Chm 310 Problem Set 2 1.

. Carbon in the Oceans (14 points) In class, we showed that the pH of the ocean is 8.2 assuming that it is at equilibrium with both atmospheric CO2 and calcium carbonate. We also qualitatively discussed the nature of the acid-base buffering provided by carbonate/bicarbonate. In this problem you are asked to quantitatively calculate the fraction of CO2 in the atmosphere/ocean system that would reside in the atmosphere at equilibrium (where we are forgetting about the biosphere for now). i. Using the equilibria expressions used in class, demonstrate that: [TCO2(aq)] = KH PCO2 (1 + Ka1/[H+] + Ka1Ka2/[H+]2) where [TCO2(aq)] is concentration of dissolved inorganic carbon (i.e. carbonic acid, bicarbonate and carbonate). The other terms are as used in class. ii. As a function of [H+] (and some constants), derive an expression for the fraction of carbon dioxide (F) that will reside in the atmosphere, when at equilibrium with the ocean. To do this, write an expression for the number of moles of CO2 in the atmosphere that includes the partial pressure of CO2 in the atmosphere and the number of moles of air in the atmosphere, and then write an expression for the number of moles of CO2 dissolved in the ocean using the expression in i. Using your favorite plotting program, plot F as a function of pH. What is the value of this fraction for our present ocean at pH = 8.2? Useful information: The number of moles of air in the atmosphere is 1.8x1020 and volume of the oceans is 1.4x1018 m3. Ka1 = 9.0 x10-7, Ka2 = 7.2 x10-10, KH = 3.0x10-2 M/atm. Keep track of your units! You should have shown that about 3% of total CO2 will reside in the atmosphere and the rest is in the oceans (dont worry if you dont get this number just keep going). But, in reality, models and observations indicate say that only about 30% of fossil fuel CO2 is presently going into the ocean, or will do so in the near future. Give three reasons why the true value is larger than the value you calculated.

iii. iv.

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2. Carbon on the Land (6 points) To the right is an expanded carbon cycle for the terrestrial biosphere (credit: Jacob. 1999, units are as in class). i. Calculate the lifetime of carbon in the soil. ii. In the context of your answer to i., describe the merits of no-till planting in a sentence or two (no more). iii. Calculate the lifetime of carbon in all the forms of vegetation relative to loss to the litter (e.g. dead eaves) and soil. iv. What fraction of litter makes its way into the soil?