Carbon dioxide dissolved in water is in equilibrium with carbonic acid:
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 disassociates 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.
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 might be 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 CO2 concentration, reducing the measured acidity. The equation may be rewritten as follows (c.f. sulfurous acid):
This figure is quoted as the dissociation constant of carbonic acid, although this is ambiguous: it might better be referred to as the acidity constant of carbon dioxide, as it is particularly useful for calculating the pH of CO2 solutions.
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)|
|10−8||7.00||3.36 × 10-10||5.71 × 10−13||1.42 × 10−9||7.90 × 10−13|
|10−6||6.81||3.36 × 10−8||5.71 × 10−11||9.16 × 10−8||3.30 × 10−11|
|10−4||5.92||3.36 × 10−6||5.71 × 10−9||1.19 × 10−6||5.57 × 10−11|
|3.5 × 10−4||5.65||1.18 × 10−5||2.00 × 10−8||2.23 × 10−6||5.60 × 10−11|
|10−3||5.42||3.36 × 10−5||5.71 × 10−8||3.78 × 10−6||5.61 × 10−11|
|10−2||4.92||3.36 × 10−4||5.71 × 10−7||1.19 × 10−5||5.61 × 10−11|
|10−1||4.42||3.36 × 10−3||5.71 × 10−6||3.78 × 10−5||5.61 × 10−11|
|1||3.92||3.36 × 10−2||5.71 × 10−5||1.20 × 10−4||5.61 × 10−11|
|2.5||3.72||8.40 × 10−2||1.43 × 10−4||1.89 × 10−4||5.61 × 10−11|
|10||3.42||0.336||5.71 × 10−4||3.78 × 10−4||5.61 × 10−11|
Remark: As noted above, [CO32−] may be neglected for this specific problem, resulting in the following very precise analytical expression for [H+]:
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.
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