Calcium carbonate

Calcium carbonate is a chemical compound with the chemical formula CaCO3. It 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 produced when calcium ions in hard water react with carbonate
ions to form 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]

Crystal structure of calcite

Chemistry

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

reacts with acids, releasing carbonic acid which quickly disintegrates into carbon dioxide and
water:
+
CaCO3(s) + 2 H (aq) → Ca2+(aq) + CO2(g) + H2O(l)

releases carbon dioxide upon heating, called a thermal decomposition reaction, or calcination (to
above 840 °C in the case of CaCO3), to form calcium oxide, CaO, commonly called quicklime, with
reaction enthalpy 178 kJ/mol:
CaCO3(s) → CaO(s) + CO2(g)
 reacts with gaseous hydrogen to form methane
Calcium carbonate
and water vapor plus solid calcium oxide or
calcium hydroxide depending on temperature
and product gas composition. Various metals
including palladium and nickel are catalysts for
the reaction.

Calcium carbonate reacts with water that is

saturated with carbon dioxide to form the soluble
calcium bicarbonate.

CaCO3(s) + CO2(g) + H2O(l) → Ca(HCO3)2(aq)

This reaction is important in the erosion of

carbonate rock, forming caverns, and leads to
hard water in many regions.
Names
An unusual form of calcium carbonate is the
hexahydrate ikaite, CaCO3·6H2O. Ikaite is stable IUPAC name
only below 8 °C. Calcium carbonate

Other names
Preparation Aragonite
Calcite
The vast majority of calcium carbonate used in Chalk
industry is extracted by mining or quarrying. Pure Lime
calcium carbonate (such as for food or Limestone

pharmaceutical use), can be produced from a Marble

pure quarried source (usually marble). Oystershell

Pearl
Alternatively, calcium carbonate is prepared from
Identifiers
calcium oxide. Water is added to give calcium
hydroxide then carbon dioxide is passed through CAS Number 471-34-1 (https://co
this solution to precipitate the desired calcium mmonchemistry.cas.

carbonate, referred to in the industry as org/detail?cas_rn=47

1-34-1)
precipitated calcium carbonate (PCC). This
process is called carbonatation:[9] 3D model (JSmol) Interactive image (htt
ps://chemapps.stola
CaO + H2O → Ca(OH)2
f.edu/jmol/jmol.php?
Ca(OH)2 + CO2 → CaCO3 + H2O
model=%5BCa%2B2%
5D.%5BO-%5DC%28%
In a laboratory, calcium carbonate can easily be 5BO-%5D%29%3D
crystallized from calcium chloride (CaCl2), by O)

placing an aqueous solution of CaCl2 in a Interactive image (htt

ps://chemapps.stola
desiccator alongside ammonium carbonate
f.edu/jmol/jmol.php?
[NH4]2CO3.[10] In the desiccator, ammonium
model=C%28%3DO%
carbonate is exposed to air and decomposes into
29%28%5BO-%5D%2
ammonia, carbon dioxide, and water. The carbon 9%5BO-%5D.%5BCa%
dioxide then diffuses into the aqueous solution of 2B2%5D)
calcium chloride, reacts with the calcium ions and
ChEBI CHEBI:3311 (https://
the water, and forms calcium carbonate.
www.ebi.ac.uk/cheb
i/searchId.do?chebiId
Structure =3311)

The thermodynamically stable form of CaCO3 ChEMBL ChEMBL1200539 (htt

under normal conditions is hexagonal β-CaCO3 ps://www.ebi.ac.uk/c

hembl/explore/comp
(the mineral calcite). Other forms can be
ound/ChEMBL12005
prepared, the denser (2.83 g/cm3) orthorhombic
39)
λ-CaCO3 (the mineral aragonite) and hexagonal μ-
CaCO3, occurring as the mineral vaterite. The ChemSpider 9708 (https://www.ch

aragonite form can be prepared by precipitation emspider.com/Chemi

cal-Structure.9708.ht
at temperatures above 85 °C; the vaterite form
ml)
can be prepared by precipitation at 60 °C. Calcite
contains calcium atoms coordinated by six DrugBank DB06724 (https://ww
oxygen atoms; in aragonite they are coordinated w.drugbank.ca/drug
by nine oxygen atoms. The vaterite structure is s/DB06724)

not fully understood.[11] Magnesium carbonate ECHA InfoCard 100.006.765 (https://

(MgCO3) has the calcite structure, whereas echa.europa.eu/subs
strontium carbonate (SrCO3) and barium tance-information/-/s
carbonate (BaCO3) adopt the aragonite structure, ubstanceinfo/100.00
reflecting their larger ionic radii. 6.765)

EC Number 207-439-9
Polymorphs
E number E170 (colours)

Calcium carbonate crystallizes in three anhydrous

KEGG D00932 (https://ww
polymorphs,[12][13] of which calcite is the w.kegg.jp/entry/D009
thermodynamically most stable at room 32)
temperature, aragonite is only slightly less so, and PubChem CID 10112 (https://pubch
[14]
vaterite is the least stable. em.ncbi.nlm.nih.gov/
compound/10112)

RTECS number FF9335000

Crystal structure
UNII H0G9379FGK (http
The calcite crystal structure is trigonal, with
s://precision.fda.gov/
space group R3c (No. 167 in the International uniisearch/srs/unii/H
[15]
Tables for Crystallography ), and Pearson 0G9379FGK)
[16]
symbol hR10. Aragonite is orthorhombic, with
CompTox Dashboard DTXSID3036238 (htt
space group Pmcn (No 62), and Pearson Symbol (EPA)
ps://comptox.epa.go
oP20.[17] Vaterite is composed of at least two
v/dashboard/chemic
different coexisting crystallographic structures.
al/details/DTXSID303
The major structure exhibits hexagonal symmetry 6238)
in space group P63/mmc, the minor structure is
still unknown.[18] InChI [show]

SMILES [show]

Crystallization Properties

Chemical formula CaCO3

Molar mass 100.0869 g/mol

Appearance Fine white powder or

colorless crystals;
chalky taste

Odor odorless

Crystal structure of calcite and

Density 2.711 g/cm3 (calcite)
aragonite
2.83 g/cm3
All three polymorphs crystallize simultaneously (aragonite)
from aqueous solutions under ambient
Melting point 1,339 °C (2,442 °F;
conditions.[14] In additive-free aqueous solutions,
1,612 K) (calcite)
calcite forms easily as the major product, while
825 °C (1,517 °F;
aragonite appears only as a minor product. 1,098 K)
(aragonite)[4][5]
At high saturation, vaterite is typically the first
phase precipitated, which is followed by a Boiling point decomposes
transformation of the vaterite to calcite.[19] This
behavior seems to follow Ostwald's rule, in which Solubility in water 0.013 g/L (25 °C)[1][2]
the least stable polymorph crystallizes first,
Solubility product 3.3 × 10−9[3]
followed by the crystallization of different (Ksp)
polymorphs via a sequence of increasingly stable
phases.[20] However, aragonite, whose stability Solubility in dilute soluble
acids
lies between those of vaterite and calcite, seems
to be the exception to this rule, as aragonite does Magnetic −3.82 × 10−5 cm3/mol
susceptibility (χ)
not form as a precursor to calcite under ambient
conditions.[14] Refractive index (nD) 1.59

Structure

Crystal structure Trigonal

Space group 32/m

Thermochemistry

Std molar 93 J/(mol·K)[6]

Microscopic calcite and vaterite
entropy (S⦵298)
Aragonite occurs in majority when the reaction
Std enthalpy of −1207 kJ/mol[6]
conditions inhibit the formation of calcite and/or formation (ΔfH⦵298)
promote the nucleation of aragonite. For example,
the formation of aragonite is promoted by the Pharmacology

presence of magnesium ions,[21] or by using ATC code A02AC01 (WHO (http

proteins and peptides derived from biological s://www.whocc.no/at
[22]
calcium carbonate. Some polyamines such as c_ddd_index/?code=
cadaverine and Poly(ethylene imine) have been A02AC01) )
shown to facilitate the formation of aragonite A12AA04 (WHO (http
s://www.whocc.no/at
over calcite.[14] Solid‑state NMR analysis has
c_ddd_index/?code=
revealed that poly‑aspartate-stabilized ACC
A12AA04) )
contains water molecules that undergo
millisecond-timescale flips, illustrating dynamic Hazards
hydration as a key factor in delaying
NFPA 704
crystallization. [23] 0
(fire diamond)
0 0

Lethal dose or concentration (LD, LC):

Selection by organisms LD50 (median dose) 6450 mg/kg (oral,
rat)
Organisms, such as molluscs and arthropods,
NIOSH (US health exposure limits):
have shown the ability to grow all three crystal
polymorphs of calcium carbonate, mainly as PEL (Permissible) TWA 15 mg/m3
protection (shells) and muscle attachments.[24] (total) TWA 5 mg/m3

Moreover, they exhibit a remarkable capability of (resp)[7]

phase selection over calcite and aragonite, and Safety data sheet ICSC 1193 (http://ww
some organisms can switch between the two (SDS) w.inchem.org/docum
polymorphs. The ability of phase selection is ents/icsc/icsc/eics1
usually attributed to the use of specific 193.htm)
macromolecules or combinations of
Related compounds
macromolecules by such organisms.[25][26][27]
Other anions Calcium bicarbonate

Occurrence Other cations Beryllium carbonate

Magnesium
carbonate
Strontium carbonate
Barium carbonate
Radium carbonate
Zinc carbonate
Cadmium carbonate
Lead(II) carbonate

Related compounds Calcium sulfate

Calcite is the most stable polymorph of
calcium carbonate. It is transparent to Except where otherwise noted, data are given
opaque. A transparent variety called for materials in their standard state (at 25 °C
Iceland spar (shown here) was used to [77 °F], 100 kPa).
create polarized light in the 19th verify (https://en.wikipedia.org/w/index.ph
century.[28]
p?title=Special:ComparePages&rev1=477003
420&page2=Calcium+carbonate) (what is
Geological sources
?)

Calcite, aragonite and vaterite are pure calcium Infobox references

carbonate minerals. Industrially important source

rocks which are predominantly calcium carbonate include limestone, chalk, marble and travertine.
Biological sources

Calcium carbonate chunks from clamshell

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 recent recognition as a source of
dietary calcium, but are also a practical industrial source.[30][31] Dark green vegetables such as
broccoli and kale contain dietarily significant amounts of calcium carbonate, but they are not
practical as an industrial source.[32]

Annelids in the family Lumbricidae, earthworms, possess a regionalization of the digestive track
called calciferous glands, Kalkdrüsen, or glandes de Morren, that processes calcium and CO2 into
calcium carbonate, which is later excreted into the dirt.[33] The function of these glands is unknown
but is believed to serve as a CO2 regulation mechanism within the animals' tissues.[34] This process
is ecologically significant, stabilizing the pH of acid soils.[35]

Extraterrestrial

Beyond Earth, strong evidence suggests the presence of calcium carbonate on Mars. Signs of
calcium carbonate have been detected at more than one location (notably at Gusev and Huygens
craters). This provides some evidence for the past presence of liquid water.[36][37]
Geology

Surface precipitation of CaCO3 as tufa in

Rubaksa, Ethiopia

Carbonate is found frequently in geologic settings and constitutes an enormous carbon reservoir.
Calcium carbonate occurs as aragonite, calcite and dolomite as significant constituents of the
calcium cycle. The carbonate minerals form the rock types: limestone, chalk, marble, travertine, tufa,
and others.

Tufa at Huanglong, Sichuan

In warm, clear tropical waters corals are more abundant than towards the poles 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 water environments where sunlight and filterable food are more abundant.
Cold-water carbonates do exist at higher latitudes but have a very slow growth rate. The
calcification processes are changed by ocean acidification.

Where the oceanic crust is subducted under a continental plate sediments will be carried down to
warmer zones in the asthenosphere and lithosphere. Under these conditions calcium carbonate
decomposes to produce carbon dioxide which, along with other gases, give rise to explosive
volcanic eruptions.
Carbonate compensation depth

The carbonate compensation depth (CCD) is the point in the ocean where the rate 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 increases. Increasing pressure also increases the
solubility of calcium carbonate. Calcium carbonate is unusual in that its solubility increases with
decreasing temperature.[38] The carbonate compensation depth ranges from 4,000 to 6,000 meters
below sea level in modern oceans, and the various polymorphs (calcite, aragonite) have different
compensation depths based on their stability.[39]

Role in taphonomy

Calcium carbonate can preserve fossils through permineralization. Most of the vertebrate fossils of
the Two Medicine Formation—a geologic formation known for its duck-billed dinosaur eggs—are
preserved by CaCO3 permineralization.[40] This type of preservation conserves high levels of detail,
even down to the microscopic level. However, it also leaves specimens vulnerable to weathering
when exposed to the surface.[40]

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 were more easily preserved than
those of other species,[41] which had purely chitinous shells.

Uses

Construction

The main use of calcium carbonate is in the construction industry, either as a building material, or
limestone aggregate for road building, as an ingredient of cement, or as the starting material for the
preparation of builders' lime by burning in a kiln. However, because of weathering mainly caused by
acid rain,[42] calcium carbonate (in limestone form) is no longer used for building purposes on its
own, but only as a raw primary substance for building materials.

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.[43]
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.[44]

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.[45]

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.[46]

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. 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,[47] 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.[47] Some typical examples include around 15–20% loading of chalk in unplasticized
polyvinyl chloride (uPVC) drainpipes, 5–15% loading of stearate-coated chalk or marble in uPVC
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.[48] Here the percentage is often 20–40%. It also routinely used as a filler in
thermosetting resins (sheet and bulk molding compounds)[48] and has also been mixed with ABS,
and other ingredients, to form some types of compression molded "clay" poker chips.[49]
Precipitated calcium carbonate, made by dropping calcium oxide into water, is used by itself or with
additives as a white paint, known as whitewashing.[50][51]

Calcium carbonate is added to a wide range of trade and do it yourself adhesives, sealants, and
decorating fillers.[47] 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.[52][53][54][55]

In ceramic glaze applications, calcium carbonate is known as whiting,[47] 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.[56]

Health and diet

500-milligram calcium supplements made

from calcium carbonate

Calcium carbonate is widely used medicinally as an inexpensive dietary calcium supplement or

gastric antacid[57] (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.[58]

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.[59]
Calcium carbonate is used therapeutically as phosphate binder in patients on maintenance
haemodialysis. It is the most common form of phosphate binder prescribed, particularly in non-
dialysis chronic kidney disease. Calcium carbonate is the most commonly used phosphate binder,
but clinicians are increasingly prescribing the more expensive, non-calcium-based phosphate
binders, particularly sevelamer.

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, alkalosis, and
hypercalcaemia, mostly in men with peptic ulcer disease. These adverse 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,[60][61]
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.[62]

As a food additive it is designated E170,[63] 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,[64] US[65] and
Australia and New Zealand.[66] It is "added by law to all UK milled bread flour except
wholemeal".[67][68] 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.[69] 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 chemical element
lead,[70] posing a public health concern.[71] Lead is commonly found in natural sources of
calcium.[70]

Agriculture and aquaculture

Agricultural lime, powdered chalk or limestone, is used as a cheap method of neutralising acidic
soil, making it suitable for planting, also used in aquaculture industry for pH regulation of pond soil
before initiating culture.[72] There is interest in understanding whether or not it can affect pesticide
adsorption and desorption in calcareous soil.[73]

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.[74] 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.[75][76] 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.[77]

Calcium carbonate is also used in flue-gas desulfurization applications eliminating harmful SO2 and
NO2 emissions from coal and other fossil fuels burnt in large fossil fuel power stations.[75]

Plastics

Calcium carbonate is commonly used in the plastic industry as a filler. When it is incorporated in a
plastic material, it can improve the hardness, stiffness, dimensional stability and processability of
the material.[78]

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 CO2
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.[79]

The table shows that this partial pressure is not achieved until the temperature is nearly 800 °C. For
the outgassing of CO2 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).[80]

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

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

Solubility

With varying CO2 pressure

Travertine calcium carbonate deposits

from a hot spring

Calcium carbonate is poorly soluble in pure water (47 mg/L at normal atmospheric CO2 partial
pressure as shown below).

The equilibrium of its solution is given by the equation (with dissolved calcium carbonate on the
right):

Ksp = 3.7 × 10−9 to 8.7 × 10−9 at

CaCO3 ⇌ Ca 2+
+ CO2−
3
25 °C
where the solubility product for [Ca2+][CO2− −9
3 ] is given as anywhere from Ksp = 3.7 × 10 to Ksp =
8.7 × 10−9 at 25 °C, depending upon the data source.[80][81] What the equation means is that the
product of molar concentration of calcium ions (moles of dissolved Ca2+ per liter of solution) with
the molar concentration of dissolved CO2−
3 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). Some of the CO2−
3 combines with H in the solution
according to

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

HCO−3 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 HCO−3 combines with H in solution according to

+
H2CO3 ⇌ H + HCO−3 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

PCO where = 29.76 atm/(mol/L) at 25 °C (Henry volatility),

⁠
[CO2] =
2

and PCO2 is the CO2 partial pressure.

For ambient air, PCO is around 3.5 × 10−4 atm (or equivalently 35 Pa). The last equation above fixes
2

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 constraint 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 [HCO−3] + [CO2−
3 ] + [OH ], make it possible to solve
simultaneously for the remaining five unknown concentrations (the Calcium ion solubility as a
previously mentioned form of the neutrality is valid only if calcium function of CO2 partial
pressure at 25 °C
carbonate has been put in contact with pure water or with a neutral pH
(Ksp = 4.47 × 10−9)
solution; in the case where the initial water solvent pH is not neutral, the
PCO2 (atm) pH [Ca2+] (mol/L)
balance is not neutral).
10−12 12.0 5.19 × 10−3
+
The adjacent table shows the result for [Ca2+] and [H ] (in the form of 10−10 11.3 1.12 × 10−3
−9
pH) as a function of ambient partial pressure of CO2 (Ksp = 4.47 × 10
10−8 10.7 2.55 × 10−4
has been taken for the calculation).
10−6 9.83 1.20 × 10−4
At atmospheric levels of ambient CO2 the table indicates that the 10−4 8.62 3.16 × 10−4
solution will be slightly alkaline with a maximum CaCO3 solubility of 3.5 × 10−4 8.27 4.70 × 10−4
47 mg/L. 10−3 7.96 6.62 × 10−4

As ambient CO2 partial pressure is reduced below atmospheric levels, 10−2 7.30 1.42 × 10−3

the solution becomes more and more alkaline. At extremely low PCO2, 10−1 6.63 3.05 × 10−3
dissolved CO2, bicarbonate ion, and carbonate ion largely evaporate 1 5.96 6.58 × 10−3
from the solution, leaving a highly alkaline solution of calcium 10 5.30 1.42 × 10−2
hydroxide, which is more soluble than CaCO3. For PCO2 = 10−12 atm,
−
the [Ca2+][OH ]2 product is still below the solubility product of Ca(OH)2 (8 × 10−6). For still lower
CO2 pressure, Ca(OH)2 precipitation will occur before CaCO3 precipitation.

As ambient CO2 partial pressure increases to levels above atmospheric, pH drops, and much of
the carbonate ion is converted to bicarbonate ion, which results in higher solubility of Ca2+.

The effect of the latter is especially evident in day-to-day life of people who have hard 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 CaCO3 dissolves according to one of the
trends above. When that same water then emerges 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 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 the concentration of about 2 mmol/L 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;[82]

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
+ +
H2CO3 ⇌ H + HCO−3 ⇌ 2 H + CO2−
3

allow the prediction of concentrations of each dissolved inorganic carbon species in solution, from
the added concentration of HCO−3 (which constitutes more than 90% of Bjerrum plot species from
pH 7 to pH 8 at 25 °C in fresh water).[83] Addition of HCO−3 will increase CO2−
3 concentration at any
−
Ksp Ka2 [HCO3]
2+ 2−
pH. Rearranging the equations given above, we can see that [Ca ] = ⁠[CO2−] ⁠, and [CO3 ] =⁠ +
[H ]
⁠.
3

Therefore, when HCO−3 concentration is known, the maximum concentration of Ca2+ ions before
scaling through CaCO3 precipitation can be predicted from the formula:
 +
Ksp [H ]
2+
[Ca ]max = ⁠K ⁠× ⁠[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,[83] 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.[84][85] 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.[86]

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

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 [Ca2+] ≈ 0.5 [A ]. When the
concentration decreases, [HCO−3] 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:
 −
[A] (mol/L) [Ca2+] ≈ 0.5 [A ] 10−1 10−2 10−3 10−4 10−5 10−6 10−7 10−10

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

For the same total acid concentration, the initial pH of the weak acid is less acid than that 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 calculated together with [HCO−3], [CO2− 2+
3 ], [Ca ], [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 (g/L of acid) 62.0 7.39 0.874 0.123 0.0536 0.0477 0.0471 0.0471 0.0470

where [A] = [H3PO4] + [H2PO−4] + [HPO2− 3−

4 ] + [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 concentration [HPO2−
4 ] is not negligible (see phosphoric acid).
See also

Electron micrograph of needle-like calcium

carbonate crystals formed as limescale in
a kettle

Around 2 g of calcium-48 carbonate

Cuttlebone

Cuttlefish

Gesso

Limescale

Marble

Ocean acidification

Whiting event
 List of climate engineering topics

Lysocline

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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-carbonat

e.org.uk/calcium-carbonate.asp) Archived (https://web.archive.org/web/20080524102528/htt
p://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/nio

sh/npg/npgd0090.html)