In Practical Chemical Thermodynamics for Geoscientists, 2013

E Carbonic acid–calcium carbonate system

We consider ionization and solubility equilibria of carbon dioxide, carbonic acid, and calcium
carbonate in some detail because of their importance for geochemistry of natural waters. The
dissolution of CO2 gas in water occurs via the reaction
(11-278)CO2(g)=CO2(aq)
(11-279)KH=aCO2(aq)fCO2(g)≅mCO2(aq)PCO2(g)
(11-280)logKH=108.3865+1.985076×10−2T−6919.53T−40.45154logT+669,365T2

At 25°C, KH = 10−1.47 (relative to one molal and one bar standard states for aqueous and gaseous
CO2). Equation (11-280) from Plummer and Busenberg (1982) is valid from 0°C to 100°C at one
bar pressure. Table 11-11 lists values of pKH (= − log KH) calculated from this equation (and the
other equilibrium constants defined below) as a function of temperature from 5°C to 45°C.
Table 11-11. Equilibrium Constants for H CO -CaCO System
2 3 3
a

T (°C) T (K) pKH pKCO2 pK1 pK2 pKs

5 278.15 1.19 2.71 3.81 10.56 8.39
15 288.15 1.34 2.67 3.75 10.43 8.43
25 298.15 1.47 2.59 3.76 10.33 8.48
35 308.15 1.58 2.53 3.78 10.25 8.54
38 311.15 1.61 2.5 3.8 10.23 8.56
45 318.15 1.67 2.49 3.8 10.2 8.62
a
Harned and Owen (1958), Harned and Scholes (1941), Plummer and Busenberg (1982).

A small fraction of the CO2 dissolved in the water is hydrated to form carbonic acid:
(11-281)CO2(aq)+H2O(liq)=H2CO3(aq)

The equilibrium constant for hydration of aqueous CO2 is

(11-282)KCO2=aH2CO3aCO2(aq)aH2O=aH2CO3aCO2(aq)≅mH2CO3mCO2

The activity of water is unity and it drops out of the equilibrium constant expression but the
ΔfGo of liquid water is needed to compute the standard Gibbs energy change for this reaction. At
25°C, KCO2 = 10−2.59 and the molar CO2/H2CO3 ratio is about 389. Furthermore, hydration of
CO2 proceeds slowly. Thus, most of the “carbonic acid” in solution is actually aqueous CO2.
Reactions (11-278) and (11-281) are often combined to give the net reaction
(11-283)CO2(g)+H2O(liq)=H2CO3(aq)

The equilibrium constant for reaction (11-283) is

(11-284)K′CO2=aH2CO3fCO2aH2O=aH2CO3fCO2≅mH2CO3PCO2

The equilibrium constant K′CO2 is the product of KH and KCO2:

(11-
285)K′CO2=KHKCO2=aCO2(aq)fCO2(g)·aH2CO3aCO2(aq)=aH2CO3fCO2≅mH2CO3PCO2

Thus, at 25°C, K′CO2 = 10−4.06. Neutral carbonic acid ionizes via the reaction
(11-286)H2CO3(aq)=HCO3−(aq)+H+(aq)

The equilibrium constant for this reaction, which is the first ionization constant (K1) for carbonic
acid, and its value at 298.15 K are
(11-287)KH2CO3=K1=aHCO3−(aq)aH+(aq)aH2CO3(aq)≅mHCO3−mH+mH2CO3=10−3.76

The sum of reactions (11-281) and (11-286) gives the ionization of aqueous CO2 in water:
(11-288)CO2(aq)+H2O(liq)=HCO3−(aq)+H+(aq)
(11-289)K′1=aHCO3−(aq)aH+(aq)aCO2(aq)≅mHCO3−mH+mCO2=10−6.35

The equilibrium constant K′1 is often quoted as the first ionization constant of carbonic acid, but
it is the ionization constant for aqueous CO2 dissolved in water.
Ionization of the aqueous bicarbonate ion occurs via
(11-290)HCO3−(aq)=CO32−(aq)+H+(aq)

The ionization constant for the bicarbonate ion, which is the second ionization constant for
carbonic acid, and its value at 298.15 K are
(11-291)KHCO3−=K2=aCO32−aH+aHCO3−≅mCO32−mH+mHCO3−=10−10.33

The dissolution of CaCO3 (calcite), its solubility product, and its value at 298.15 K are
(11-292)CaCO3(calcite)=Ca2+(aq)+CO32−(aq)
(11-293)Ks=aCa2+aCO32−≅mCa2+mCO32−=10−8.48

Plummer and Busenberg (1982) give the following equation for the temperature dependence of
the solubility product for calcite between 0°C and 90°C:
(11-294)logKs=−171.9065−7.7993×10−2T+2839.319T+71.595logT

These reactions and equilibrium constants allow us to consider a number of interesting problems
applicable to the geochemistry of natural waters. One example is given here, and others are given
in problems at the end of this chapter.
Example 11-13. Calculate the pH of rainwater equilibrated with atmospheric CO2 at the global
mean temperature and pressure of 15°C and one atmosphere (∼1.013 bar). As of August 2008,
Earth’s atmosphere contained about 385 parts per million by volume (385 ppmv) CO2. We
assume that dissolved carbonic acid is the only source of acidity in the rainwater and that
activities and fugacities can be approximated by molalities and partial pressures.
We first calculate the CO2 partial pressure in Earth’s atmosphere. This is
(11-295)PCO2=XCO2PT=(385×10−6)(1.013bar)=3.9×10−4bar
Equilibration of rainwater with this CO2 partial pressure gives a carbonic acid molality of
(11-296)mH2CO3≅(K′CO2)(PCO2)=(10−4.01)(3.9×10−4)=10−7.42=3.81×10−8

The carbonic acid molality in rainwater remains constant because any H2CO3 that ionizes is
replenished by CO2 from air. Ionization of carbonic acid produces hydrogen ions and bicarbonate
ions on a one-to-one basis. Hence, the hydrogen ion molality is given by
(11-297)mH+=[(K1)(mH2CO3)]1/2=(10−3.75·10−7.42)1/2=10−5.59

The pH of the rainwater is 5.59 due only to atmospheric carbon dioxide. You should convince
yourself that you get the same answer by calculating the molality of aqueous CO2 and its
subsequent ionization.