Titration Calculations

Strong Acid/Strong Base Calculations

(1) Use balanced equation to do stoichiometric calculation.

(2) Determine pH from amount of strong acid/base that is in excess.
Note: At stoichiometry point of equal acid and base, pH =7.

Example:
What is pH after 0.0 mL, 10.0mL, at equivalence point, and 50.0 mL of base has been
added during a titration to 25.0 mL of a 0.12M HCl solution with 0.15M NaOH solution?

For strong acid/base titration, perform stoichiometry calculation first; then calculation
resulting concentration with total volume; finally, calculate pH directly.

(A) 0.0 mL base: Solution is 0.12M HCl pH = -log[H+] = -log(0.12) = 0.92

(B) 10.0mL added base:

HCl(aq) + NaOH(aq) -> H2O(l) + NaCl(aq)
(0.0250L)(0.12M) (0.0100L)(0.15M)
0.0030 mol 0.0015 mol 0
–0.0015 mol –0.0015 mol +0.0015 mol
0.0015 mol 0 0.0015 mol

[HCl] = 0.0015 mol/0.0350L = 0.043 M

Therefore since strong acid: [H+] = 0.043 M so pH = –log (0.043) = 1.37

(C) At Equivalence Point:

Volume of base added = (0.0030mol HCl)(1mol NaOH/1mol HCl)(1L/0.15mol NaOH)
= 0.020 L = 20. mL added base

Since NaCl does not hydrolyze water, pH is neutral 7.00.

(D) 50.0mL added base:

HCl(aq) + NaOH(aq) -> H2O(l) + NaCl(aq)
(0.0250L)(0.12M) (0.0500L)(0.15M)
0.0030 mol 0.0075 mol 0
–0.0030 mol –0.0030 mol +0.0030 mol
0 mol 0.0045 mol 0.0030 mol

[NaOH] = 0.0045 mol/0.0750L = 0.060 M

Therefore since strong base left: [OH–] = 0.060 M so pOH = –log (0.060) = 1.22
pH = 12.78
 Weak Acid/Strong Base Calculations

What is pH after 0.0 mL, 10.0mL, at equivalence point, and 50.0 mL of base has been
added during a titration to 25.0 mL of a 0.12M HF solution with 0.15M NaOH solution?
Ka = 6.8 x 10–4

(1) Use balanced equation to do stoichiometric calculation.

(2) Determine new concentrations by dividing by total volume.
(3) Use appropriate equilibrium reaction and ICE chart to determine pH.

Stoichiometric Reaction:
HF(aq) + NaOH(aq) -> H2O(l) + NaF(aq)

Equilibrium Reaction:
HF(aq) + H2O(l) -> H3O+(aq) + F–(aq)

(A) Addition of 0.0 mL of base:

Only weak acid present.

HF (aq) + H 2O  H3O+(aq) + F– (aq)

I 0.12 M 0 0
C -x +x +x
E 0.12 - x x x

[H 3O+ ][F− ] x2
Ka = 6.8x10−4 =
[HF] (0.12 − x)

x = 8.7 X 10–3 M pH = ‐log (8.7 X 10–3) = 2.06

€
 (B) What is pH after 10.0mL of 0.15M NaOH solution has been added to
25.0 mL of 0.12M HF solution? Ka = 6.8 x 10–4

(1) Use balanced equation to do stoichiometric calculation.

(2) Determine new concentrations by dividing by total volume.
(3) Use appropriate equilibrium reaction and ICE chart to determine pH.

(1) Stoichiometric Reaction:

HF(aq) + NaOH(aq) -> H2O(l) + NaF(aq)

(0.0250L)(0.12M) (0.0100L)(0.15M)
0.0030 mol 0.0015 mol 0
–0.0015 mol –0.0015 mol +0.0015 mol
0.0015 mol 0 mol 0.0015 mol

(2) New concentrations:

[HF] = 0.0015 mol/ 0.0350L = 0.043M

[F–] = 0.0015 mol/ 0.0350L = 0.043M

(3) Equilibrium Reaction:

HF (aq) + H 2O  H3O+(aq) + F– (aq)

I 0.043M 0 0.043M
C -x +x +x
E 0.043 - x x 0.043 + x

[H 3O+ ][F− ] (x (0.43 + x))

Ka = 6.8x10−4 =
[HF] (0.43 − x)

x = 6.8 x 10–4 M pH = ‐log (6.8 x 10–4) = 3.17

€
Note: Could also use Henderson‐Hasselbalch equation since this is buffer region of
titration curve.
 (C) What is pH at equivalence point?

First need to determine volume at equivalence point.

 0.12mol HF 1mol NaOH  1L 

(0.0250 L )    = 0.0200 L or 20.0 mL
 1L  1mol HF  0.15mol NaOH 

(1) Use balanced equation to do stoichiometric calculation.

€ (2) Determine new concentrations by dividing by total volume.
(3) Use appropriate equilibrium reaction and ICE chart to determine pH.

(1) Stoichiometric Reaction:

HF(aq) + NaOH(aq) -> H2O(l) + NaF(aq)

(0.0250L)(0.12M) (0.0200L)(0.15M)
0.0030 mol 0.0030 mol 0
– 0.0030 mol – 0.0030 mol + 0.0030 mol
0 0 0.0030 mol

(2) New concentrations:

[HF] = 0 mol/0.0450L = 0 M

1x10−14
[F–] = 0.0030 mol/0.0450L = 0.067 M Kb = −4
= 1.5x10−11
6.8x10

(3) Equilibrium Reaction:

€
Only conjugate base now left. So must use equilibrium reaction for conjugate base and
calculate Kb.

F– (aq) + H 2O  OH–(aq) + HF (aq)

I 0.067 M 0 0
C -x +x +x
E 0.067 - x x x

[OH− ][HF] x2
Kb = 1.5x10 –11 =
[F – ] (0.067 − x)

x = 1.0 x 10–6 M pOH = ‐log (1.0 x 10–6) = 6.00 so pH = 8.00

€
 (D) What is pH after 50.0mL of 0.15M NaOH solution has been added to
25.0 mL of 0.12M HF solution? Ka = 6.8 x 10–4

(1) Use balanced equation to do stoichiometric calculation.

(2) Determine new concentrations by dividing by total volume.
(3) Use appropriate equilibrium reaction and ICE chart to determine pH.

(1) Stoichiometric Reaction:

HF(aq) + NaOH(aq) -> H2O(l) + NaF(aq)
(0.0250L)(0.12M) (0.0500L)(0.15M)
0.0030 mol 0.0075 mol 0
– 0.0030 mol – 0.0030 mol + 0.0030 mol
0 0.0045 mol 0.0030 mol

(2) New concentrations:

[OH-] = 0.0045 mol/0.0750L = 0.060 M

1x10−14
[F-] = 0.0030 mol/0.0750L = 0.040 M Kb = −4
= 1.5x10−11
6.8x10

(3) Equilibrium Reaction:

€
F– (aq) + H 2O  OH–(aq) + HF (aq)
I 0.040 M 0.060 M 0
C -x +x +x
E 0.040 - x 0.060 + x x

[OH− ][HF] (x (0.060 + x))

Kb = –
1.5x10 –11 =
[F ] (0.040 − x)

x = 1.0 x 10–11 M pOH = ‐log (1.0 x 10–11) = 11.00 so pH = 3.00 ???

€
NOTE: “x” is NOT the OH- concentration. The OH- concentration is 0.060M +x.
Since there is excess strong base in this last addition, the pH is determined by the
strong base concentration. The weak conjugate base F- adds an insignificant
amount.

[OH–] = 0.060 + x = 0.060 M + 1.0 x 10–11 M = 0.060 M

pOH = –log (0.060) = 1.22 so pH = 12.78