A 27.9 mL sample of 0.289 M dimethylamine, (CH3)2NH, is titrated with 0.286 M hydrobromic acid. (1) Before the addition of any hydrobromic acid, the pH is.
(2) After adding 12.0 mL of hydrobromic acid, the pH is.
(3) At the titration midpoint, the pH is.
(4) At the equivalence point, the pH is.
(5) After adding 45.1 mL of hydrobromic acid, the pH is.

(1) Before the addition of any HBr, the pH is 12.02

(2) After adding 12.0 mL of HBr, the pH is 10.86

(3) At the titration midpoint, the pH is 10.73

(4) At the equivalence point, the pH is 5.79

(5) After adding 45.1 mL of HBr, the pH is 1.18

Explanation:

First of all, we have a weak base:

(CH₃)₂NH  + H₂O  ⇄  (CH₃)₂NH₂⁺  +  OH⁻            Kb = 5.4×10⁻⁴

0.289 - x                             x                x

Kb = x² / 0.289-x

Kb . 0.289 - Kbx - x²

1.56×10⁻⁴ - 5.4×10⁻⁴x - x²

After the quadratic equation is solved x = 0.01222 → [OH⁻]

- log  [OH⁻] = pOH → 1.91

pH = 12.02   (14 - pOH)

We determine the mmoles of H⁺, we add:

0.286 M . 12 mL = 3.432 mmol

We determine the mmoles of base⁻, we have

27.9 mL . 0.289 M = 8.0631 mmol

When the base, react to the protons, we have the protonated base plus water (neutralization reaction)

(CH₃)₂NH     +      H₃O⁺        ⇄  (CH₃)₂NH₂⁺  +  H₂O

8.0631 mm       3.432 mm                 -

4.6311 mm                                  3.432 mm

We substract to the dimethylamine mmoles, the protons which are the same amount of protonated base.

[(CH₃)₂NH] → 4.6311 mm / Total volume (27.9 mL + 12 mL) = 0.116 M

[(CH₃)₂NH₂⁺] → 3.432 mm / 39.9 mL = 0.0860 M

We have just made a buffer.

pH = pKa + log (CH₃)₂NH  / (CH₃)₂NH₂⁺

pH = 10.73 + log (0.116/0.0860) = 10.86

mmoles of base = mmoles of acid

Let's find out the volume

0.289 M . 27.9 mL = 0.286 M . volume

volume in Eq. point = 28.2 mL

(CH₃)₂NH     +      H₃O⁺        ⇄  (CH₃)₂NH₂⁺  +  H₂O

8.0631 mm       8.0631mm               -

                                                8.0631 mm

We do not have base and protons, we only have the conjugate acid

We calculate the new concentration:

mmoles of conjugated acid / Total volume (initial + eq. point)

[(CH₃)₂NH₂⁺] = 8.0631 mm /(27.9 mL + 28.2 mL)  = 0.144 M

(CH₃)₂NH₂⁺   +  H₂O   ⇄   (CH₃)₂NH  +  H₃O⁻       Ka = 1.85×10⁻¹¹

 0.144 - x                                  x               x

[H₃O⁺] = √ (Ka . 0.144) →  1.63×10⁻⁶ M  

pH = - log [H₃O⁺] = 5.79

This is the point where we add, the half of acid. (14.1 mL)

This is still a buffer area.

mmoles of H₃O⁺ = 4.0326 mmol (0.286M . 14.1mL)

mmoles of base = 8.0631 mmol - 4.0326 mmol

[(CH₃)₂NH] = 4.0305 mm / (27.9 mL + 14.1 mL) = 0.096 M

[(CH₃)₂NH₂⁺] = 4.0326 mm (27.9 mL + 14.1 mL) = 0.096 M

pH = pKa + log (0.096M / 0.096 M)

pH = 10.73 + log 1 =  10.73

Both concentrations are the same, so pH = pKa. This is the  maximum buffering capacity.

mmoles of acid = 45.1 mL . 0.286 M = 12.8986 mmol

mmoles of base = 8.0631 mmoles

This is an excess of H⁺, so, the new [H⁺] = 12.8986 - 8.0631 / Total vol.

(CH₃)₂NH     +      H₃O⁺        ⇄  (CH₃)₂NH₂⁺  +  H₂O

8.0631 mm     12.8986 mm             -

       -               4.8355 mm                        

[H₃O⁺] = 4.8355 mm / (27.9 ml + 45.1 ml)

[H₃O⁺] = 4.8355 mm / 73 mL → 0.0662 M

- log [H₃O⁺] = pH

- log 0.0662 = 1.18 → pH

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