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Spring 2007
Dr. S.A. Skrabal
SOLUTIONS TO PROBLEM SET 11
Polyprotic acid-base equilbria
24 April 2007
Please refer to Appendix G in your textbook for required values of Ka.
Note: I have expressed values of pH and pOH to only two decimal places for convenience.
1. Indicate whether an aqueous solution of the following compounds is acidic, neutral, or basic. Explain
your answer. (A) CH3CO2NH4 (ammonium acetate) (B) Na2C2O4 (disodium oxalate) (C) NaNO2 (sodium
nitrite) (D) Na2HPO4 (disodium hydrogen phosphate) (E) Na3PO4 (trisodium phosphate
(F) NaHC2O4 (sodium hydrogen oxalate)
(A) CH3CO2NH4 --> CH3CO2- + NH4+. CH3CO2- is a weak acid with Kb = Kw/Ka = 1.00 x 10-14/1.75 x 10-5 =
5.71 x 10-10 and NH4+ is a weak acid with Ka = 5.70 x 10-10. Values of K are essentially the same, so
substance should be essentially neutral (same tendency to act as acid as base). (B) Na2C2O4 dissolves
to give 2 Na+ + C2O42-; C2O42- is fully basic form of diprotic base, so will form basic solution. (C) NaNO2
dissolves to form Na+ + NO2-; NO2- is conjugate base to HNO2 (nitrous acid; Ka = 7.1 x 10-4), so solution
should be basic. (D) Na2HPO4 dissolves to form 2 Na+ + HPO42-, the second intermediate form of
H3PO4. Solutions of this intermediate form have pH (pKa2 + pKa3)/2 (7.199 + 12.15)/2 9.67, so
basic. (E) Na3PO4 dissolves to give 3 Na+ + PO43-, the fully basic form of H3PO4. This is weak base, so
basic. (F) NaHC2O4. This dissolves to give HC2O4-, the intermediate form of the diprotic acid, oxalic
acid. Solutions of intermediate forms have pH (pKa1 + pKa2)/2 (1.252 + 4.266)/2 2.759, so acidic.
2. Calculate the pH of a solution that is 0.0500 M in: (A) H3PO4 (B) H3PO3 (C) H2S (D) H2C2O4
(E) H2SO3
(A) 0.0500 M H3PO4 (phosphoric acid). Fully acidic form of triprotic weak acid. Ka1 = x2/(F x) = 7.11 x
10-3 = x2/(0.0500 x); x2 + 7.11 x 10-3x 3.56 x 10-4 = 0; x = [H3O+] = 1.56 x 10-2 M; pH = 1.81.
(B) 0.0500 M H3PO3 (phosphorous acid); Ka1 = 3.0 x 10-2 = x2/(0.0500 x); x2 + 3.0 x 10-2x 1.50 x 10-3
= 0; x = [H3O+] = 2.65 x 10-2 M; pH = 1.58 (C) 0.0500 M H2S (hydrogen sulfide);
Ka1 = 9.5 x 10-8 = x2/(0.0500 x); x2 + 9.5 x 10-8x 4.75 x 10-9 = 0; x = [H3O+} = 6.89 x 10-5 M; pH = 4.16.
(D) 0.0500 M H2C2O4 (oxalic acid); Ka1 = 5.60 x 10-2 = x2/(0.0500 x); x2 + 5.60 x 10-2 2.80 x 10-3 = 0;
x = [H3O+] = 3.19 x 10-2 M; pH = 1.50 (E) 0.0500 M H2SO3 (sulfurous acid); Ka1 = 1.23 x 10-2 = x2/
(0.0500 x); x2 + 1.23 x 10-2x 6.15 x 10-4 = 0; x = [H3O+] = 1.94 x 10-2 M; pH = 1.71.
3. Calculate the pH of a solution that is 0.0500 M in (A) NaH2PO4 (B) NaHC2O4 (C) NaH2PO3
(D) NaHSO3 (E) NaHS.
(A) [H3O+]
K a1 K a 2 F K a1 K w
=
K a1 F
or pH = (pKa1 + pKa2) / 2
(B) 0.0500 M NaHC2O4; HC2O4- is intermediate species (H2C2O4 is oxalic acid); same approach as
above:
[H3O+]
(5.60 x10 2 )(5.42 x10 5 )(0.0500) (5.60 x10 2 )(1.00 x10 14 )
1.197 x10 3 M ; pH 2.92
2
5.60 x10 0.0500
(C) 0.0500 M NaH2PO3; H2PO3- is amphiprotic species (H3PO3 is phosphorous acid); same approach as
above:
(3.0 x10 2 )(1.62 x10 7 )(0.0500) (3.0 x10 2 )(1.00 x10 14 )
5.511x10 5 M ; pH 4.26
3.0 x10 2 0.0500
(D) 0.0500 M NaHSO3; HSO3- is intermediate species (H2SO3 is sulfurous acid); same approach as
above:
4. Calculate the pH of a solution that is 0.0500 M in (A) Na3PO4 (B) Na2C2O4 (C) Na2HPO3
(D) Na2SO3 (E) Na2S
(A) 0.0500 M Na3PO4; PO43- is base; Kb1 = Kw/Ka3 = (1.00 x 10-14/7.1 x 10-13) = 1.41 x 10-2 = x2/(0.0500
x); x2 + 1.41 x 10-2x 7.05 x 10-4 = 0; x = [OH-] = 2.04 x 10-2 M; pOH = 1.69; pH = 12.31 (B) 0.0500 M
Na2C2O4; C2O42- is base; Kb1 = Kw/Ka2 = (1.00 x 10-14/5.42 x 10-5) = 1.85 x 10-10 = x2/(0.0500 x); x2 +
1.85 x 10-10x 9.25 x 10-12 = 0; x = [OH-] = 3.04 x 10-6 M; pOH = 5.52; pH = 8.48 (C) 0.0500 M
Na2HPO3; HPO32- is fully basic form of the diprotic acid, H3PO3, phosphorous acid. Kb1 = Kw/Ka2 = (1.00
x 10-14/1.62 x 10-7) = 6.17 x 10-8 = x2/(0.0500 x); x2 + 6.17 x 10-8x 3.08 x 10-9 = 0; x = [OH-] = 5.55 x
10-5 M; pOH = 4.26; pH = 9.74 (D) 0.0500 M Na2SO3; SO32- is fully basic form of H2SO3, sulfurous acid;
Kb1 = Kw/Ka2 = (1.00 x 10-14/6.6 x 10-8) = 1.52 x 10-7 = x2/(0.0500 x); x2 + 1.52 x 10-7x 7.60 x 10-9 = 0; x
= [OH-] = 8.71 x 10-5 M; pOH = 4.06; pH = 9.94
(E) 0.0500 M Na2S; S2- is fully basic form of H2S; Kb1 = Kw/Ka2 = (1.00 x 10-14/1.3 x 10-14) = 7.69 x 10-1 =
x2/(0.0500 x); x2 + 7.69 x 10-1x 3.84 x 10-2 = 0; x = [OH-] = 4.71 x 10-2 M; pOH = 1.33; pH = 12.67.
5. Calculate the pH of a solution that is made up to contain the following formal concentrations:
(A) 0.0400 M H3AsO4 and 0.0250 M NaH2AsO4 (B) 0.0500 M NaH2AsO4 and 0.0300 M Na2HAsO4
(C) 0.0300 M Na2CO3 and 0.0600 M NaHCO3 (D) 0.0500 M H3PO4 and 0.0200 M NaH2PO4
(E) 0.0600 M NaHSO4 and 0.0300 M Na2SO4
(A) pH = pKa1 + log ([H2AsO4-]/[H3AsO4] = 2.24 + log (0.0250/0.0400) = 2.04
(B) pH = pKa2 + log([HAsO42-]/[H2AsO4-] = 6.96 + log(0.0300/0.0500) = 6.74
K a1 K a 2 F K a1 K w
K a1 F
9.00 x10 7 M