Calcium carbonate

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Calcium carbonate
Other names Limestone; calcite; aragonite; chalk; marble
Identifiers
CAS number 471-34-1
Properties
Molecular formula CaCO3
Molar mass 100.087 g/mol
Appearance White powder.
Density 2.83 g/cm³, solid.
Melting point

825 °C

Boiling point

Decomposes

Solubility in water Insoluble
Structure
Molecular shape Linear
Hazards
Main hazards Not hazardous.
R-phrases R36, R37, R38
S-phrases S26, S36
Flash point Non-flammable.
Except where noted otherwise, data are given for
materials in their standard state
(at 25 °C, 100 kPa)

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Calcium carbonate is a chemical compound, with the chemical formula CaCO3. It is a common substance found as rock in all parts of the world, and is the main component of shells of marine organisms, snails, and eggshells. Calcium carbonate is the active ingredient in agricultural lime, and is usually the principal cause of hard water. It is commonly used medicinally as a calcium supplement or as an antacid.

Occurrence

Calcium carbonate is found naturally as the following minerals and rocks: Aragonite, Calcite, Vaterite or (μ-CaCO3), Chalk, Limestone, Marble and Travertine

To test whether a mineral or rock contains calcium carbonate, strong acids, such as hydrochloric acid, can be added to it. If the sample does contain calcium carbonate, it will fizz and produce carbon dioxide and water. Weak acids such as acetic acid will react, albeit less vigorously. All of the rocks/minerals mentioned above will react with acid.

Chemical properties

See also: Carbonate

Calcium carbonate shares the typical properties of other carbonates. Notably:

  1. it reacts with strong acids, releasing carbon dioxide:
    CaCO3 + 2HCl → CaCl2 + CO2 + H2O

Calcium carbonate will react with water that is saturated with carbon dioxide to form the soluble calcium bicarbonate.

CaCO3 + CO2 + H2O → Ca(HCO3)2

Preparation

The vast majority of calcium carbonate used in industry is extracted by mining or quarrying. Pure calcium carbonate (e.g. for food or pharmaceutical use), can be produced from a pure quarried source (usually marble).

Alternatively, calcium oxide is prepared by calcining crude calcium carbonate. Water is added to give calcium hydroxide, and carbon dioxide is passed through this solution to precipitate the desired calcium carbonate, referred to in the industry as precipitated calcium carbonate (PCC):[1]

CaCO3 → CaO + CO2
CaO + H2O → Ca(OH)2
Ca(OH)2 + CO2 → CaCO3 + H2O

Uses

Health and dietary applications

Calcium carbonate is widely used medicinally as an inexpensive dietary calcium supplement or antacid.[1] It may be used as a phosphate binder for the treatment of hyperphosphatemia (primarily in patients with chronic renal failure) when lanthanum carbonate is not prescribed. It is also used in the pharmaceutical industry as an inert filler for tablets and other pharmaceuticals.[1]

As a food additive, it is used in some soy milk products as a source of dietary calcium; one study concludes that calcium carbonate is as bioavailable as ordinary cow's milk.[1]

Solubility

With varying pH

We now consider the problem of the maximum solubility of calcium carbonate in normal atmospheric conditions (\scriptstyle P_{\mathrm{CO}_2} = 3.5 × 10−4 atm) when the pH of the solution is adjusted. This is for example the case in a swimming pool where the pH is maintained between 7 and 8 (by addition of NaHSO4 to decrease the pH or of NaHCO3 to increase it). From the above equations for the solubility product, the hydratation reaction and the two acid reactions, the following expression for the maximum [Ca2+] can be easily deduced:

[\mathrm{Ca}^{2+}]_\mathrm{max} = \frac{K_\mathrm{sp}k_\mathrm{H}} {K_\mathrm{h}K_\mathrm{a1}K_\mathrm{a2}} \frac{[\mathrm{H}^+]^2}{P_{\mathrm{CO}_2}}

showing a quadratic dependence in [H+]. The numerical application with the above values of the constants gives

pH 7.0 7.2 7.4 7.6 7.8 8.0 8.2 8.27 8.4
[Ca2+]max (10-4mol/L or °F) 1590 635 253 101 40.0 15.9 6.35 4.70 2.53
[Ca2+]max (mg/L) 6390 2540 1010 403 160 63.9 25.4 18.9 10.1

Comments:

  • decreasing the pH from 8 to 7 increases the maximum Ca2+ concentration by a factor 100
  • note that the Ca2+ concentration of the previous table is recovered for pH = 8.27
  • keeping the pH to 7.4 in a swimming pool (which gives optimum HClO/OCl ratio in the case of "chlorine" maintenance) results in a maximum Ca2+ concentration of 1010 mg/L. This means that successive cycles of water evaporation and partial renewing may result in a very hard water before CaCO3 precipitates. Addition of a calcium sequestrant or complete renewing of the water will solve the problem.

Solubility in a strong or weak acid solution

Solutions of strong (HCl) or weak (acetic, phosphoric) acids are commercially available. They are commonly used to remove limescale deposits. The maximum amount of CaCO3 that can be "dissolved" by one liter of an acid solution can be calculated using the above equilibrium equations.

  • In the case of a strong monoacid with decreasing concentration [A] = [A], we obtain (with CaCO3 molar mass = 100 g):
[A] (mol/L) 1 10−1 10−2 10−3 10−4 10−5 10−6 10−7 10−10
Initial pH 0.001.002.003.004.005.006.006.797.00
Final pH 6.757.257.758.148.258.268.268.268.27
Dissolved CaCO3 (g per liter of acid) 50.05.000.5140.08490.05040.04740.04710.04700.0470

where the initial state is the acid solution with no Ca2+ (not taking into account possible CO2 dissolution) and the final state is the solution with saturated Ca2+. For strong acid concentrations, all species have a negligible concentration in the final state with respect to Ca2+ and A so that the neutrality equation reduces approximately to 2[Ca2+] = [A] yielding \scriptstyle[\mathrm{Ca}^{2+}] \simeq \frac{[\mathrm{A}^-]}{2}. When the concentration decreases, [HCO3] becomes non negligible so that the preceding expression is no longer valid. For vanishing acid concentrations, we recover the final pH and the solubility of CaCO3 in pure water.

  • In the case of a weak monoacid (here we take acetic acid with pKA = 4.76) with decreasing concentration [A] = [A]+[AH], we obtain:
[A] (mol/L) 1 10−1 10−2 10−3 10−4 10−5 10−6 10−7 10−10
Initial pH 2.382.883.393.914.475.156.026.797.00
Final pH 6.757.257.758.148.258.268.268.268.27
Dissolved CaCO3 (g per liter of acid) 49.54.990.5130.08480.05040.04740.04710.04700.0470

We see that for the same total acid concentration, the initial pH of the weak acid is less acid than the one of the strong acid; however, the maximum amount of CaCO3 which can be dissolved is approximately the same. This is because in the final state, the pH is larger that the pKA, so that the weak acid is almost completely dissociated, yielding in the end as many H+ ions as the strong acid to "dissolve" the calcium carbonate.

  • The calculation in the case of phosphoric acid (which is the most widely used for domestic applications) is more complicated since the concentrations of the four dissociation states corresponding to this acid must be calculated together with [HCO3], [CO32−], [Ca2+], [H+] and [OH]. The system may be reduced to a seventh degree equation for [H+] the numerical solution of which gives
[A] (mol/L) 1 10−1 10−2 10−3 10−4 10−5 10−6 10−7 10−10
Initial pH 1.081.622.253.054.015.005.976.747.00
Final pH 6.717.177.638.068.248.268.268.268.27
Dissolved CaCO3 (g per liter of acid) 62.07.390.8740.1230.05360.04770.04710.04710.0470

where [A] = [H3PO4] + [H2PO4] + [HPO42−] + [PO43−]. We see that phosphoric acid is more efficient than a monoacid since at the final almost neutral pH, the second dissociated state concentration [HPO42−] is not negligible (see phosphoric acid ).

References


External links

ar:كربونات كالسيوم cs:Uhličitan vápenatý da:Calciumcarbonat de:Calciumcarbonat et:Kaltsiumkarbonaatfr:Carbonate de calcium it:Carbonato di calcio he:סידן פחמתי lv:Kalcija karbonāts hu:Kalcium-karbonát nl:Calciumcarbonaat ja:炭酸カルシウム no:Kalsiumkarbonat nn:Kalsiumkarbonatsimple:Calcium carbonate sk:Uhličitan vápenatý sl:Kalcijev karbonat sr:Калцијум карбонат fi:Kalsiumkarbonaatti sv:Kalciumkarbonat th:แคลเซียมคาร์บอเนต vi:Cacbonat canxi uk:Карбонат кальцію

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Some of the initial content on this page may be incorporated in part from copyleft sources in the public domain including wikis such as Wikipedia and AskDrWiki. Drug information for patients came from the The National Library of Medicine. Infectious disease information may have come from the Centers for Disease Control (CDC). Differential Diagnoses are drawn from clinicians as well as an amalgamation of 3 sources: 1.The Disease Database; 2. Kahan, Scott, Smith, Ellen G. In A Page: Signs and Symptoms. Malden, Massachusetts: Blackwell Publishing, 2004:3; 3. Sailer, Christian, Wasner, Susanne. Differential Diagnosis Pocket. Hermosa Beach, CA: Borm Bruckmeir Publishing LLC, 2002:7 .

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