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Reaction: 2CrO4 + 2H+ <--> Cr2O72- + H2O

The following absorbance data were obtained for a 2 x 10-4M solution of K2Cr2O7 in H2SO4 and NaOH. Measurement were made at wavelengths of 348nm and 372 nm, with 1cm cells.

K2Cr2O7 (2mL) + H2SO4 (0.2mL): A(348) =0.466, A(372) = 0.298


K2Cr2O7(2mL) + H2O(7.5mL) + NaOH(0.5mL):  A(348) = 0.197, A(372) = 0.372


In the H2SO4 solution, most of the chromium are in the dichromate form (Cr2O7), and the concentration of the solution is about 1.8 x 10-4M.

In the NaOH solution, all of the chromium are in the chromate form, and the concentration of the solution = 8 x 10-5M.

Questions

a) Find the molar absorptivities for CrO4 and Cr2O7 at 348nm, and 372nm.

b)
i) Calculate the equilibrium constant for the reaction, if a 5mL of pH 4.5 buffer containing 5mL of 2x10-4M KCr2O7 exhibits an absorbance of 0.314 at 348nm, and 0.222 at 372nm. (1cm cells).

ii) Calculate the equilibrium constant at pH 5.5, and 5.8.
pH 5.5: A(348) = 0.359, A(372) = 0.381
pH 5.8: A(348) = 0.382, A(372) = 0.468


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