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The pKb values for the dibasic base B are pKb1 = 2.10 and pKb2 = 7.77. Calculate

ID: 929122 • Letter: T

Question

The pKb values for the dibasic base B are pKb1 = 2.10 and pKb2 = 7.77. Calculate the pH at each of the following points in the titration of 50.0 mL of a 0.75 M B(aq) with 0.75 M HCl(aq).

(a) Since Kb1 >> Kb2, you can ignore the second ionization. However, you'll need to use either the quadratic equation or successive approximations to solve for [H ].

(b) 25.0 mL is half way to the first equivalence point, so pOH = pKb1.

(c) 50.0 mL is the first equivalence point. BH is amphoteric, so use pH = 1/2(pKa1 pKa2), where pKa = 14.00 – pKb.

(d) 75.0 mL is half way to the second equivalence point, so pOH = pKb2.

(e) 100.0 mL is the second equivalence point. The final product, BH22 , is a weak acid with Ka1 = Kw/Kb2.

PLEASE ANSWER ALL PARTS. THANK YOU!

Explanation / Answer

a)

B + H2O <----------------> BH+    + OH-

0.75                               0             0 -----------------> initial

0.75-x                              x             x -------------------> equilibrium

Kb1 = [BH+][OH-]/[B]

Kb1 = x^2 / 0.75 -x

7.94 x 10^-3 = x^2 / 0.75 -x

x = 0.0733

x = [OH-] = 0.0733 M

pOH = -log [0.0733 ]

pOH = 1.14

pH + pOH = 14

pH = 14-pOH

pH = 12.86

c) after addition of 50.0 ml :

this is first equivalence point. so here

pOH = pKb1 + pKb2 / 2

         = 2.1 + 7.77 / 2

         = 4.94

pH = 9.06

e) addition of 100 ml:

here acid salt remains

concentration of acid salt = 0.75 x 50 / total volume

                                         = 37.5 / (100+50)

                                         = 0.25

BH2+   -------------------> BH+ + H+

0.25                                  0          0

0.25-x                               x           x

Ka2 = [BH+][H+] / [BH2+]

5.89 x 10^-7 = x^2 / 0.25 - x

x = 3.83 x 10^-4

[H+] = 3.83 x 10^-4 M

pH = 3.42

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