subject: Carbonic Acid [print this page] Role of carbonic acid in blood Role of carbonic acid in blood
Carbonic acid is an intermediate step in the transport of CO2 out of the body via respiratory gas exchange. The hydration reaction of CO2 is generally very slow in the absence of a catalyst, but red blood cells contain carbonic anhydrase which both increases the reaction rate and dissociates a hydrogen ion (H+) from the resulting carbonic acid, leaving bicarbonate (HCO3-) dissolved in the blood plasma. This catalysed reaction is reversed in the lungs, where it converts the bicarbonate back into CO2 and allows it to be expelled.
Carbonic acid also plays a very important role as a buffer in mammalian blood. The equilibrium between carbon dioxide and carbonic acid is very important for controlling the acidity of body fluids, and the carbonic anhydrase increases the reaction rate by a factor of nearly a billion to keep the fluids at a stable pH.
Role of carbonic acid in anthropogenic climate change
The oceans of the world have absorbed almost half of the CO2 emitted by humans from the burning of fossil fuels. The extra dissolved carbon dioxide has caused the ocean's average surface pH to shift by about 0.1 unit from pre-industrial levels. This process is known as ocean acidification.
Acidity of carbonic acid
Carbonic acid is diprotic: it has two hydrogen atoms which may dissociate from the parent molecule. Thus there are two dissociation constants, the first one for the dissociation into the bicarbonate (also called hydrogen carbonate) ion HCO3:
and the second for the dissociation of the bicarbonate ion into the carbonate ion CO32:
HCO3 CO32 + H+
Ka2 = 5.611011; pKa2 = 10.33 at 25 C and Ionic Strength = 0.0.(NIST CRITICAL Database)
Care must be taken when quoting and using the first dissociation constant of carbonic acid. The value given above is correct for the H2CO3 molecule, and shows that it is a stronger acid than acetic acid or formic acid. This is expected from the influence of the electronegative oxygen substituent. However, in aqueous solution carbonic acid only exists in equilibrium with carbon dioxide, and the concentration of H2CO3 there is much lower than the dissolved CO2 concentration, thus reducing the measured acidity. Since it is not possible to distinguish between H2CO3 and dissolved CO2 (referred to as CO2(aq)) by conventional methods, H2CO3* is used to represent the two species when writing the aqueous chemical equilibrium equation. The equation may be rewritten as follows (c.f. sulfurous acid):
H2CO3* HCO3 + H+
Ka = 4.30107; pKa = 6.352 at 25 C and Ionic Strength = 0.0.(NIST CRITICAL Database)
While this pKa is quoted as the dissociation constant of carbonic acid, it is ambiguous: it might better be referred to as the acidity constant of dissolved carbon dioxide, as it is particularly useful for calculating the pH of CO2-containing solutions.
pH and Composition of a Carbonic Acid Solution
At a given temperature, the composition of a pure carbonic acid solution (or of a pure CO2 solution) is completely determined by the partial pressure of carbon dioxide above the solution. To calculate this composition, account must be taken of the above equilibria between the three different carbonate forms (H2CO3, HCO3 and CO32) as well as of the hydration equilibrium between dissolved CO2 and H2CO3 with constant (see above) and of the following equilibrium between the dissolved CO2 and the gaseous CO2 above the solution:
CO2(gas) CO2(dissolved) with where kH=29.76 atm/(mol/L) at 25C (Henry constant)
The corresponding equilibrium equations together with the relation and the neutrality condition result in six equations for the six unknowns [CO2], [H2CO3], [H+], [OH, [HCO3 and [CO32, showing that the composition of the solution is fully determined by . The equation obtained for [H+] is a cubic whose numerical solution yields the following values for the pH and the different species concentrations:
(atm)
pH
[CO2] (mol/L)
[H2CO3] (mol/L)
[HCO3 (mol/L)
[CO32 (mol/L)
108
7.00
3.36 1010
5.71 1013
1.42 109
7.90 1013
106
6.81
3.36 108
5.71 1011
9.16 108
3.30 1011
104
5.92
3.36 106
5.71 109
1.19 106
5.57 1011
3.5 104
5.65
1.18 105
2.00 108
2.23 106
5.60 1011
103
5.42
3.36 105
5.71 108
3.78 106
5.61 1011
102
4.92
3.36 104
5.71 107
1.19 105
5.61 1011
101
4.42
3.36 103
5.71 106
3.78 105
5.61 1011
1
3.92
3.36 102
5.71 105
1.20 104
5.61 1011
2.5
3.72
8.40 102
1.43 104
1.89 104
5.61 1011
10
3.42
0.336
5.71 104
3.78 104
5.61 1011
We see that in the total range of pressure, the pH is always largely lower than pKa2 so that the CO32 concentration is always negligible with respect to HCO3 concentration. In fact CO32 plays no quantitative role in the present calculation (see remark below).
For vanishing , the pH is close to the one of pure water (pH = 7) and the dissolved carbon is essentially in the HCO3 form.
For normal atmospheric conditions ( atm), we get a slightly acid solution (pH = 5.7) and the dissolved carbon is now essentially in the CO2 form. From this pressure on, [OH becomes also negligible so that the ionized part of the solution is now an equimolar mixture of H+ and HCO3.
For a CO2 pressure typical of the one in soda drink bottles ( ~ 2.5 atm), we get a relatively acid medium (pH = 3.7) with a high concentration of dissolved CO2. These features contribute to the sour and sparkling taste of these drinks.
Between 2.5 and 10 atm, the pH crosses the pKa1 value (3.60) giving a dominant H2CO3 concentration (with respect to HCO3) at high pressures.
Remark: As noted above, [CO32 may be neglected for this specific problem, resulting in the following very precise analytical expression for [H+]:
Instability of carbonic acid
It has long been recognized that it is impossible to obtain pure carbonic acid at room temperatures (about 20 C or about 70 F). However, in 1991 scientists at NASA's Goddard Space Flight Center (USA) succeeded in making the first pure H2CO3 samples. They did so by exposing a frozen mixture of water and carbon dioxide to high-energy radiation, and then warming to remove the excess water. The carbonic acid that remained was characterized by infrared spectroscopy. The fact that the carbonic acid was prepared by irradiating a solid H2O + CO2 mixture has given rise to suggestions that H2CO3 might be found in outer space, where frozen ices of H2O and CO2 are common, as are cosmic rays and ultraviolet light, to help them react. The same carbonic acid polymorph (denoted beta-carbonic acid) was prepared by a cryotechnique at the University of Innsbruck: alternating layers of glassy aqueous solutions of bicarbonate and acid were heated in vacuo, which causes protonation of bicarbonate, and the solvent was subsequently removed. A second polymorph (denoted alpha-carbonic acid) was prepared by the same technique at the University of Innsbruck using methanol rather than water as a solvent.
It has since been shown, by theoretical calculations, that the presence of even a single molecule of water causes carbonic acid to revert to carbon dioxide and water fairly quickly. Pure carbonic acid is predicted to be stable in the gas phase, in the absence of water, with a calculated half-life of 180,000 years.
There is a hypothetical acid orthocarbonic acid which is even more hydrated, being H4CO4.
See also
Carbonated water
Ocean acidification
Carbon dioxide
References
Welch, M. J.; Lipton, J. F.; Seck, J. A. (1969). "Tracer studies with radioactive oxygen-15. Exchange between carbon dioxide and water". J. Phys. Chem. 73 (335): 3351. doi:10.1021/j100844a033.
Jolly, W. L. (1991). Modern Inorganic Chemistry (2nd Edn.). New York: McGraw-Hill. ISBN 0-07-112651-1.
Moore, M. H.; Khanna, R. (1991). "Infrared and Mass Spectral Studies of Proton Irradiated H2O+Co2 Ice: Evidence for Carbonic Acid Ice: Evidence for Carbonic Acid". Spectrochimica Acta 47A: 255262. doi:10.1016/0584-8539(91)80097-3.
Loerting, T.; Tautermann, C.; Kroemer, R.T.; Kohl, I.; Mayer, E.; Hallbrucker, A.; Liedl, K. R. (2001). "On the Surprising Kinetic Stability of Carbonic Acid". Angew. Chem. Int. Ed. 39: 891895. doi:10.1002/(SICI)1521-3773(20000303)39:53.0.CO;2-E.
W. Hage, K. R. Liedl; Mayer, E. (1998). "Carbonic Acid in the Gas Phase and Its Astrophysical Relevance". Science 279: 13321335. doi:10.1126/science.279.5355.1332. PMID 9478889.
Hage, W.; Hallbrucker, A.; Mayer, E. (1993). "Carbonic Acid: Synthesis by Protonation of Bicarbonate and Ftir Spectroscopic Characterization Via a New Cryogenic Technique". J. Am. Chem. Soc. 115: 84278431. doi:10.1021/ja00071a061.
Hage, W.; Hallbrucker, A.; Mayer, E. (1995). "A Polymorph of Carbonic Acid and Its Possible Astrophysical Relevance". J. Chem. Soc. Farad. Trans. 91: 28232826. doi:10.1039/ft9959102823.
References
^ Sabine, C.L.; et al. (2004). " "The Oceanic Sink for Anthropogenic CO2". Science 305 (5682): 367371. doi:10.1126/science.1097403. http://www.sciencemag.org/cgi/content/short/305/5682/367".
^ Infrared and mass spectral studies of proton irradiated H + CO ice: evidence for carbonic acid, by Moore, M. H.; Khanna, R. K.
External links
Ask a Scientist: Carbonic Acid Decomposition
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Carbonic acid/bicarbonate/carbonate equilibrium in water: pH of solutions, buffer capacity, titration and species distribution vs. pH computed with a free spreadsheet
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Oxocarbons
Common oxides
CO2 CO
Exotic oxides
C2O2 C3O2 C4O2 C5O2 C2O CO3 CO4
Compounds derived from oxides
Metal carbonyls Carbonic acid Bicarbonates Carbonates
Categories: Acids | Inorganic carbon compounds | CarbonatesHidden categories: All articles with unsourced statements | Articles with unsourced statements from October 2009
