Calcium carbonate

Calcium carbonate is a chemical compound with the chemical formula CaCO3. It

Calcium carbonate
is a common substance found in rocks as the minerals calcite and aragonite, most
notably in chalk and limestone, eggshells, gastropod shells, shellfish skeletons and
pearls. Materials containing much calcium carbonate or resembling it are described
as calcareous. Calcium carbonate is the active ingredient in agricultural lime and is
created when calcium ions in hard water react with carbonate ions to create
limescale. It has medical use as a calcium supplement or as an antacid, but
excessive consumption can be hazardous and cause hypercalcemia and digestive
issues.[8]

Chemistry
Calcium carbonate shares the typical properties of other carbonates. Notably it

▪ reacts with acids, releasing carbon dioxide (technically speaking,

carbonic acid, but that disintegrates quickly to CO2 and H2O):

Names
▪ releases carbon dioxide upon heating, called a thermal decomposition IUPAC name
reaction, or calcination (to above 840 °C in the case of CaCO3), to form Calcium carbonate
calcium oxide, CaO, commonly called quicklime, with reaction enthalpy Other names
178 kJ/mol: Aragonite; calcite; chalk; lime;
limestone; marble; oyster; pearl
Identifiers

Calcium carbonate reacts with water that is saturated with carbon dioxide to form CAS Number 471-34-1 (https://co
the soluble calcium bicarbonate. mmonchemistry.cas.
org/detail?cas_rn=47
1-34-1)

This reaction is important in the erosion of carbonate rock, forming caverns, and 3D model Interactive image (htt
leads to hard water in many regions. (JSmol) ps://chemapps.stolaf.
edu/jmol/jmol.php?m
An unusual form of calcium carbonate is the hexahydrate ikaite, CaCO3·6H2O. odel=%5BCa%2B2%
Ikaite is stable only below 8 °C. 5D.%5BO-%5DC%2
8%5BO-%5D%29%3
Preparation DO)
Interactive image (htt
The vast majority of calcium carbonate used in industry is extracted by mining or ps://chemapps.stolaf.
quarrying. Pure calcium carbonate (such as for food or pharmaceutical use), can be
edu/jmol/jmol.php?m
produced from a pure quarried source (usually marble).
odel=C%28%3DO%
Alternatively, calcium carbonate is prepared from calcium oxide. Water is added to 29%28%5BO-%5D%
give calcium hydroxide then carbon dioxide is passed through this solution to 29%5BO-%5D.%5B
precipitate the desired calcium carbonate, referred to in the industry as precipitated Ca%2B2%5D)
calcium carbonate (PCC) This process is called carbonatation:[9]
 ChEBI CHEBI:3311 (https://
www.ebi.ac.uk/chebi/
searchId.do?chebiId
In a laboratory, calcium carbonate can easily be crystallized from calcium chloride =3311)
(CaCl2), by placing an aqueous solution of CaCl2 in a desiccator alongside
ammonium carbonate (NH4)2CO3.[10] In the desiccator, ammonium carbonate is ChEMBL ChEMBL1200539 (ht
exposed to air and decomposes into ammonia, carbon dioxide, and water. The tps://www.ebi.ac.uk/c
carbon dioxide then diffuses into the aqueous solution of calcium chloride, reacts hembldb/index.php/c
with the calcium ions and the water, and forms calcium carbonate. ompound/inspect/Ch
EMBL1200539)
Structure ChemSpider 9708 (https://www.ch
emspider.com/Chemi
The thermodynamically stable form of CaCO3 under normal conditions is cal-Structure.9708.ht
hexagonal β-CaCO3 (the mineral calcite).[11] Other forms can be prepared, the ml)
denser (2.83 g/cm3) orthorhombic λ-CaCO3 (the mineral aragonite) and hexagonal
DrugBank DB06724 (https://ww
μ-CaCO3, occurring as the mineral vaterite.[11] The aragonite form can be prepared
w.drugbank.ca/drugs
by precipitation at temperatures above 85 °C; the vaterite form can be prepared by
/DB06724)
precipitation at 60 °C.[11] Calcite contains calcium atoms coordinated by six
oxygen atoms; in aragonite they are coordinated by nine oxygen atoms.[11] The ECHA 100.006.765 (https://
vaterite structure is not fully understood.[12] Magnesium carbonate (MgCO3) has InfoCard echa.europa.eu/subs
the calcite structure, whereas strontium carbonate (SrCO3) and barium carbonate tance-information/-/s
(BaCO3) adopt the aragonite structure, reflecting their larger ionic radii.[11] ubstanceinfo/100.00
6.765)
EC Number 207-439-9
Polymorphs
E number E170 (colours)
Calcium carbonate crystallizes in three anhydrous polymorphs,[13][14]
of which KEGG D00932 (https://ww
calcite is the thermodynamically most stable at room temperature, aragonite is only
w.kegg.jp/entry/D009
slightly less so, and vaterite is the least stable.[15]
32)
PubChem CID 10112 (https://pubch
Crystal Structure em.ncbi.nlm.nih.gov/
compound/10112)
The calcite crystal structure is trigonal, with space group (No. 167 in the
International Tables for Crystallography[16]), and Pearson symbol .[17] RTECS FF9335000
Aragonite is orthorhombic, with space group (No 62), and Pearson Symbol number
.[18] Vaterite is composed of at least two different coexisting crystallographic UNII H0G9379FGK (http
structures. The major structure exhibits hexagonal symmetry in space group s://precision.fda.gov/
, the minor structure is still unknown.[19] uniisearch/srs/unii/H
0G9379FGK)
Crystallization CompTox DTXSID3036238 (htt
Dashboard ps://comptox.epa.go
All three polymorphs crystallize simultaneously from aqueous solutions under (EPA)
v/dashboard/chemic
ambient conditions.[15] In additive-free aqueous solutions, calcite forms easily as al/details/DTXSID30
the major product, while aragonite appears only as a minor product.
36238)
At high saturation, vaterite is typically the first phase precipitated, which is InChI [show]
followed by a transformation of the vaterite to calcite.[20] This behavior seems to InChI=1S/CH2O3.Ca/c2-1(3)4;/h(H2,2,
follow Ostwald's rule, in which the least stable polymorph crystallizes first, 3,4);/q;+2/p-2
followed by the crystallization of different polymorphs via a sequence of Key: VTYYLEPIZMXCLO-UHFFFAOY
increasingly stable phases.[21] However, aragonite, whose stability lies between SA-L
those of vaterite and calcite, seems to be the exception to this rule, as aragonite InChI=1/CH2O3.Ca/c2-1(3)4;/h(H2,2,
does not form as a precursor to calcite under ambient conditions.[15] 3,4);/q;+2/p-2
Aragonite occurs in majority when the reaction conditions inhibit the formation of Key: VTYYLEPIZMXCLO-NUQVWON
calcite and/or promote the nucleation of aragonite. For example, the formation of BAS
aragonite is promoted by the presence of magnesium ions,[22] or by using proteins SMILES [show]
and peptides derived from biological calcium carbonate.[23] Some polyamines such
[Ca+2].[O-]C([O-])=O
as cadaverine and Poly(ethylene imine) have been shown to facilitate the formation
of aragonite over calcite.[15] C(=O)([O-])[O-].[Ca+2]

Properties

Selection by organisms Chemical CaCO3

formula
Organisms, such as molluscs and arthropods, have shown the ability to grow all Molar mass 100.0869 g/mol
three crystal polymorphs of calcium carbonate, mainly as protection (shells) and Appearance Fine white powder;
muscle attachments.[24] Moreover, they exhibit a remarkable capability of phase chalky taste
selection over calcite and aragonite, and some organisms can switch between the
two polymorphs. The ability of phase selection is usually attributed to the use of Odor odorless
specific macromolecules or combinations of macromolecules by such organisms. Density 2.711 g/cm3 (calcite)
[25][26][27]
2.83 g/cm3
(aragonite)
Occurrence Melting point 1,339 °C (2,442 °F;
1,612 K) (calcite)
825 °C (1,517 °F;
Geological sources 1,098 K) (aragonite)
[4][5]
Calcite, aragonite and vaterite are pure calcium carbonate minerals. Industrially
important source rocks which are predominantly calcium carbonate include Boiling point decomposes
limestone, chalk, marble and travertine. Solubility in 0.013 g/L (25 °C)[1][2]
water
Solubility 3.3 × 10−9[3]
Biological sources product (Ksp)
Solubility in soluble
Eggshells, snail shells and most seashells are predominantly calcium carbonate and
can be used as industrial sources of that chemical.[29] Oyster shells have enjoyed dilute acids
recent recognition as a source of dietary calcium, but are also a practical industrial Acidity (pKa) 9.0
source.[30][31] Dark green vegetables such as broccoli and kale contain dietarily Magnetic −3.82 × 10−5 cm3/mol
significant amounts of calcium carbonate, but they are not practical as an industrial susceptibility
source.[32] (χ)
Refractive 1.59
index (nD)
Extraterrestrial
Structure
Beyond Earth, strong evidence suggests the presence of calcium carbonate on Crystal Trigonal
Mars. Signs of calcium carbonate have been detected at more than one location structure
(notably at Gusev and Huygens craters). This provides some evidence for the past Space group 32/m
presence of liquid water.[33][34]
Thermochemistry
Std molar 93 J·mol−1·K−1[6]
Geology entropy
(S⦵298)
Carbonate is found frequently in geologic settings and constitutes an enormous Std enthalpy −1207 kJ·mol−1[6]
carbon reservoir. Calcium carbonate occurs as aragonite, calcite and dolomite as of
significant constituents of the calcium cycle. The carbonate minerals form the rock formation
types: limestone, chalk, marble, travertine, tufa, and others. (ΔfH⦵298)

In warm, clear tropical waters corals are more abundant than towards the poles Pharmacology
where the waters are cold. Calcium carbonate contributors, including plankton
(such as coccoliths and planktic foraminifera), coralline algae, sponges,
brachiopods, echinoderms, bryozoa and mollusks, are typically found in shallow ATC code A02AC01 (WHO (htt
water environments where sunlight and filterable food are more abundant. Cold- ps://www.whocc.no/a
water carbonates do exist at higher latitudes but have a very slow growth rate. The tc_ddd_index/?code
calcification processes are changed by ocean acidification.
=A02AC01))
Where the oceanic crust is subducted under a continental plate sediments will be A12AA04 (WHO (htt
carried down to warmer zones in the asthenosphere and lithosphere. Under these ps://www.whocc.no/a
conditions calcium carbonate decomposes to produce carbon dioxide which, along tc_ddd_index/?code
with other gases, give rise to explosive volcanic eruptions. =A12AA04))
Hazards
Carbonate compensation depth NFPA 704
(fire diamond)
0
The carbonate compensation depth (CCD) is the point in the ocean where the rate 0 0
of precipitation of calcium carbonate is balanced by the rate of dissolution due to
the conditions present. Deep in the ocean, the temperature drops and pressure
Lethal dose or concentration (LD,
increases. Calcium carbonate is unusual in that its solubility increases with
LC):
decreasing temperature.[35] Increasing pressure also increases the solubility of
calcium carbonate. The carbonate compensation depth can range from 4,000 to LD50 6450 mg/kg (oral,
6,000 meters below sea level. (median rat)
dose)
NIOSH (US health exposure limits):
Role in taphonomy PEL TWA 15 mg/m3
(Permissible) (total) TWA 5 mg/m3
Calcium carbonate can preserve fossils through permineralization. Most of the
vertebrate fossils of the Two Medicine Formation—a geologic formation known (resp)[7]
for its duck-billed dinosaur eggs—are preserved by CaCO3 permineralization.[36] Safety data ICSC 1193 (http://ww
This type of preservation conserves high levels of detail, even down to the sheet (SDS) w.inchem.org/docum
microscopic level. However, it also leaves specimens vulnerable to weathering ents/icsc/icsc/eics11
when exposed to the surface.[36] 93.htm)
Related compounds
Trilobite populations were once thought to have composed the majority of aquatic
life during the Cambrian, due to the fact that their calcium carbonate-rich shells Other anions Calcium bicarbonate
were more easily preserved than those of other species,[37] which had purely Other cations Beryllium carbonate
chitinous shells. Magnesium
carbonate
Uses Strontium carbonate
Barium carbonate
Radium carbonate
Construction Related Calcium sulfate
compounds
The main use of calcium carbonate is in the construction industry, either as a
Except where otherwise noted, data
building material, or limestone aggregate for road building, as an ingredient of
are given for materials in their
cement, or as the starting material for the preparation of builders' lime by burning standard state (at 25 °C [77 °F],
in a kiln. However, because of weathering mainly caused by acid rain,[38] calcium 100 kPa).
carbonate (in limestone form) is no longer used for building purposes on its own,
verify (what is ?)
but only as a raw primary substance for building materials.
Infobox references
Calcium carbonate is also used in the purification of iron from iron ore in a blast
furnace. The carbonate is calcined in situ to give calcium oxide, which forms a slag with various impurities present, and
separates from the purified iron.[39]

In the oil industry, calcium carbonate is added to drilling fluids as a formation-bridging and filtercake-sealing agent; it is
also a weighting material which increases the density of drilling fluids to control the downhole pressure. Calcium carbonate
is added to swimming pools, as a pH corrector for maintaining alkalinity and offsetting the acidic properties of the
disinfectant agent.[40]
It is also used as a raw material in the refining of sugar from sugar beet; it is calcined
in a kiln with anthracite to produce calcium oxide and carbon dioxide. This burnt
lime is then slaked in fresh water to produce a calcium hydroxide suspension for the
precipitation of impurities in raw juice during carbonatation.[41]

Calcium carbonate in the form of chalk has traditionally been a major component of
blackboard chalk. However, modern manufactured chalk is mostly gypsum, hydrated
calcium sulfate CaSO4·2H2O. Calcium carbonate is a main source for growing
biorock. Precipitated calcium carbonate (PCC), pre-dispersed in slurry form, is a
common filler material for latex gloves with the aim of achieving maximum saving
in material and production costs.[42]

Fine ground calcium carbonate (GCC) is an essential ingredient in the microporous

film used in diapers and some building films, as the pores are nucleated around the
calcium carbonate particles during the manufacture of the film by biaxial stretching.
GCC and PCC are used as a filler in paper because they are cheaper than wood fiber. Crystal structure of calcite
Printing and writing paper can contain 10–20% calcium carbonate. In North
America, calcium carbonate has begun to replace kaolin in the production of
glossy paper. Europe has been practicing this as alkaline papermaking or acid-free
papermaking for some decades. PCC used for paper filling and paper coatings is
precipitated and prepared in a variety of shapes and sizes having characteristic
narrow particle size distributions and equivalent spherical diameters of 0.4 to 3
micrometers.

Calcium carbonate is widely used as an extender in paints,[43] in particular matte

emulsion paint where typically 30% by weight of the paint is either chalk or
marble. It is also a popular filler in plastics.[43] Some typical examples include
around 15 to 20% loading of chalk in unplasticized polyvinyl chloride (uPVC)
Crystal Structure of Calcite and
drainpipes, 5% to 15% loading of stearate-coated chalk or marble in uPVC
Aragonite
window profile. PVC cables can use calcium carbonate at loadings of up to 70 phr
(parts per hundred parts of resin) to improve mechanical properties (tensile
strength and elongation) and electrical properties (volume resistivity). Polypropylene
compounds are often filled with calcium carbonate to increase rigidity, a requirement
that becomes important at high usage temperatures.[44] Here the percentage is often
20–40%. It also routinely used as a filler in thermosetting resins (sheet and bulk
molding compounds)[44] and has also been mixed with ABS, and other ingredients,
to form some types of compression molded "clay" poker chips.[45] Precipitated
calcium carbonate, made by dropping calcium oxide into water, is used by itself or
with additives as a white paint, known as whitewashing.[46][47]
Microscopic Calcite and Vaterite
Calcium carbonate is added to a wide range of trade and do it yourself adhesives,
sealants, and decorating fillers.[43] Ceramic tile adhesives typically contain 70% to
80% limestone. Decorating crack fillers contain similar levels of marble or dolomite. It is also mixed with putty in setting
stained glass windows, and as a resist to prevent glass from sticking to kiln shelves when firing glazes and paints at high
temperature.[48][49][50][51]

In ceramic glaze applications, calcium carbonate is known as whiting,[43] and is a common ingredient for many glazes in its
white powdered form. When a glaze containing this material is fired in a kiln, the whiting acts as a flux material in the
glaze. Ground calcium carbonate is an abrasive (both as scouring powder and as an ingredient of household scouring
creams), in particular in its calcite form, which has the relatively low hardness level of 3 on the Mohs scale, and will
therefore not scratch glass and most other ceramics, enamel, bronze, iron, and steel, and have a moderate effect on softer
metals like aluminium and copper. A paste made from calcium carbonate and deionized water can be used to clean tarnish
on silver.[52]

Health and diet

Calcium carbonate is widely used medicinally as an inexpensive dietary calcium
supplement for gastric antacid[53] (such as Tums and Eno). It may be used as a
phosphate binder for the treatment of hyperphosphatemia (primarily in patients with
chronic kidney failure). It is used in the pharmaceutical industry as an inert filler for
tablets and other pharmaceuticals.[54]

Calcium carbonate is used in the production of calcium oxide as well as toothpaste

and has seen a resurgence as a food preservative and color retainer, when used in or
with products such as organic apples.[55]

Calcium carbonate is used therapeutically as phosphate binder in patients on Calcite is the most stable
maintenance haemodialysis. It is the most common form of phosphate binder polymorph of calcium carbonate. It
prescribed, particularly in non-dialysis chronic kidney disease. Calcium carbonate is is transparent to opaque. A
the most commonly used phosphate binder, but clinicians are increasingly transparent variety called Iceland
prescribing the more expensive, non-calcium-based phosphate binders, particularly spar (shown here) was used to
sevelamer. create polarized light in the 19th
century.[28]
Excess calcium from supplements, fortified food, and high-calcium diets can cause
milk-alkali syndrome, which has serious
toxicity and can be fatal. In 1915, Bertram
Sippy introduced the "Sippy regimen" of
hourly ingestion of milk and cream, and the
gradual addition of eggs and cooked cereal,
for 10 days, combined with alkaline powders,
which provided symptomatic relief for peptic
ulcer disease. Over the next several decades,
the Sippy regimen resulted in kidney failure, Calcium carbonate chunks from
alkalosis, and hypercalcaemia, mostly in men clamshell
Surface precipitation of CaCO3 as with peptic ulcer disease. These adverse
tufa in Rubaksa, Ethiopia effects were reversed when the regimen
stopped, but it was fatal in some patients with
protracted vomiting. Milk-alkali syndrome
declined in men after effective treatments for peptic ulcer disease arose. Since the
1990s it has been most frequently reported in women taking calcium supplements
above the recommended range of 1.2 to 1.5 grams daily, for prevention and treatment
of osteoporosis,[56][57] and is exacerbated by dehydration. Calcium has been added to
over-the-counter products, which contributes to inadvertent excessive intake.
Excessive calcium intake can lead to hypercalcemia, complications of which include
vomiting, abdominal pain and altered mental status.[58] Tufa at Huanglong, Sichuan

As a food additive it is designated E170,[59] and it has an INS number of 170. Used
as an acidity regulator, anticaking agent, stabilizer or color it is approved for usage in
the EU,[60] US[61] and Australia and New Zealand.[62] It is "added by law to all UK
milled bread flour except wholemeal".[63][64] It is used in some soy milk and almond
milk products as a source of dietary calcium; at least one study suggests that calcium
carbonate might be as bioavailable as the calcium in cow's milk.[65] Calcium
carbonate is also used as a firming agent in many canned and bottled vegetable
products.

Several calcium supplement formulations have been documented to contain the 500-milligram calcium supplements
chemical element lead,[66] posing a public health concern.[67] Lead is commonly made from calcium carbonate
found in natural sources of calcium.[66]

Agriculture and aquaculture

Agricultural lime, powdered chalk or limestone, is used as a cheap method for neutralising acidic soil, making it suitable for
planting, also used in aquaculture industry for pH regulation of pond soil before initiating culture. [68]

Household cleaning

Calcium carbonate is a key ingredient in many household cleaning powders like Comet and is used as a scrubbing agent.

Pollution mitigation

In 1989, a researcher, Ken Simmons, introduced CaCO3 into the Whetstone Brook in Massachusetts.[69] His hope was that
the calcium carbonate would counter the acid in the stream from acid rain and save the trout that had ceased to spawn.
Although his experiment was a success, it did increase the amount of aluminium ions in the area of the brook that was not
treated with the limestone. This shows that CaCO3 can be added to neutralize the effects of acid rain in river ecosystems.
Currently calcium carbonate is used to neutralize acidic conditions in both soil and water. [70][71][72] Since the 1970s, such
liming has been practiced on a large scale in Sweden to mitigate acidification and several thousand lakes and streams are
limed repeatedly.[73]

Calcium carbonate is also used in flue gas desulfurisation applications eliminating harmful SO2 and NO2 emissions from
coal and other fossil fuels burnt in large fossil fuel power stations.[70]

Calcination equilibrium
Calcination of limestone using charcoal fires to produce quicklime has been practiced since antiquity by cultures all over
the world. The temperature at which limestone yields calcium oxide is usually given as 825 °C, but stating an absolute
threshold is misleading. Calcium carbonate exists in equilibrium with calcium oxide and carbon dioxide at any temperature.
At each temperature there is a partial pressure of carbon dioxide that is in equilibrium with calcium carbonate. At room
temperature the equilibrium overwhelmingly favors calcium carbonate, because the equilibrium CO 2 pressure is only a tiny
fraction of the partial CO2 pressure in air, which is about 0.035 kPa.

At temperatures above 550 °C the equilibrium CO2 pressure begins to exceed the CO2 pressure in air. So above 550 °C,
calcium carbonate begins to outgas CO2 into air. However, in a charcoal fired kiln, the concentration of CO2 will be much
higher than it is in air. Indeed, if all the oxygen in the kiln is consumed in the fire, then the partial pressure of CO2 in the
kiln can be as high as 20 kPa.[74]

The table shows that this partial pressure is not achieved until the temperature is nearly 800 °C. For the outgassing of CO 2
from calcium carbonate to happen at an economically useful rate, the equilibrium pressure must significantly exceed the
ambient pressure of CO2. And for it to happen rapidly, the equilibrium pressure must exceed total atmospheric pressure of
101 kPa, which happens at 898 °C.

Equilibrium pressure of CO2 over CaCO3 (P) versus temperature (T).[75]

P
0.055 0.13 0.31 1.80 5.9 9.3 14 24 34 51 72 80 91 101 179 901 3961
(kPa)

T
550 587 605 680 727 748 777 800 830 852 871 881 891 898 937 1082 1241
(°C)

Solubility

With varying CO2 pressure

Calcium carbonate is poorly soluble in pure water (47 mg/L at normal atmospheric CO 2 partial pressure as shown below).
The equilibrium of its solution is given by the equation (with dissolved calcium
carbonate on the right):

2− Ksp = 3.7 × 10−9 to 8.7 × 10−9 at

CaCO3 ⇌ Ca2+ + CO3
25 °C

2−
where the solubility product for [Ca2+][CO3 ] is given as anywhere from Ksp =
3.7 × 10−9 to Ksp = 8.7 × 10−9 at 25 °C, depending upon the data source.[75][76] What
Travertine calcium carbonate
the equation means is that the product of molar concentration of calcium ions (moles
deposits from a hot spring
of dissolved Ca2+ per liter of solution) with the molar concentration of dissolved
2−
CO3 cannot exceed the value of Ksp. This seemingly simple solubility equation,
however, must be taken along with the more complicated equilibrium of carbon dioxide with water (see carbonic acid).
2− +
Some of the CO3 combines with H in the solution according to

− + 2−
HCO3 ⇌ H + CO3 Ka2 = 5.61 × 10−11 at 25 °C

−
HCO3 is known as the bicarbonate ion. Calcium bicarbonate is many times more soluble in water than calcium carbonate
—indeed it exists only in solution.
− +
Some of the HCO3 combines with H in solution according to

+ −
H2CO3 ⇌ H + HCO3 Ka1 = 2.5 × 10−4 at 25 °C

Some of the H2CO3 breaks up into water and dissolved carbon dioxide according to

H2O + CO2(aq) ⇌ H2CO3 Kh = 1.70 × 10−3 at 25 °C

And dissolved carbon dioxide is in equilibrium with atmospheric carbon dioxide according to

where kH = 29.76 atm/(mol/L) at

PCO2
25 °C (Henry constant), PCO2 being
[CO2] = kH
the CO2 partial pressure.

For ambient air, PCO2 is around 3.5 × 10−4 atmospheres (or equivalently 35 Pa). The last equation above fixes the
concentration of dissolved CO2 as a function of PCO2, independent of the concentration of dissolved CaCO3. At
atmospheric partial pressure of CO2, dissolved CO2 concentration is 1.2 × 10−5 moles per liter. The equation before that
fixes the concentration of H2CO3 as a function of CO2 concentration. For [CO2] = 1.2 × 10−5, it results in [H2CO3] =
2.0 × 10−8 moles per liter. When [H2CO3] is known, the remaining three equations together with

+ −
H2O ⇌ H + OH K = 10−14 at 25 °C

(which is true for all aqueous solutions), and the fact that the solution must be electrically neutral, i.e., the overall charge of
+
dissolved positive ions [Ca2+] + 2 [H ] must be cancelled out by the overall charge of dissolved negative ions
− 2− −
[HCO3 ] + [CO3 ] + [OH ], make it possible to solve simultaneously for the remaining five unknown concentrations (note
that the previously mentioned form of the neutrality is valid only if calcium carbonate has been put in contact with pure
water or with a neutral pH solution; in the case where the initial water solvent pH is not neutral, the balance is not neutral).
+
The adjacent table shows the result for [Ca2+] and [H ] (in the form of pH) as a function of ambient partial pressure of CO2
(Ksp = 4.47 × 10−9 has been taken for the calculation).

▪ At atmospheric levels of ambient CO2 the table indicates that the solution will be slightly alkaline with a
 maximum CaCO3 solubility of 47 mg/L. Calcium ion solubility as a function of
CO2 partial pressure at 25 °C
▪ As ambient CO2 partial pressure is reduced below atmospheric levels, the
(Ksp = 4.47 × 10−9)
solution becomes more and more alkaline. At extremely low PCO2,
dissolved CO2, bicarbonate ion, and carbonate ion largely evaporate from PCO2 (atm) pH [Ca2+] (mol/L)
the solution, leaving a highly alkaline solution of calcium hydroxide, which 10−12 12.0 5.19 × 10−3
is more soluble than CaCO3. Note that for PCO2 = 10−12 atm, the
− 10−10 11.3 1.12 × 10−3
[Ca2+][OH ]2 product is still below the solubility product of Ca(OH)2
10−8 10.7 2.55 × 10−4
(8 × 10−6). For still lower CO2 pressure, Ca(OH)2 precipitation will occur
before CaCO3 precipitation. 10−6 9.83 1.20 × 10−4
▪ As ambient CO2 partial pressure increases to levels above atmospheric, 10−4 8.62 3.16 × 10−4
pH drops, and much of the carbonate ion is converted to bicarbonate ion,
3.5 × 10−4 8.27 4.70 × 10−4
which results in higher solubility of Ca2+.
10−3 7.96 6.62 × 10−4
The effect of the latter is especially evident in day-to-day life of people who have hard
10−2 7.30 1.42 × 10−3
water. Water in aquifers underground can be exposed to levels of CO2 much higher
than atmospheric. As such water percolates through calcium carbonate rock, the 10−1 6.63 3.05 × 10−3
CaCO3 dissolves according to the second trend. When that same water then emerges 1 5.96 6.58 × 10−3
from the tap, in time it comes into equilibrium with CO2 levels in the air by outgassing
its excess CO2. The calcium carbonate becomes less soluble as a result, and the excess 10 5.30 1.42 × 10−2

precipitates as lime scale. This same process is responsible for the formation of
stalactites and stalagmites in limestone caves.

Two hydrated phases of calcium carbonate, monohydrocalcite CaCO3·H2O and ikaite CaCO3·6H2O, may precipitate from
water at ambient conditions and persist as metastable phases.

With varying pH, temperature and salinity: CaCO3 scaling in swimming pools

In contrast to the open equilibrium scenario above, many swimming pools are
managed by addition of sodium bicarbonate (NaHCO3) to about 2 mM as a buffer,
then control of pH through use of HCl, NaHSO4, Na2CO3, NaOH or chlorine
formulations that are acidic or basic. In this situation, dissolved inorganic carbon
(total inorganic carbon) is far from equilibrium with atmospheric CO2. Progress
towards equilibrium through outgassing of CO2 is slowed by

1. the slow reaction

H2CO3 ⇌ CO2(aq) + H2O;[77]
2. limited aeration in a deep water column; and
3. periodic replenishment of bicarbonate to maintain buffer capacity (often
estimated through measurement of total alkalinity).

In this situation, the dissociation constants for the much faster reactions
+ − + 2−
H2CO3 ⇌ H + HCO3 ⇌ 2 H + CO3

allow the prediction of concentrations of each dissolved inorganic carbon species in solution, from the added concentration
−
of HCO3 (which constitutes more than 90% of Bjerrum plot species from pH 7 to pH 8 at 25 °C in fresh water).[78]
− 2−
Addition of HCO3 will increase CO3 concentration at any pH. Rearranging the equations given above, we can see that
−
Ksp Ka2 [HCO3 ]
2− −
[Ca2+] = [CO2−] , and [CO3 ] = +
[H ] . Therefore, when HCO3 concentration is known, the maximum concentration of
3
Ca2+ ions before scaling through CaCO3 precipitation can be predicted from the formula:
 +
K [H ]
[Ca2+]max = Ksp × [HCO−]
a2 3

The solubility product for CaCO3 (Ksp) and the dissociation constants for the dissolved inorganic carbon species (including
Ka2) are all substantially affected by temperature and salinity,[78] with the overall effect that [Ca2+]max increases from
freshwater to saltwater, and decreases with rising temperature, pH, or added bicarbonate level, as illustrated in the
accompanying graphs.

The trends are illustrative for pool management, but whether scaling occurs also depends on other factors including
−
interactions with Mg2+, [B(OH)4] and other ions in the pool, as well as supersaturation effects.[79][80] Scaling is commonly
observed in electrolytic chlorine generators, where there is a high pH near the cathode surface and scale deposition further
increases temperature. This is one reason that some pool operators prefer borate over bicarbonate as the primary pH buffer,
and avoid the use of pool chemicals containing calcium.[81]

Solubility in a strong or weak acid solution

Solutions of strong (HCl), moderately strong (sulfamic) or weak (acetic, citric, sorbic, lactic, phosphoric) acids are
commercially available. They are commonly used as descaling agents 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 acid concentration [A] = [A ], we obtain (with CaCO3 molar
mass = 100 g/mol):

[A] (mol/L) 1 10−1 10−2 10−3 10−4 10−5 10−6 10−7 10−10

Initial pH 0.00 1.00 2.00 3.00 4.00 5.00 6.00 6.79 7.00

Final pH 6.75 7.25 7.75 8.14 8.25 8.26 8.26 8.26 8.27

Dissolved CaCO3
50.0 5.00 0.514 0.0849 0.0504 0.0474 0.0471 0.0470 0.0470
(g/L of acid)

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 [Ca2+] ≈ 0.5 [A ]. When the concentration decreases,
−
[HCO3] becomes non-negligible so that the preceding expression is no longer valid. For vanishing acid
concentrations, one can 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 total acid
−
concentration [A] = [A ] + [AH], we obtain:

[Ca2+] ≈ 0.5
[A] (mol/L) − 10−1 10−2 10−3 10−4 10−5 10−6 10−7 10−10
[A ]

Initial pH 2.38 2.88 3.39 3.91 4.47 5.15 6.02 6.79 7.00

Final pH 6.75 7.25 7.75 8.14 8.25 8.26 8.26 8.26 8.27

Dissolved CaCO3
49.5 4.99 0.513 0.0848 0.0504 0.0474 0.0471 0.0470 0.0470
(g/L of acid)

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 than 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
− 2− + −
calculated together with [HCO3], [CO3 ], [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 1.08 1.62 2.25 3.05 4.01 5.00 5.97 6.74 7.00

Final pH 6.71 7.17 7.63 8.06 8.24 8.26 8.26 8.26 8.27

Dissolved CaCO3
62.0 7.39 0.874 0.123 0.0536 0.0477 0.0471 0.0471 0.0470
(g/L of acid)

− 2− 3−
where [A] = [H3PO4] + [H2PO4] + [HPO4 ] + [PO4 ] is the total acid concentration. Thus phosphoric acid is
more efficient than a monoacid since at the final almost neutral pH, the second dissociated state
2−
concentration [HPO4 ] is not negligible (see phosphoric acid).

See also
▪ Cuttlebone
▪ Cuttlefish
▪ Gesso
▪ Limescale
▪ Marble
▪ Ocean acidification
▪ Whiting event
▪ List of climate engineering topics
▪ Lysocline

Electron micrograph of needle-like

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External links
▪ International Chemical Safety Card 1193 (https://www.ilo.org/dyn/icsc/showcard.display?p_lang=en&p_card_
id=1193&p_version=2)
▪ CID 516889 (https://pubchem.ncbi.nlm.nih.gov/compound/516889) from PubChem
▪ ATC codes: A02AC01 (WHO (https://www.whocc.no/atc_ddd_index/?code=A02AC01)) and A12AA04 (WHO
(https://www.whocc.no/atc_ddd_index/?code=A12AA04))
▪ The British Calcium Carbonate Association – What is calcium carbonate (http://calcium-carbonate.org.uk/cal
cium-carbonate.asp) Archived (https://web.archive.org/web/20080524102528/http://www.calcium-carbonate.
org.uk/calcium-carbonate.asp) 24 May 2008 at the Wayback Machine
▪ CDC – NIOSH Pocket Guide to Chemical Hazards – Calcium Carbonate (https://www.cdc.gov/niosh/npg/npg
d0090.html)

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