The changing patterns of rainfall and snowmelt, when recharging ground water in

karstified carbonate rocks, can be captured in speleothems via the hydrological

behaviour of the drips

The most common stalactites are speleothems, which occur in limestone caves. They
form through deposition of calcium carbonate and other minerals, which
is precipitated from mineralized water solutions. Limestone is the chief form of
calcium carbonate rock which is dissolved by water that contains carbon dioxide,
forming a calcium bicarbonate solution in underground caverns.[4] The chemical
formula for this reaction is:[5]

Ca2+(aq) + 2HCO3-(aq) ⇄ CaCO3(s) + H2O(l) + CO2(g);

This solution travels through the rock until it reaches an edge and if this is on the roof
of a cave it will drip down. When the solution comes into contact
with air the chemical reactionthat created it is reversed and particles of calcium
carbonate are deposited. The reversed reaction is:[5]
 stalactite and stalagmite in limestone caves is the result of the following reversible
reaction:
CaCO3(s) + H2O(l) + CO2(aq) ⇄ Ca2+(aq) + 2 HCO3-(aq)

As the ground temperature surrounding a cave increases, stalactite and stalagmite

growth is found to decrease. What is the best explanation for this?
Increasing temperature decreases the aqueous solubility of CaCO3
CaCO3 is one of the exceptions to general solubility rules because its solubility in
water actually decreases with increasing temperature. If less CaCO3 gets dissolved,
less will be available to precipitate in the cave as a stalactite or stalagmite.

Calcium carbonate has a very low solubility in pure water (15 mg/L at 25°C), but in
rainwater saturated with carbon dioxide, its solubility increases due to the formation
of more soluble calcium bicarbonate. Calcium carbonate is unusual in that its
solubility increases as the temperature of the water decreases.

The increased solubility of calcium carbonate in rainwater saturated

with carbon dioxide is the driving force behind the erosion of limestone rocks, leading
to the formation over long periods of time of caverns, caves, stalagmites and
stalactites. Rainwater is weakly acidic, and when it meets with limestone, some of the
calcium carbonate reacts to form a solution of calcium bicarbonate.

he formation of stalactites and stalagmites is in effect a reversal of this dissolving

process in that the bicarbonate-rich water that drips from the ceiling of the cave
partially evaporates, leaving behind a calcium carbonate deposit.

Equations
HCO3− ⇌ H+ + CO32− , H2O + CO2(dissolved) ⇌ H2CO3 , CaCO3 ⇌ Ca2+ + CO32−,

Equilbrium changes of CaCO3(s) + H2O(l) + CO2(aq) ⇄ Ca2+(aq) + 2 HCO3-(aq)

- when the temperature increases the equation shifts to the left as the products
form to create more reactants since CaCo3 is getting dissolved at a high rate.
 - Increase of concentration of reactants shifts to the right.
Extra info -
As water percolates down through the soil and rock above the cave, it becomes
enriched in dissolved carbon dioxide and calcium, such that its emergence into the
cave environment, where the partial pressure of CO2 is lower, is accompanied by
outgassing of CO2. This, in turn, raises the pH slightly, rendering calcium carbonate
slightly supersaturated.

High solubility high Ksp. Changes in enthalpy and entropy affects Ksp.
Disassociation is the seperation of positive ad negative ions from a solidionic
compund to for hydrated ions due to the attarction between dipoles that are oppositely
charged. Dynamic equilbrium ab2 (s) -> a2+ (aq) +2B-(aq) ( insoluable salts less
than 1gperL common ion affect. Added to saturated solution to decrease solubility of
salt.

Diagenetic: Diagenesis refers to the chemical, physical and biological changes

experienced by sediment after its initial deposition and during and after it forms solid
rock. During lithification, sediments compact under pressure. Diagenesis occurs when
this occurs at relatively low temperatures and pressures, in contrast to metamorphism.