Solving Acid-Base Titration Problems

Definition: The end point is when stoichiometric equivalent amounts of base and acid have combined.
There are 4 different stages of titration and they are defined as follows:
1. At the start
2. After the start, but before the equivalence point
3. At the equivalence point
4. After the equivalence point
There are also 3 conditions of reactions that must be considered:
1. Strong acid and strong base
2. Weak acid and strong base
3. Strong acid and weak base
Solutions of these stages and conditions require different approaches as follows:
A. Strong Acids and Strong Bases
Strong acids and strong bases dissociate 100%. Therefore, the pH will be directly related to
the concentration of the excess reactant in the adjusted solution volume. At the equivalence
point, where both reactants have equal moles, the pH equals 7. If the initial solution is a strong
acid, the pH will be acidic and become less acidic as base is added. When the equivalence point is
reached the pH will be 7 and will continue to rise as base is added.
1. To determine the initial pH, before any titrant has been added, one knows that the pH of 25
mL of a solution will be directly calculated with the concentration of acid or base (e.g.) 0.200
m HCl = [H] = 0.200 m. pH = -log(0.200) = 0.7
2. After the start, but before equivalence point, find the concentration of the excess reactant by
first calculating amount of HCl initially present in 25 mL of HCl.
25 mL HCl x 0.200 m HCl
1000 mL HCl solution = 5x10-3 moles HCl
Next add 10 mL of 0.20 m of NaOH.
Moles of NaOH added equals: 10 mL NaOH x 0.200 m NaOH = 2 x 10-3 mol NaOH
1000 mL
Subtract the moles of the smaller amount of acid or base from the larger number. This will represent
the excess acid or base and the amount of that excess.
In this example, subtract the moles of NaOH (2 x 10-3) from the moles of HCl (5 x 10-3). The result is
an excess of 3 x 10-3 mol of HCl.
Obtain the concentration and then the pH of the solution.
The concentration is dependent on the total volume of the new solution and the remaining amount of
unreacted HCl. Therefore, the new HCl concentration will be equal to
11/14/11 rev. 10/29/12, 4/3/13, 5/13/13, 5/11/15
Indian River State College, ASC

3 x 10-3 mol of HCl (the excess amount) (Divided by the total amount of solution)
0.03500 L new solution (created by adding 10 mL NaOH to the 25 mL of HCl)
3 x 10-3
35
[H] = 8.57 x 10-2 m
pH = -Log (8.57 x 10-2 m) = 1.07
3. At the equivalence point use the equation
MHCl x VHCl
=
MNaOH x VNaOH (at equivalence point)
(0.200 m) (25 mL) = (0.200 m) (VNaOH)
NaOH = 25 mL
The same concentration of NaOH is required to neutralize HCl, therefore
the same volume of NaOH is required.
4. After the equivalence point, by definition there will be an excess of base, as NaOH will
continue to be added. Now do a calculation similar to the one used above in paragraph #2.
Determine the value of pH to be found after adding another 5 mL of 0.200 m NaOH.
Excess NaOH = 5 mL NaOH x 0.200 m NaOH = 1 x 10-3 moles NaOH
[OH] = 1 x 10-3 moles NaOH_______________ = 1 x 10-3 moles NaOH
25 mL HCl + 25 mL NaOH + 5 mL NaOH
0.055 L

Excess base means there

is [OH] concentration
to calculate = 0.02 moles
pOH = -Log[OH] = 1.698
pH = 14 pOH = 12.3
B. Weak Acid and Strong Base
Since a weak acid does not ionize 100%, the pH of the solution will be dependent on how
much acid dissociates which is a function of KA. Use the appropriate KA equation to
determine the pH. As base is added, the pH will rise. At the equivalency point, the pH will
be above 7. At the same molarity more OH- than H+ will be generated due to the 100%
dissociation of the strong base. At the equivalence point, use KB to determine the OHconcentration.
Use the same acid and same volume concentration from the strong acid/strong base problem.
HC2H3O2 (aq) + NaOH Na C2H3O2 + H2O
Weak acid

Ionic Equation:

Strong Base

HC2H3O2 (aq) + Na+ OH- Na+ + C2H3O2- + H2O

The original net ionic equation must be created. It is:

HC2H3O2 + OH- C2H3O2- + H2O
11/14/11 rev. 10/29/12, 4/3/13, 5/13/13, 5/11/15
Indian River State College, ASC

1. To determine the initial pH, first determine the concentration of H+ that will give the initial
pH of the solution. ( HC2H3O2 H+ + C2H3O2- ) This is the only acid in the solution.
KA = [H+][ C2H3O2-]
[HC2H3O2]
(This number is from
1.8 x 10-5 = [x][x]
= [x][x]
the table)
(0.200-x)
(0.200)
(x will be very small, ignore it.)
3.6 x 10-6 = x2

1.9 x 10-3 = x

pH = -Log[H+] = 2.72 (before any NaOH is added)

2. Between the start and the equivalence point As NaOH is added to the HC2H3O2, C2H3O2- is
produced. The solution contains both HC2H3O2 and C2H3O2-. It is a buffered solution. Now
rearrange the equilibrium law (kA) to read: H+ = kA [mol HC2H3O2]
mol C2H3O2Add 10 mL of NaOH (strong base). The initial moles of acetic acid:
(HC2H3O2) = (.200m)(.0250 L) = 5 x 10-3 mol HC2H3O2
Moles of NaOH added = (.200 m)(.0100 L) = 2 x 10-3 mol NaOH =
Moles of acetic acid remaining:
5 x 10-3 mol (HC2H3O2) - 2 x 10-3 mol NaOH (neutralization)
equals
3 x 10-3 mol HC2H3O2 remaining (unreacted)
Note: Moles of NaOH = moles of acetate formed, based on the 1:1 relationship from the
balanced equation.
[H+] = (1.8 x 10-5)(3 x 10-3 mol HC2H3O2 remaining)
(2 x 10-3 mol produced)

= 2.7 x 10-5 m

pH = -Log(2.7 x 10-5 m) = 4.57

3. At the equivalence point
All the acetic acid has now reacted and the solution contains the product Na C2H3O2 (this is a
soluble mixture of Na+ and C2H3O2-). Using the same kA equation, the initial amount of
C2H3O2- produced = 5 x 10-3 mol. It is totally consumed in the reaction with NaOH.
conc [C2H3O2-] = ____5 x 10-3 mol_____________
25 mL NaOH + 25 mL (HC2H3O2)
(Need equivalent amounts of
NaOH to neutralize the HC2H3O2)

= 5 x 10-3 mol = .1 M
.0500 L

Note: C2H3O2- is a conjugate base of HC2H3O2)

11/14/11 rev. 10/29/12, 4/3/13, 5/13/13, 5/11/15
Indian River State College, ASC

C2H3O2- + H2O HC2H3O2 + OHUse kB, since OH- is in the equation.

kB = [ C2H3O2-][OH-] = [x][x] = 5.6 x 10-10
C2H3O2
.100
Note: kA kB = 1 x 10-14

kB = 1 x 10-14 = 5.6 x 10-10

1.85 x 10-5

X2 = 5.6 x 10-11
X = 7.5 x 10-6 = [OH] = pOH = 5.12
pH = 14 5.12
pH = 8.88
4. Note that after adding more NaOH (5 mL), after the equivalence point, the solution will
become more basic and should be treated as the only substance remaining.
Excess NaOH = 5 mL NaOH x .200 m NaOH = 1 x 10-3 NaOH moles
1000 mL
[OH-] = _________1 x 10-3 NaOH m _____________ = 1 x 10-3 NaOH m = 0.2
25 mL C2H3O2- + 25 mL NaOH + 5 mL NaOH
.055 L
pOH = -Log [OH] = 1.698
pH = 14 pOH (1.698) = 12.3

Acid-Base Titration Problems

Problem 1
30 mL of 1100M solution of HNO2
ka HNO2 = 4.6 x 10-4
Initially treat this problem as a weak acid in a solution of water. Use ICE.
HNO2
H+ + NO2Concentration of HNO2 = 100 molar

11

-x

11-x

Ka = [x] [x] = 4.6 x 10-4

11

X2 = 4.6 x 10-5

x = 100678

-Log [.00678] = 2.168 = pH

11/14/11 rev. 10/29/12, 4/3/13, 5/13/13, 5/11/15
Indian River State College, ASC

Problem 2

11/14/11 rev. 10/29/12, 4/3/13, 5/13/13, 5/11/15

Indian River State College, ASC