Acid-Base Titration

Titration of Strong Acid with Strong Base

50.00 mL of 0.0200 M KOH with 0.1000 M HBr

H+ + OH- → H2O k = 1/Kw = 1 x 1014

Ve (0.1000 M) = 50.00 mL (0.02000 M)

Ve = 10.00 mL

Region 1 – Before the equivalence point, e.g. 3 mL HBr

50mL(0.02mmol OH-) – 3mL(0.10mmol H+) = 0.0132 M

-
[OH ] = ( mL ) ( mL )
(50mL + 3mL)

[H+] = Kw = 1 x 10-14 = 7.58 x 10-13 → pH = 12.12

[OH-] 0.0132

Region 2 – at the equivalence point

H2O ↔ H+ + OH-
X x

Kw = x2 x = 1 x 10-3 M → pH = 7.00 (at 25oC for any strong acid vs strong base)

Region 3 – after the equivalence point e.g. 10.50 mL

- pH is determined with excess H+

[H+] = (0.1000)( 0.50 ) = 8.26 x 10-4 M pH = 3.08

(50 + 10.5)

Titration of Weak Acid with Strong Base

50.00 mL of 0.0200 M HA with 0.1000 M NaOH pKa = 6.15

HA + OH- → A- + H2O Ka = 7.08 x 10-7 Kb = 1.43 x 10-8

Ve(0.1000 M) = 50.00(0.0200 M)

Ve = 10.00 mL

Region 1 – before base is added

HA ↔ H+ + A- Ka = 7.08 x 10-7
M-x x x

x2 = Ka x = 1.19 x 10-4(QE) pH = 3.93

M-x without QE, x = 1.19 x 10-4 M (same)
Region 2 – before equivalence point e.g. V = 3.0 mL
- once OH is added, a mixture of HA and A- is created. Thus, the mixture is a buffer and
-

Henderson-Hasselbalch equation can be used to solve for pH.

HA + OH- → A- + H2O

50mL(0.02mmol OH-) – 3mL(0.10mmol H+) = 0.0132 M

[HA] = ( mL ) ( mL )
(50mL + 3mL)
3mL(0.10mmol OH-)
[A-] = ( mL ) = 5.66 x 10-3 M
(50mL + 3mL)

pH = pKa + log [A-] = 6.15 + log (5.66 x 10-3 M) = 5.78

[HA] (0 0312M)

The point at which the volume of titrant is ½ Ve in any titration is

HA + OH- → A- + H2O
Initial 1 ½ --- ---
Final ½ --- ½ ---

pH = pKa + log (1/2) = pKa

(1/2)

When the volume of titrant is ½ Ve, pH = pKa for the acid HA. If you have an experimental
titration curve, you can find the approximate value of pKa by reading pH at ½ Ve (to find the
true value of pKa requires activity coefficient)

Region 3 – at the equivalence point

HA + OH- → A- + H2O
Initial 1 1 --- ---
Final --- --- 1 ---

The resulting solution contains only “just A-“

We could have the same solution by dissolving salt Na+A- in distilled water. A solution of
Na+A- is merely a solution of a weak base.

A- + H2O → HA + OH- Kb = Kw/Ka

M-x x x

The molar concentration of A- is no longer 0.0200 M because it is diluted by NaOH.

M’ = 0.0200 M(50.00 ) = 0.0167 M

(50.00 + 10.00)

x2 = Kb = Kw = 1.43 x 10-8 x = 1.54 x 10-5 M = [OH-] pH = 9.18

M’-x Ka
 pH at equivalence point is 9.18 and not 7.00. The equivalence point pH will always be above
7 for titration of a weak acid because the acid is converted to its conjugate base at the equivalence
point.

Region 4 – after the equivalence point

- The base NaOH is much stronger than base A- that it can be approximated by the excess
OH-

[OH-] = 0.1000(____0.10 ) = 1.66 x 10-4 M pH = 10.22

(50.00 + 10.00)

Titration of Weak Base with Strong Acid

B + H+ → BH+

Regions

1. Before Acid is Added

B + H2O ↔ BH+ + OH- Kb

M-x x x

x2 = Kb pH = -log Kw
M-x x

2. Before the Equivalence Point (buffer)

pH = pKa (for BH+ ) + log [B]

[BH+]

3. At the Equivalence Point, B has converted to BH+, a weak acid.

BH+ ↔ B + H+ Ka
M’ –x x x
pH at the equivalence point must be below 7.00

4. After the Equivalence Point. The excess strong acid determines the pH.

Titration of Weak Base with Strong acid (Sample Problem)

50.00 mL of 0.050 M NaCN with 0.1000 M HCl

Ve (0.1000) = 0.0500 (50 mL) Ve = 25.00 mL

V = 0.00 mL (before acid is added)

CN- + H2O → HCN + OH- Ka = 6.2 x 10-10 Kb = 1.61 x 10-5

M-x x x
 x2 = Kb
M-x

x2 = (1.61 x 10-5)(0.05 –x) [H3O+] = 1.12 x 10-11 M pH = 10.95

x2 + 1.61 x 10-5 x + 8.05 x 10-7

x = 8.89 x 10-4 M if QE is not used: 1.11 x 10-11 M pH = 10.95

V = 10.00 mL (before equivalence point)

CN- + H+ → HCN

50mL(0.02mmol OH-) – 3mL(0.10mmol H+)

-
[CN ] = ( mL ) ( mL )
(50mL + 10mL)

[H+] = 10mL (0.10 mmol H+) = 0.01667 M

( mL )

pH = pKa + log 0.025 = 9.38

0.01667

V = 25 mL (Ve)

HCN + H2O ↔ H3O+ + CN- Ka = 6.2 x 10-10

M-x x x

M’ = 0.05 (50 ) = 0.033 M

(50 + 25)

x2 = Ka x2 =(6.2 x 10-10)(M-x)
M-x x = 4.546 x 10-6 M = [H3O+] pH = 5.34

V = 26.0 mL

[H3O+] = 0.1000 (1 ) = 1.316 x 10-3 M pH = 2.88

(50 + 26)

Titrations in Diprotic System

Titration of 10.00 mL base with 0.1000 M HCl pKb1 = 4.0

pKB2 = 9.0
B + H+ → BH+

BH+ + H+ → BH22+

Ve(0.1000 M) = 10.00 mL(0.1000 M)

Ve = 10.00 mL
Volume at the 2nd equivalence point = 2 Ve = 20.00 mL because the second reaction requires
exactly the same number of moles of HCl as the first reaction.

V= 0
1. Before any acid is added

B + H2O → BH+ + OH- Kb = 1 x 10-4

M-x x x

x2 = 1 x 10-4 x = 3.11 x 10-3 M = [OH-] pH = 11.49

M-x without quadratic equation: 3.16 x 10-3 M pH = 11.50

2. a) Before the first equivalence point V = 5.00 mL (buffer containing B and BH+)

pH = pK1 + log [B] = 10.00 + log 1 = 10.00

[BH+]

b) If V = 1.5,
10mL(0.10mmol OH-) – 1.5mL(0.10mmol H+) = 0.0739 M
2-
[A ] = ( mL ) ( mL )
(10mL + 1.5mL)
3mL(0.10mmol OH-)
[HA] = 1.5mL ( 0.10mmol HA ) = 0.013 M pH = 10.75
( mL )
3. At the first equivalence point

B has been converted to BH+, the intermediate form of BH22+

_____________
[H+] = /K1K2M + K1Kw
√ K1 + M

M = 0.1000 M (10.00) = 0.05000 M

(20.00)
__________________________________________
[H+] = /(1 x 10-5)(1 x 10-10)(0.0500M) + (1 x 10-5)(1 x 10-14)
√ (1 x 10-5) + 0.0500

= 3.16 x 10-8 M pH = 7.50

4. Before the second equivalence point V = 15.00 mL

Buffer containing BH+ and BH22+

pH = pK1 + log [BH+] = 5.00 + log 1 = 5.00

[BH22+]

5. At the second equivalence point V = 20.00 mL

M’’ = 0.1000 M (10.00) = 0.0333 M

(30.00)

BH22+ ↔ BH+ + H+ Ka1 = Kw

Kb2
 x2 = 1 x 10-5 M x = 5.72 x 10-4 M pH = 3.24
0.0333-x without quadratic equation x = 5.77 x 10-4 M pH = 3.24

6. Beyond the second equivalence point

The pH of the solution can be calculated from the strong acid added to the solution.
e.g. at 25.00 mL, therefore there is 5.00 mL excess HCl

[H+]= 0.1000 (5.00 ) = 1.43 x 10-2 M pH = 1.85

(10.00 + 25.00)

Acid-Base titration Curve

Sample Problems

Titration of Strong Acid with Strong Base (Sample Problem)

50.00 mL of 0.0500 M HCl with 0.1000 M NaOH

Ve (0.1000) = 50.00 (0.0500M) Ve =25mL

Region 1: V= 10.00 mL

50mL(0.05mmol OH-) – 10mL(0.10mmol H+)

[A2-] = ( mL ) ( mL ) = 0.025M
(50mL + 10mL)

Region 2: at the equivalence point

Kw = x2 = 1 x 10-14
 x = 1 x 10-7 M pH = 7.00

Region 3: V = 25.10 mL

[OH-] = 0.10 (0.10 ) = 1.33 x 10-4M

(50 + 25.10)

[H3O+] = Kw = 7.51 x 10-11 M pH = 10.12

[OH-]

Titration of Weak Acid with Strong Base

50.00 mL 0.1000 M HAc with 0.1000 M NaOH Ka = 1.75 x 10-5

Ve (0.1000)= 50.00 (0.1000M) Ve = 50.00 mL

V= 10.00 mL (before the equivalence point)

HA + OH- → A- + H2O

50mL(0.10mmol OH-) – 10mL(0.10mmol H+)

[HA] = ( mL ) ( mL ) = 0.0667M
(50mL + 10mL)

[A-] = 10mL ( 0.10mmol HA ) = 0.01667 M

( mL )

pH = pKa + log (0.01667 M) = 4.15

( 0.0667 M )

Ve = 50.00 mL

A- + H2O → HA + OH- Kb = Kw = 5.71 x 10-10

M-x x x 1.75 x 10-5

M’ = 0.10 (50 ) = 0.050 M

(50 + 50)

x2 = 5.71 x 10-10
M’-x

x2 = 5.71 x 10-10 (0.05 – x)

x2 + 5.71 x 10-10 x – 2.855 x 10-11 = 0

[OH-] = x = 5.34 x 10-6 M (QE) if no quadratic equation: x = 5.34 x 10-6 M

[H3O+] = Kw = 1.87 x 10-9M pH = 8.73

[OH-]
V = 50.10 (after the equivalence point)

[OH-] = 0.10 (0.10 ) = 9.99 x 10-5 M

(50 + 50.10)

[H3O+] = Kw = 1.001 x 10-10M pH = 10.00

[OH-]

Diprotic Acid vs Strong Base

Consider titration of 50.0 mL of 0..050 M malonic acid (diprotic acid) with 0.1000 M NaOH

Ve = 25 mL

H2A + H2O → HA- + H3O+ Ka1 = 1.42 x 10-3 pK1 = 2.848

Ka2 = 2.01 x 10-6 pK2 = 5.697

V= 0.00 mL (use quadratic equation)

x = 7.75 x 10-3 M pH = 2.11

V = 8.00 mL

H2A + OH- ↔ HA- + H2O

50mL(0.05mmol H2A) – 8mL(0.10mmol H+)

[H2A] = ( mL ) ( mL ) = 0.0293M
(50mL + 8mL)

[HA] = 8mL ( 0.10mmol OH- ) = 0.0138 M

( 50mL + 8mL )

pH = pK1 + log 0.0138/0.0293 = 2.52

V = 12.5 (halfway the equivalence point) pH = pK1 = 2.85

V = 19.3

50mL(0.05mmol H2A) – 19.3mL(0.10mmol H+)

[H2A] = ( mL ) ( mL ) = 8.225 x 10-3 M
(50mL + 19.3mL)

[HA] = 19.3mL ( 0.10mmol OH- ) = 0.0278 M

( 50mL + 19.3mL )

pH = pK1 + log 0.0278M/8.225 x 10-3 M = 3.38

at 25.00 mL(first equivalence point) H2A has been converted to HA-

 M’ = 0.050 (50 ) = 0.033M
(50+25)
_______________
H+] = /K1K2 (M’) + K1Kw = 5.23 x 10-5 M pH = 4.28
√ K1 + M’

V = 37.5 mL (3/2 Ve) pH = pK2 = 5.70

V = 50.0 mL

M2- + H2O ↔ HM- + OH- Kb1 = Kw = 4.975 x 10-5

M’’-x x x Ka3

M” = 0.050 (50 ) = 0.025 M

(50 + 50)

x2 = 4.975 x 10-5 M x = 1.12 x 10-5 M = OH- pH = 9.05

0.025-x

V = 56.3 mL

[OH-] = (6.3 ) (0.10) = 5.93 x 10-3 M pH = 11.77

(50 + 56.3)

Application of Acid-Base Titration

Kjeldahl Nitrogen analysis – one of the most accurate and widely-used methods for the determining
nitrogen in substances such as milk, cereal, and flour. The solid is first digested
(decomposed and dissolved) in boiling sulfuric acid which converts nitrogen to ammonium
ions, oxides, and other elements present.
boiling
Organic matter (C, H, N) → NH4+ + CO2 + H2O
H2SO4

Mercury, copper and selenium compounds catalyze the digestion process. To speed up the
rate of reaction, the boiling point of concentrated H2SO4 is raised by adding K2SO4. Digestion is
carried out in a long neck Kjeldahl flask that prevents loss of sample by spattering.

After digestion, the solution containing NH4+ is made basic, and the liberated NH3 is
distilled into a receiver containg a known amount of HCl. Excess unreacted HCl is then titrated with
standard NaOH to determine how much HCl was consumed by NH3.

Neutralization of NH4+ : NH4+ + OH- → NH3 + H2O

Distillation of NH3 into standard HCl: NH3 + H+ → NH4+
Titration of unreacted HCl w/ NaOH: H+ + OH- → H2O

Sample problem:

A typical protein contains 16.2 wt% of nitrogen. A 0.500 mL aliquot of protein solution was
digested, and the liberated NH3 was distilled into 10 mL of 0.02140 M HCl. The unreacted HCl
required 3.26 mL of 0.0198M NaOH for complete titration. Find the concentration of protein in the
original sample in mg/mL.

mmol NH3 = mmol HCl - mmol NaOH

mmol HCl = 10.00 (0.02140 mmol/mL) = 0.2140 mmol

NaOH required for titration of unreacted HCl

= 3.26 mL(0.0198mmol/mL) = 0.0645 mmol

mmol NH3 = 0.1495

Mass N = 0.1495 mmol NH3 (1 mmol N ) (14 mg ) = 2.093 mg

(1 mmol NH3 )(1mmol N)

mg/mL N = 2.093 mg (1 )(1 ) = 25.8 mg/mL or 25.8 mg/mL protein

(0.162)(0.50mL)

Analysis of Mixtures

In titrimetric analysis, the method is not limited to using only a single indicator. Analyses
involving the use of two indicators may also be performed. The analysis involves two (2) endpoints
in a single titration. The double indicator method is employed to determine the proportions of the
components of certain mixtures. The volumes of titration solution required for the respective
endpoints give a direct measure of the amounts of substance present. One application of this
double indicator method of titration is in the analysis of carbonate mixtures.

Substance Relation for qualitative Millimoles of substance

identification present
NaOH V2 = 0 M x V1
Na2CO3 V1 = V2 M x V1 x 2
NaHCO3 V1 = 0 M x V2
NaOH + Na2CO3 V1 > V2 NaOH: M(V1 - V2)
Na2CO3: M x V2 x 2
NaHCO3 + Na2CO3 V1 < V2 NaHCO3: M(V2 - V1)
Na2CO3: M x V1 x 2

Sample Problems

1. A 1.2000 g sample mixture of NaOH and Na2CO3 containing inert impurities is dissolved and
titrated cold with 0.5000 N HCl. With phenolphthalein as indicator, the solution turns
colorless after the addition of 30.00 mL of the acid. Methyl orange is then added, and 5.00
mL more of the acid is required before this indicator changes color. What is the percentage
of NaOH and Na2CO3 in the sample?
2. A 1.2000 g sample of impure mixture of Na2CO3 and NaHCO3 containing only inert
impurities is dissolved and titrated cold with 0.5000 N HCl. With phenolphthalein as
indicator, the solution turns colorless after the addition of 15.00 mL of the acid. Methyl
orange is then added, and 22.00 mL more of the acid is required to change the color of this
indicator. What is the %Na2CO3 and of %NaHCO3 in the sample?

3. A solution contains NaHCO3, Na2CO3 and NaOH. Titration of 50.00 mL to a phenolphthalein

endpoint requires 48.40 mL HCl with bromocresol green (BCG) endpoint. Calculate the
molar solute concentration of the original solution.

4. A sample of material contains for its active components, NaOH, Na2CO3, NaHCO3 or
compatible mixtures of these. Two samples each weighing 1.0000 g are dissolved in water.
To one sample , phenolphthalein is added and the solution is titrated cold with 1.038 N acid
of which 17.96 mL is required. The other sample is titrated cold, with methyl orange as
indicator and 21.17 mL of the same acid is required. What alkalis are present and what is
the percentage of each in the original solution?

5. Analysis of mixture consisting of NaOH + Na2CO3 + inert matter gives the following data:
sample = 10 g. Its aqueous solution is diluted to 250 mL and two separate 25.00 mL portions
are titrated. With one portion, an endpoint with phenolphthalein is obtained in cold
solution with 4.52 mL of 0.5000N HCl. The other portion requires 46.53 mL of the acid for
an endpoint with methyl orange. Calculate the % composition of the original sample.

6. A 300.3 mg sample containing Na2CO3, NaHCO3 and NaOH and inert material either alone or
in some combination, was dissolved and titrated with 0.1000 M HCl. The titration required
24.41 mL to reach the phenolphthalein endpoint and an additional 8.67 mL to reach the
methyl orange endpoint. Determine the composition of the sample and calculate the % of
each titrated component.