Chapter 9 Part C Buffer Solutions
9C-1 Calculation of the pH of buffer solutions
By definition, a buffer solution resists changes in pH with dilution or with addition
of acids, or bases - Buffer solutions are prepared from conjugated acid/base pair.
The Henderson-Hasselbalch equation
cNaA − log[H 3O ] = − log K a + log cHA cNaA pH = pK a + log cHA
+
Example 9-1:
What is the pH of a solution that is 0.400 M in formic acid and 1.00 M in sodium formate?
Example 9-2:
Calculate the pH

Attribution Non-Commercial (BY-NC)

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Chapter 9 Part C Buffer Solutions
9C-1 Calculation of the pH of buffer solutions
By definition, a buffer solution resists changes in pH with dilution or with addition
of acids, or bases - Buffer solutions are prepared from conjugated acid/base pair.
The Henderson-Hasselbalch equation
cNaA − log[H 3O ] = − log K a + log cHA cNaA pH = pK a + log cHA
+
Example 9-1:
What is the pH of a solution that is 0.400 M in formic acid and 1.00 M in sodium formate?
Example 9-2:
Calculate the pH

Attribution Non-Commercial (BY-NC)

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Buffer Solutions

9C-1 Calculation of the pH of buffer solutions

of acids, or bases

- Buffer solutions are prepared from conjugated acid/base pair.

cNaA

− log[H 3O ] = − log K a + log

+

cHA

cNaA

pH = pK a + log

cHA

Example 9-1:

What is the pH of a solution that is 0.400 M in formic acid and 1.00 M in sodium

formate?

Example 9-2:

Calculate the pH of a solution that is 0.200 M in NH3 and 0.300 M in NH4Cl?

9C-2 Properties of buffer solutions

Example 9-3: The effect of added acids and bases

Calculate the pH change that takes place when a 100-mL portion of (a) 0.0500 M NaOH

and (b) 0.0500 M HCl is added to 400 mL of the buffer solution that was described in

Example 9-2.

The composition of buffer solutions as a function of pH

Buffer Capacity: β of a solution is defined as the number of moles of a strong acid

or a strong base that causes 1.00 L of the buffer to undergo a 1.00-unit change in

pH.

dcb dca

β= =−

dpH dpH

Example 9-4: Preparation of buffers

Describe how you might prepare approximately 500.0 mL or pH 4.5 buffer solution from

1.00 M acetic (HOAc) and sodium (NaOAc).

Chapter 10

10A The effect of electrolytes on chemical equilibria

Electrostatic forces cause each ion from a dissociated species/reactant to be surrounded

by a “sheath” of oppositely charged ions from the added electrolyte. This has several

effect:

(1) The affinity of an ion for its original counter ion is reduced (Keq gets bigger because

the reverse reformation reaction is inhibited.)

(2) Solubility usually goes up as more ion are “pulled” into solution.

(3) The greater the number of electrolyte ions present, the greater the effect.

(4) In dilute solutions, “sheaths” of counter ions are not likely; solubility and Keq

approach a limiting value.

(5) These effects collectively are called “electrolyte effects”

The electrolyte effect is dependent upon the chemical nature of the electrolyte

involved and upon its ionic strength.

1

µ = ([ A ]Z 2A + [ B]Z 2B + [C]Z C2 + ...)

2

Example 10-1:

Calculate the ionic strength of (a) a 0.1 M solution of KNO3 and (b) a 0.1 M solution of

Na2SO4?

Example 10-2:

What is the ionic strength of a solution that is 0.05 M in KNO3 and 0.1 M in Na2SO4?

The stoichiometry of the electrolyte determines the ionic strength:

Properties of activity coefficients:

10B Activity coefficients

strength. Chemists use “activity” to describe the effective concentration.

aX = [ X ]γ X

K sp = a m ⋅ a Ym = [ X ]γ X

X

The Debye-Hückel equation:

0.51Z 2X µ

− log γ X =

1 + 3.3α X µ

where

γ X = activity coefficient of the species X

ZX = charge on the species X

µ = ionic strength of the solution

α X = effective diameter of the hydrated ion X in nm (10-9 m)

Example 10-3:

(a) Use the Debye-Hückel equation to calculate the activity coeffiecient for Hg2+ in a

solution that has an ionic strength of 0.085 M. Use 0.5 nm for the effective diameter of

the ion. (b) Compare the value obtained in (a) with the activity coefficient obtained by

linear interpolation of the data in Table 10-2 for coefficient of the ion at ionic strengths

of 0.1 M and 0.05 M.

Example 10-4: Equilibrium calculations using activity coefficients

Use activities to calculate the hydronium ion concentration in a 0.120 M solution of

HNO2 that is also 0.050 M NaCl. What is the relative percent error incurred by neglecting

activity corrections?

Find the relactive error introduced by neglecting activities in calculating the solubility of

Ba(IO3)2 in a 0.033 M colution of Mg(IO3)2. The thermodynamic solubility product for

Ba(IO3)2 is 1.57× 10-9 .

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