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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 of a solution that is 0.200 M in NH3 and 0.300 M in NH4Cl?
9C-2 Properties of buffer solutions

 The effect of dilution


 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

Effect of Electrolyte on Chemical Equilibria


10A The effect of electrolytes on chemical equilibria

 Concentration-based equilibrium constants vs. thermodynamic values


 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

 “Effective” concentration of a species depends upon and is a function of ionic


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

aX = [ X ]γ X

 The thermodynamic equilibrium constant should be:

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?

 Example 10-5: Equilibrium calculations using activity coefficients


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 .