]
Upon heating to around 150°C, gypsum loses three-quarters of its water of hydration to form hemihydrate (CaSO₄·0.5H₂O), known as plaster of Paris, which sets rapidly upon rehydration to regenerate the dihydrate structure. [60][62]
The dihydrate has low solubility in water (about 0.21 g/100 mL at 20°C) and is chemically stable under neutral conditions. [63][64] Calcium nitrate (Ca(NO₃)₂) is a highly water-soluble salt (solubility ≈ 121 g/100 mL at 20°C), often encountered as the tetrahydrate (Ca(NO₃)₂·4H₂O), which is colorless and deliquescent. [65][66]
It can be synthesized by dissolving limestone in nitric acid or via the reaction of calcium hydroxide with nitric acid. [65][67]
The anhydrous form melts at 561°C and decomposes at higher temperatures, while its solutions are neutral to slightly acidic due to partial hydrolysis. [68][69]
Organocalcium compounds
Organocalcium compounds, featuring direct calcium-carbon bonds, are exceedingly rare owing to the element's pronounced reactivity, rendering most species highly unstable toward air and moisture; consequently, they must be synthesized and manipulated under strict inert atmospheric conditions. These compounds exhibit bonding that is predominantly ionic, reflecting calcium's electropositive nature, yet displays subtle covalent character in the Ca-C interaction, which contributes to their enhanced nucleophilicity compared to analogous magnesium species. In the gas phase, computational and spectroscopic studies reveal that many such compounds favor dimeric structures, stabilized by bridging ligands or metal-metal interactions. Prominent examples include calcium cyclopentadienide (), a metallocene analog of ferrocene featuring two -coordinated cyclopentadienyl rings, first synthesized in the late 1960s by the reaction of calcium metal with cyclopentadiene in tetrahydrofuran, yielding an insoluble polymeric solid. Another key representative is calcium acetylide (), formed via the high-temperature reaction of elemental calcium with carbon (typically above 2000°C), which serves as the primary industrial organocalcium species and is hydrolyzed to generate acetylene gas for organic synthesis. The practical applications of organocalcium compounds remain confined largely to academic research, where their strong nucleophilicity enables roles as initiators in anionic polymerization processes, such as the ring-opening polymerization of lactones or the synthesis of polyolefins, often outperforming traditional Grignard reagents due to reduced side reactions under optimized conditions. Advancements in stabilization have yielded notable complexes like bis[tris(trimethylsilyl)methyl]calcium (), prepared in the 1990s through metathesis of calcium diiodide with the corresponding lithium alkyl in hydrocarbon solvents; the enormous steric bulk of the ligands shields the reactive Ca-C bonds, enabling isolation as a two-coordinate, bent monomeric species stable enough for structural characterization and reactivity studies.Industrial applications
Metallurgical uses
Calcium plays a critical role in steel production through desulfurization processes, where it is added to molten steel in amounts of 0.1–0.3% to react with sulfur, forming calcium sulfide (CaS) inclusions.[70] These spherical CaS inclusions replace elongated manganese sulfide inclusions, which can cause brittleness and reduce ductility during hot working; the modification improves the steel's toughness and machinability by preventing crack propagation along inclusion boundaries.[71] This treatment is typically performed in the ladle during secondary metallurgy, using calcium wire or cored wire injection to ensure uniform distribution and minimize losses due to calcium's high reactivity with oxygen.[72] In lead alloys for maintenance-free batteries, calcium is incorporated at levels of 0.03–0.15% in combination with lead-antimony (Pb-Sb) to enhance grid performance.[73] The addition reduces self-discharge rates by forming stable passivation layers on the grid surfaces, minimizing corrosion and water loss, which extends battery life and eliminates the need for electrolyte maintenance.[74] These Pb-Ca-Sb alloys are cast into grids for automotive and industrial lead-acid batteries, where the calcium stabilizes the alloy against grid growth during charge-discharge cycles.[75] Calcium also contributes to aluminum alloys through the intermetallic compound CaAl₂, which acts as a grain refiner to promote finer equiaxed grains during solidification.[76] This refinement enhances the alloy's mechanical strength, fatigue resistance, and castability by increasing nucleation sites and restricting dendrite growth, particularly in wrought aluminum alloys used for aerospace and automotive components.[77] The addition is controlled to avoid excess calcium, which could lead to brittle phases. In rare earth metal production, calcium serves as a reducing agent to eliminate fluoride impurities during vacuum distillation.[78] High-purity calcium is added to rare earth fluorides (e.g., NdF₃ or DyF₃) in a sealed retort under vacuum, where it preferentially reduces the fluorides to volatile CaF₂, allowing distillation of the pure rare earth metal at temperatures around 1000–1400°C.[79] This calciothermic process is essential for achieving metallic purity above 99.5%, as residual fluorides degrade magnetic properties in applications like permanent magnets.[80]Chemical and construction uses
Calcium compounds play a pivotal role in construction and chemical industries, particularly through the use of calcium oxide (CaO) and its derivatives. In cement production, limestone is calcined to produce CaO, which constitutes 60–67% of Portland cement clinker and reacts with silicates, aluminates, and ferrites to form the binding phases essential for hydraulic cement.[81] Global Portland cement output reached 4.1 gigatons in 2023, underscoring its scale in infrastructure development.[82] Lime, primarily as calcium hydroxide (Ca(OH)₂), is widely employed in water treatment for softening hard water and adjusting pH. The process involves raising the water's pH to precipitate hardness-causing ions as calcium carbonate (CaCO₃), effectively removing temporary hardness while stabilizing alkalinity for downstream coagulation and corrosion control.[83][84] This application reduces scaling in pipes and improves water quality in municipal systems. In fertilizers, calcium cyanamide (CaCN₂) serves as a slow-release nitrogen source derived from nitrogen fixation processes, providing both nitrogen and calcium to enhance soil health and suppress weeds or pathogens.[85] Its use has declined relative to synthetic alternatives like urea due to handling requirements and slower nutrient release, though it remains valued in niche applications for sustainable agriculture.[86] Calcium oxide is integral to the paper and sugar industries for purification and bleaching. In papermaking, quicklime (CaO) is used to regenerate caustic soda in the Kraft process and produce calcium hypochlorite for bleaching pulp, aiding lignin removal and brightness enhancement.[87] In sugar refining, lime clarifies raw juice by neutralizing acids, precipitating impurities, and forming calcium saccharate for filtration, typically at rates of 0.25 tons per ton of sugar.[88] Calcium fluoride (CaF₂) finds application in toothpaste formulations as a mild abrasive, polishing tooth surfaces while releasing fluoride ions to support remineralization and caries prevention.[89] This dual functionality makes it suitable for sensitive enamel formulations.Biological role
Dietary sources and nutrition
Calcium is an essential mineral obtained primarily through dietary sources, with recommended daily intakes varying by age, sex, and physiological status to support bone health and other functions. According to the National Institutes of Health (NIH), adults aged 19 to 50 years require 1,000 mg of calcium per day, while women over 50 and men over 70 need 1,200 mg; for pregnant and lactating individuals, the recommended dietary allowance (RDA) is 1,300 mg for those aged 14 to 18 and 1,000 mg for ages 19 to 50.[90][91] These guidelines align with broader international recommendations from organizations like the International Osteoporosis Foundation, emphasizing intakes around 1,000 mg for most adults to prevent deficiency.[92] These elevated requirements for older adults support bone strength and help mitigate age-related bone loss, with calcium often paired with vitamin D to enhance absorption and efficacy in preventing osteoporosis.[93][94] Healthiest calcium sources prioritize high bioavailability, nutrient density, and minimal added sugars, saturated fats, or processing. Dairy products are primary sources for many people and provide highly bioavailable calcium with approximately 30% absorption. Examples include cow's milk (approximately 300 mg per cup), yogurt (approximately 450 mg per cup), and hard cheeses such as cheddar (approximately 200 mg per ounce). Fortified foods achieve similar absorption rates and include calcium-fortified orange juice (approximately 300 mg per 8 oz) and fortified soy milk (200–400 mg per cup). Non-dairy options encompass calcium-set tofu (250–750 mg per 4 oz, depending on processing with calcium salts), canned fish with edible bones such as sardines (approximately 370 mg per 3 oz) and salmon (170–210 mg per 3 oz), and low-oxalate leafy green vegetables such as kale (around 150 mg per 100 g), broccoli, and bok choy. Other good sources include almonds and fortified cereals. Foods highest in calcium per typical serving include dairy products and fortified foods. Top sources are:- Plain nonfat yogurt: 488 mg per 8 oz
- Plain low-fat yogurt: 448 mg per 8 oz
- Fortified almond milk: 442 mg per cup
- Tofu prepared with calcium sulfate: 434 mg per ½ cup
- Fortified orange juice: 349 mg per cup
- Sardines canned with bones: 325 mg per 3 oz
- Milk (nonfat or low-fat): ~300 mg per cup
- Yogurt (1 cup): 450 mg
- Milk (1 cup): 300 mg
- Fortified orange juice (8 oz): 300 mg
- Fortified soy milk (1 cup): 200–400 mg
- Tofu (firm, calcium-set, 4 oz): 250–750 mg
- Hard cheese (e.g., cheddar, 1 oz): 200 mg
- Sardines, canned with bones (3 oz): 370 mg
- Salmon, canned with bones (3 oz): 170–210 mg


