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19-1 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Chapter 19
19-2
Ionic Equilibria in Aqueous Systems
19-3
Acid-Base Buffers
19-4
Figure 19.1 The effect of adding acid or base to an unbuffered
solution.
19-5
Figure 19.2 The effect of adding acid or base to a buffered
solution.
19-6
Buffers and the Common-ion Effect
A buffer works through the common-ion effect.
19-8
How a Buffer Works
19-9
Figure 19.3 How a buffer works.
Buffer has more HA after Buffer has equal Buffer has more A- after
addition of H3O+. concentrations of A- and HA. addition of OH-.
H3O+ OH-
19-10
Relative Concentrations of Buffer Components
[CH3COOH] [CH3COO−]
Since Ka is constant, the [H3O+] of the solution depends
on the ratio of buffer component concentrations.
[HA]
If the ratio − increases, [H3O+] decreases.
[A ]
[HA]
If the ratio − decreases, [H3O+] increases.
[A ]
19-11
Sample Problem 19.1 Calculating the Effect of Added H3O+ or
OH− on Buffer pH
PROBLEM: Calculate the pH:
(a) Of a buffer solution consisting of 0.50 M CH3COOH and 0.50 M
CH3COONa
(b) After adding 0.020 mol of solid NaOH to 1.0 L of the buffer solution
(c) After adding 0.020 mol of HCl to 1.0 L of the buffer solution in (a).
Ka of CH3COOH = 1.8 x 10−5. (Assume the additions cause a negligible
change in volume.)
19-12
Sample Problem 19.1
SOLUTION: (a)
Concentration (M) CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)
Initial 0.50 - 0.50 0
Change −x - +x +x
Equilibrium 0.50 - x - 0.50 + x x
Since Ka is small, x is small, so we assume
[CH3COOH] = 0.50 – x ≈ 0.50 M and [CH3COO-] = 0.50 + x ≈ 0.50 M
[CH3COOH]
x = [H3O+] = Ka x ≈ 1.8x10−5 x 0.50 = 1.8x10−5 M
[CH3COO−] 0.50
Checking the assumption: pH = -log(1.8x10−5) = 4.74
1.8x10-5 M x 100 = 3.6x10−3% (< 5%; assumption is justified.)
0.50 M
19-13
Sample Problem 19.1
0.020 mol
(b) [OH−]added = = 0.020 M OH−
1.0 L soln
Setting up a reaction table for the stoichiometry:
Concentration (M) CH3COOH(aq) + OH−(aq) → CH3COO−(aq) + H2O(l)
Initial 0.50 0.020 0.50 -
Change -0.020 -0.020 +0.020 -
Equilibrium 0.48 0 0.52 -
Setting up a reaction table for the acid dissociation, using new initial [ ]:
Concentration (M) CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)
Initial 0.48 - 0.52 0
Change −x - +x +x
Equilibrium 0.48 - x - 0.52 + x x
19-14
Sample Problem 19.1
19-15
Sample Problem 19.1
0.020 mol
(c) [H3O+]added = = 0.020 M H3O+
1.0 L soln
Setting up a reaction table for the stoichiometry:
Concentration (M) CH3COO−(aq) + H3O+(aq) → CH3COOH(aq) + H2O(l)
Initial 0.50 0.020 0.50 -
Change -0.020 -0.020 +0.020 -
Equilibrium 0.48 0 0.52 -
Setting up a reaction table for the acid dissociation, using new initial [ ]:
Concentration (M) CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)
Initial 0.52 - 0.48 0
Change −x - +x +x
Equilibrium 0.52 - x - 0.48 + x x
19-16
Sample Problem 19.1
19-17
The Henderson-Hasselbalch Equation
[H3O+][A−] [HA]
Ka = [H3O+] = Ka x
[HA] [A−]
[HA]
-log[H3O ] = -logKa – log
+
[A−]
[base]
pH = pKa + log
[acid]
19-18
Buffer Capacity
19-19
Figure 19.4 The relation between buffer capacity and pH change.
This graph shows the final pH values for four different buffer solutions after
the addition of strong base.
19-20
Buffer Range
19-21
Sample Problem 19.2 Using Molecular Scenes to Examine Buffers
19-22
Sample Problem 19.2
PLAN: Since the volumes of the solutions are equal, the scenes
represent molarities as well as numbers. We count the
particles of each species present in each scene and calculate
the ratio of the buffer components.
SOLUTION:
[A−]/[HA] ratios: sample 1, 3/3 = 1; sample 2, 2/4 = 0.5; sample 3,
4/4 = 1; and sample 4, 4/2 = 2.
19-23
Sample Problem 19.2
(a) As the pH rises, more HA will be converted to A-. The scene with
the highest [A−]/[HA] ratio is at the highest pH. Sample 4 has the
highest pH because it has the highest ratio.
(b) The buffer with the greatest capacity is the one with the [A−]/[HA]
closest to 1. Sample 3 has the greatest buffer capacity.
19-24
Preparing a Buffer
• Choose the conjugate acid-base pair.
– The pKa of the weak acid component should be close to the
desired pH.
• Calculate the ratio of buffer component concentrations.
[base]
pH = pKa + log
[acid]
19-25
Sample Problem 19.3 Preparing a Buffer
19-26
Sample Problem 19.3 Preparing a Buffer
Ka[HCO3−] (4.7x10-11)(0.20)
[CO ] =
3
2− = = 0.094 M
[H3O ]
+ 1.0x10 -10
1 L soln
= 0.14 mol CO32−
19-27
Acid-Base Indicators
19-28
Figure 19.5 Colors and approximate pH range of some
common acid-base indicators.
pH
19-29
Figure 19.6 The color change of the indicator bromthymol blue.
19-30
Acid-Base Titrations
In an acid-base titration, the concentration of an acid (or a
base) is determined by neutralizing the acid (or base) with
a solution of base (or acid) of known concentration.
19-31
Figure 19.7 Curve for a strong acid–strong base titration.
19-32
Calculating the pH during a
strong acid–strong base titration
Initial pH
[H3O+] = [HA]init
pH = -log[H3O+]
19-33
Calculating the pH during a
strong acid–strong base titration
pH at the equivalence point
pH = 7.00 for a strong acid-strong base titration.
19-34
Example:
Initial mol of H3O+ = 0.04000 L HCl x 0.1000 mol = 4.000x10−3 mol H3O+
1L
OH- added = 0.02000 L NaOH x 0.1000 mol = 2.000x10−3 mol OH-
1L
The OH- ions react with an equal amount of H3O+ ions, so
19-35
2.000x10−3 mol
[H3O ] = +
= 0.03333 M
0.04000 L + 0.02000 L
pH = -log(0.03333) = 1.48
The equivalence point occurs when mol of OH- added = initial mol of
HCl, so when 40.00 mL of NaOH has been added.
1.000x10−3 mol
[OH ] =
-
= 0.01111 M
0.04000 L + 0.05000 L
19-36
Figure 19.8 Curve for a weak acid–strong base titration.
19-37
Calculating the pH during a
weak acid–strong base titration
Initial pH
[H3O+][A−]
Ka = [H3O+] = K a x [HA]init)
[HA]
pH = -log[H3O+]
[H3O+] = Ka x [HA] or
[A−]
[base]
pH = pKa + log
[acid]
19-38
Calculating the pH during a
weak acid–strong base titration
pH at the equivalence point
A-(aq) + H2O(l) HA(aq) + OH-(aq)
[OH-] = K b x [A-]
mol HAinit Kw
where [A-] = and Kb =
Vacid + Vbase Ka
Kw
[H3O+] ≈ and pH = -log[H3O+]
K b x [A-])
19-40
Sample Problem 19.4
19-41
Sample Problem 19.4
pH = -log(1.6x10-9) = 8.80
19-42
Sample Problem 19.4
Kw 1x10 -14
[H3O+] = = = 9.0x10−13 M
[OH−] 0.01111
pH = -log(9.0x10-13) = 12.05
19-43
Figure 19.9 Curve for a weak base–strong acid titration.
The pH decreases
gradually in the buffer
region. The weak base
and its conjugate acid
are both present in The pH at the equivalence
solution. point is < 7.00 due to the
reaction of the conjugate
acid with H2O.
19-44
Equilibria of Slightly Soluble Ionic Compounds
Any “insoluble” ionic compound is actually slightly
soluble in aqueous solution.
We assume that the very small amount of such a compound that
dissolves will dissociate completely.
Qc = [Pb 2+
][F ]
− 2
Qsp = Qc[PbF2] = [Pb2+][F−]2
[PbF2]
19-45
Qsp and Ksp
Qsp is called the ion-product expression for a slightly
soluble ionic compound.
For any slightly soluble compound MpXq, which consists
of ions Mn+ and Xz-,
Qsp = [Mn+]p[Xz-]q
19-46
Metal Sulfides
Metal sulfides behave differently from most other slightly
soluble ionic compounds, since the S2- ion is strongly
basic.
We can think of the dissolution of a metal sulfide as a
two-step process:
MnS(s) Mn2+(aq) + S2-(aq)
S2−(aq) + H2O(l) → HS−(aq) + OH−(aq)
Ksp = [Mn2+][HS−][OH−]
19-47
Sample Problem 19.5 Writing Ion-Product Expressions
19-48
Sample Problem 19.5
Ksp = [Ag+]2[HS−][OH−]
19-49
Table 19.2 Solubility-Product Constants (Ksp) of Selected
Ionic Compounds at 25°C
19-50
Sample Problem 19.6 Determining Ksp from Solubility
19-51
Sample Problem 19.6
SOLUTION:
(a) PbSO4(s) Pb2+(aq) + SO42−(aq) Ksp = [Pb2+][SO42−]
19-52
Sample Problem 19.6
19-53
Sample Problem 19.7 Determining Solubility from Ksp
19-54
Sample Problem 19.7
S = 3 K sp
4
=
3 6.5x10-6
4
= 1.2x10−2 M
19-55
No. of Ions Formula Cation/Anion Ksp Solubility (M)
2 MgCO3 1/1 3.5x10−8 1.9x10−4
2 PbSO4 1/1 1.6x10−8 1.3x10−4
2 BaCrO4 1/1 2.1x10−10 1.4x10−5
19-56
Figure 19.10 The effect of a common ion on solubility.
19-57
Sample Problem 19.8 Calculating the Effect of a Common Ion
on Solubility
PROBLEM: In Sample Problem 19.7, we calculated the solubility of
Ca(OH)2 in water. What is its solubility in 0.10 M
Ca(NO3)2? Ksp of Ca(OH)2 is 6.5x10−6.
SOLUTION:
Ca(OH)2(s) Ca2+(aq) + 2OH−(aq) Ksp = [Ca2+][OH−]2
19-58
Sample Problem 19.8
[Ca2+]init = 0.10 M because Ca(NO3)2 is a soluble salt, and dissociates
completely in solution.
Concentration (M) Ca(OH)2(s) Ca2+(aq) + 2OH−(aq)
Initial - 0.10 0
Change - +S + 2S
Equilibrium - 0.10 + S 2S
4S ≈
2
6.5x10-6
0.10
so S ≈
6.5x10-5
4
= 4.0x10−3 M
0.10 M
19-59
Effect of pH on Solubility
Changes in pH affects the solubility of many slightly
soluble ionic compounds.
The addition of H3O+ will increase the solubility of a salt
that contains the anion of a weak acid.
CaCO3(s) Ca2+(aq) + CO32−(aq)
19-60
Figure 19.11 Test for the presence of a carbonate.
19-61
Sample Problem 19.9 Predicting the Effect on Solubility of
Adding Strong Acid
PROBLEM: Write balanced equations to explain whether addition of
H3O+ from a strong acid affects the solubility of each ionic
compound:
(a) lead(II) bromide (b) copper(II) hydroxide (c) iron(II) sulfide
SOLUTION:
(a) PbBr2(s) Pb2+(aq) + 2Br−(aq)
Br- is the anion of HBr, a strong acid, so it does not react with H3O+. The
addition of strong acid has no effect on its solubility.
19-62
Sample Problem 19.9
19-63
Predicting the Formation of a Precipitate
For a saturated solution of a slightly soluble ionic salt,
Qsp = Ksp.
19-64
Sample Problem 19.10 Predicting Whether a Precipitate Will
Form
PROBLEM: A common laboratory method for preparing a precipitate is
to mix solutions containing the component ions. Does a
precipitate form when 0.100 L of 0.30 M Ca(NO3)2 is mixed
with 0.200 L of 0.060 M NaF?
PLAN: First we need to decide which slightly soluble salt could form,
look up its Ksp value in Appendix C, and write the dissolution
equation and Ksp expression. We find the initial ion
concentrations from the given volumes and molarities of the
two solutions, calculate the value for Qsp and compare it to Ksp.
SOLUTION:
The ions present are Ca2+, NO3−, Na+, and F−. All Na+ and NO3− salts are
soluble, so the only possible precipitate is CaF2 (Ksp = 3.2x10−11).
CaF2(s) Ca2+(aq) + 2F-(aq) Ksp = [Ca2+][F−]2
19-65
Sample Problem 19.10
[F ]init =
- 0.012 mol F- = 0.040 M F-
0.100 L + 0.200 L
Qsp = [Ca2+]init[F−]2init = (0.10)(0.040)2 = 1.6x10−
Since Qsp > Ksp, CaF2 will precipitate until Qsp = 3.2x10−11.
19-66
Sample Problem 19.11 Using Molecular Scenes to Predict
Whether a Precipitate Will Form
PROBLEM: These four scenes represent solutions of silver (gray) and
carbonate (black and red) ions above solid silver
carbonate. (The solid, other ions, and water are not
shown.)
(a) Which scene best represents the solution in equilibrium with the
solid?
(b) In which, if any, other scene(s) will additional solid silver
carbonate form?
(c) Explain how, if at all, addition of a small volume of concentrated
strong acid affects the [Ag+] in scene 4 and the mass of solid
present.
19-67
Sample Problem 19.11
PLAN: We need to determine the ratio of the different types of ion in
each solution. A saturated solution of Ag2CO3 should have
2Ag+ ions for every 1 CO32− ion. For (b) we need to compare
Qsp to Ksp. For (c) we recall that CO32− reacts with H3O+.
SOLUTION:
First we determine the Ag+/CO32− ratios for each scene.
Scene 1: 2/4 or 1/2 Scene 2: 3/3 or 1/1
Scene 3: 4/2 or 2/1 Scene 4: 3/4
(a) Scene 3 is the only one that has an Ag+/CO32− ratio of 2/1, so this
scene represents the solution in equilibrium with the solid.
19-68
Sample Problem 19.11
(b) We use the ion count for each solution to determine Qsp for each
one. Since Scene 3 is at equilibrium, its Qsp value = Ksp.
Scene 1: Qsp = (2)2(4) = 16 Scene 2: Qsp = (3)2(3) = 27
Scene 3: Qsp = (4)2(2) = 32 Scene 4: Qsp = (3)2(4) = 36
Scene 4 is the only one that has Qsp > Ksp, so a precipitate forms in
this solution.
(c) Ag2CO3(s) 2Ag+(aq) + CO32−(aq)
CO32-(aq) + 2H3O+(aq) → [H2CO3(aq)] + 2H2O(l) → 3H2O(l) + CO2(g)
19-69
Figure 19.12 Formation of acidic precipitation.
Since pH affects the solubility of many slightly soluble ionic compounds, acid
rain has far-reaching effects on many aspects of our environment.
19-70
Figure 19.13 Cr(NH3)63+, a typical complex ion.
19-71
Figure 19.14 The stepwise exchange of NH3 for H2O in M(H2O)42+.
19-72
Sample Problem 19.12 Calculating the Effect of Complex-Ion
Formation on Solubility
PROBLEM: In black-and-white film developing, excess AgBr is
removed from the film negative by “hypo”, an aqueous
solution of sodium thiosulfate (Na2S2O3), which forms the
complex ion Ag(S2O3)23−. Calculate the solubility of AgBr
in (a) H2O; (b) 1.0 M hypo.
Kf of Ag(S2O3)23− is 4.7x1013 and Ksp AgBr is 5.0x10−13.
PLAN: After writing the equation and the Ksp expression, we use the
given Ksp value to solve for S, the molar solubility of AgBr. For
(b) we note that AgBr forms a complex ion with S2O32−, which
shifts the equilibrium and dissolves more AgBr. We write an
overall equation for the process and set up a reaction table to
solve for S.
19-73
Sample Problem 19.12
SOLUTION:
(a) AgBr(s) Ag+(aq) + Br−(aq) Ksp = [Ag+][Br−] = 5.0x10−13
S = [AgBr]dissolved = [Ag+] = [Br−]
Ksp = [Ag+][Br−] = S2 = 5.0x10-13 S = 7.1x10−7 M
[Br−][Ag(S2O3)23−]
Koverall = Ksp x Kf = = (5.0x10−13)(4.7x1013) = 24
[S2O32−]2
19-74
Sample Problem 19.12
Initial - 1.0 0 0
Change - -2S +S +S
Equilibrium - 1.0 - 2S S S
S2 S
Koverall = = 24 so = 24 = 4.9
(1.0 - 2S) 2
1.0 - 2S
S = [Ag(S2O3)23−] = 0.45 M
19-75