Chapter 9: Monoprotic Acid-Base Equilibria Chapter 11: Acid-Base Titrations

Example: Determination of HCl concentration by titration with NaOH

I. Solutions and Indicators for Neutralization Titrations

A. Standard Solutions: The standards solutions used as titrants for unknown w eak acids or bases are alw ays strong bases or acids, respectively. Standard titrant acids: dilute solutions of HCl, HClO 4 , or H 2 SO 4 . Standard titrant bases: dilute solutions of NaOH, KOH. The primary standards may not be strong acids or bases (e.g., potassium acid phthalate, sodium oxalate, sodium bicarbonate).

B. The Theory of Indicator Behavior 1. pH-sensitive dyes have long been used as indicators. Normally, the basic form (In) on the dye has a color different from the acid form, HIn: HIn + H2O <====> H3O+ + InIn + H2O <====> OH- + HIn+
Ka = [H 3O + ][In ] [HIn] [OH ][HIn + ] [In]

[Eq.1]

Kb =

[Eq. 2]

We can see that both equilibrium constant expressions above can be written:
[ H 3O + ] = Ka[HIn] [In ]
Ka[HIn + ] [In]

[Eq. 1]

[ H 3O ] =

{Note: Kw =KaKb = [OH-][H+]}

[Eq. 2]

Therefore, the [H3O+] determines the ratio of the acid/conjugate base form of the indicator. To see the color of a particular form (acid or base) of the indicator, that form must be present at tenfold higher concentration.

For example, To see the color of acid form, the ratio [HIn]/[In] must be equal to or greater than 10. To see the color of base form, the ratio [HIn]/[In] must be equal to or less than 0.1. This means that: For acid color [H3O+] > Ka (10/1) For base color [H3O+] < Ka (1/10) Hence: indicator range = pKa 1, and the pH change in the area of the equivalence point must match this range or at least overlap it significantly to use this indicator for endpoint detection. (note: how to select the indicator)

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C.

Titration Curves may be linear-segment curve or a sigmoidal curve depending on what is plotted on the y-axis. The X-axis units are always reagent or titrant volume. The Y-axis may be in increments of analyte reacted or product formed (linear-segment curve) or a p-function such as pH (s-curve). The equivalence point is characterized by large changes in the relative concentrations of the reagent and analyte. (See Table 10-2)

Titration Curves

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D. The Titration of a Strong Acid with a Strong Base

Example: Determination of HCl concentration by titration with NaOH

NaOH + HCl

NaCl + H2O

moles = CNaOHVNaOH = CHClVHCl

1. H3O+ in the titration medium has two sources a. From the H2O solvent b. From the acid solute - usually this is in great excess relative contribution from water because the Kw is so small c. The mass balance equation describing this situation is:
[ H 3 O + ] = C H C l + [ O H -] = C HCl

d . T h e s a m e is tr u e fo r a s tr o n g b a s e a n d w e c a n w r ite : [ O H -] = C N a O H + [ H 3 O + ] = C N a O H

2. Before the equivalence point We calculate the pH of the titration medium from the concentration of unreacted strong acid:
Moles of [ H 3O + ] Moles of [OH ] [ H 3O ] = Vacid + Vbase
+

pH = - log [H3O+] 3. At the equivalence point All of the acid has reacted with the titrant base. For a strong acid titrated with a strong base, the salt is a strong electrolyte and therefore completely dissociated. It does not react with H2O. The resulting solution is neutral (pH = 7.00) because: HCl + NaOH <====> H2O + Na+ + Cl2 H2O <====> H3O+ + OH4. After the equivalence point we calculate the pH of the titration medium from the concentration of unreacted strong base:
Kw Moles of [OH ]added Moles of [ H 3O + ] = [OH ] = [ H 3O + ] Vacid + Vbase

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9-1

9-2

Any Questions?

5. The Effect of Concentration on the shape of the curve: With a very dilute solution of strong acid which is titrated with a very dilute solution of strong base, there will be a smaller relative change in the pH immediately before and after the equivalence point

6.

The selection of an indicator The indicator range (detectable color change) should occur in the area of the equivalence point. Concentration effect i. titration of 0.0500 M HCl with 0.1000 M NaOH three indicators (phenolphthalein, bromothymol blue, Bromocresol green) have color changes in this range. ii. for the more dilute titration medium (0.000500 M HCl with 0.001000 M NaOH), only one of the indicators (bromothymol blue) is now suitable. iii. This is because the relative pH change for the second curve is so small that two of the indicators change color before or after the equivalence point.

Any Questions?

E.

Buffer Solutions: A buffer solution resists changes in pH. Buffers usually consist of a weak acid/conjugate base pair mixture in solution. Since the titration of a weak acid (or base) with a strong base (or acid) will form a buffer solution, the curves constructed for these titration systems will appear quite different from those where all the reactants are completely

E1. The Calculation of the pH of Buffer Solutions: Example: We are preparing a buffer in which the acid, HA, and its salt, NaA, are being added to the solution to give CHA and CNaA For the species HA and A- we can write: a. Pertinent Equilibria HA + H2O <====> A- + H3O+ A-+ H2O <====> HA + OH-

2H2O <====> H3O+ + OHb. Equilibrium Expressions

[H 3 O + ][A - ] Ka = [HA] [OH ][HA] Kb = [A - ]

[Eq. 1] [Eq. 2] [Eq. 3]

Kw =[H3O+] [OH-] c. Mass balance equations: [HA] = CHA - [H3O+] + [OH-] [A-] = CNaA + [H3O+] - [OH-]

[Eq. 4] [Eq. 5]

d. Approximations: Since the concentrations of these species are likely to be negligible relative the CHA and CNaA, we can approximate: [HA] = CHA [A-] = CNaA This assumption is true only when Ka < 10-3 and the relative concentrations of the acid or its conjugate base are relatively high. e. Solving equations If we rearrange Eq.1 and solve for [H3O+] then
[H 3O + ] = K a [HA] [A - ]

[Eq.1]

Taking -log of both sides of Eq.1

pH = pK a log C [HA] [A - ] = pK a + log = pK a + log NaA [A - ] [HA] C HA

This equation implies that the pH of a buffer solution is independent of the dilution of the solution since the relative concentrations of conjugate base/acid do not change upon dilution

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HCOO- + H2O < ==> HCOOH + H3O+

pH = pK a + log C NaA C HA

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pH = pK a + log

C NH 3 C NH +
4

pH = pK a + log

C NH 3 C NH +
4

Any Questions?

F. Properties of Buffer Solutions 1. Effect of Dilution: Theoretically, pH does not change with dilution. However, ionic strength changes with dilution (and therefore so will Ka). For buffers whose Ka values are strongly influenced by ionic strength, we may see a pH change over large changes in concentration. 2. Effect of Temperature: Since Ka changes as a function of temperature, we can expect buffer pH to change with changes in temperature. 3. Effect of Added Acids or Bases: Buffer solutions tend to resist pH change, although the ratio of base/acid changes depending on the amount of acid or base added 4. Buffer Capacity: The number of moles of strong acid or strong base that causes the pH of 1.00 L of buffer to change by 1.00 pH unit. The buffering capacity of the system for acid or base falls off as the concentration ratio of weak acid to conjugate base in the solution becomes larger or smaller than 1.

If ([A-]/[HA])<<1, the system will not buffer acid effectively; If ([A-]/[HA])>>1, the system will not buffer base effectively. If ([A-]/[HA])= 1, buffering capacity to both acids and bases is considered most effective and the pKa for the system is within 1 unit of the desired

G.

Titration Curves for Weak Acids: There are 4 areas to consider

1) 2) 3) 4)

before the addition of base before the equivalence point (buffer region 1) at the equivalence point after the equivalence point

1. Before the addition of base: Calculated from the concentration and Ka of the weak acid. 2. After the addition of strong base but before the equivalence point:
Moles of [OH ]added Vtotal Moles of [OH ]added = pK a + log pH = pK a + log Moles of [H 3O + ] Moles of [H 3O + ] Vtotal

Note: The half-neutralized point pH = pKa and hence you can measure pKa from titration curve. The half-neutralized point means pH at
Vb = 1 Ve 2

Note: Vb : volume of titrant Ve: volume of titrant needed to reach the equivalence point Note: You will need these questions and concepts for the calculation in Chem 322 (potentiometric titration experiments).

3. At the equivalence point: The predominant equilibrium is the hydrolysis of H2O by the salt of the weak acid: A- + H2O <====> HA + OH[OH ][HA] Kb = [A - ]

Generally, you can solve the equilibrium constant equation for [OH-] and assume that
[A ] =
-

Moles of [H 3O + ] Vtotal

[OH ] = K b C b Thus,

For weak acids that are titrated with strong bases, the pH at the equivalence point will be basic. 4. Beyond the equivalence point: Both the anion of the weak acid and the excess base are sources of [OH-]. However, due to LeChatelier's Principle the addition of [OH-] in the form of a strong base will suppress the hydrolysis by the weak acid anion so that:
Moles of [OH ]added Moles of [H 3O + ] [OH ] = Vtotal

9-5 9-4 HOAC + H2O H3O+ + OAC-

[ H 3O + ] = K a C a

Moles of [OH ]added pH = pK a + log Moles of [H 3O + ]

[OH ] = K b C b

Moles of [OH ]added Moles of [H 3O + ] [OH ] = Vtotal

H.

Titration Curves for Weak Bases: There are 4 areas to consider

1) 2) 3) 4)

before the addition of acid before the equivalence point (buffer region 1) at the equivalence point after the equivalence point

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[OH ] = K b C b

Moles of [OH ] pH = pK a + log Moles of [H 3O + ]

[ H 3O + ] = K a C a

Moles of [H 3O ]added Moles of [OH ] [ H 3O ] = Vtotal

+

I. The Effect of Concentration: Again, as with the titration of strong acids with strong bases, as the concentration of the weak acid or base becomes more dilute, the relative change in pH at the equivalence point decreases making the endpoint less sharp.

A: 0.1000 M acid with 0.1000 M base B: 0.001000 M acid with 0.001000 M base

I. The Effect of Reaction Completeness: The smaller the Ka, the less sharp the endpoint when a weak acid is titrated with a strong base (Figure 10-11). This depends also on concentration, so that weaker acids can be titrated if concentrated solutions are used.

Any Questions?

Summary
How to select standard solutions and indicators for neutralization titrations Theory of Indicator Behavior Titration Curves Theories: Plots and shapes of plots
Parameters: pH, Volume of titrants, equivalence point Calculations: Ka, pH, indicator choices, half-neutralized point Effects: Concentration, reaction, composition, temperature, equilibrium constants The titration of a strong acid with a strong base The titration of a week acid with a strong base The titration of a strong base with a strong acid The titration of a week base with a strong acid

Buffer solutions:
Definition and properties (e.g., buffer capacity) Calculation of pH of the buffer solution Applications

Homework
9-B, D, E, 2, 5, 6, 22, 23, 27, 28, 33 11-A, B, F, 3, 6, 14

Before working on Homework,

Practice with all examples that we discussed in the class and examples in the textbook!!