Chapter 19 Powerpoint L

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Chapter 19
Ionic Equilibria in Aqueous Systems
19-1
Ionic Equilibria in Aqueous Systems
19.1 Equilibria of Acid-Base Buffer Systems
19.2 Acid-Base Titration Curves
19.3 Equilibria of Slightly Soluble Ionic Compounds
19.4 Equilibria Involving Complex Ions
19-2
Figure19.1
The effect of addition of acid or base to
acid added
Figure19.2
an unbuffered solution
acid added
19-3
base added
or a buffered solution
base added
Table 19.1
The Effect of Added Acetate Ion on the Dissociation of Acetic Acid
[CH3COOH]initial
[CH3COO-]added
pH
0.10
0.00
1.3
2.89
0.10
0.050
0.036
4.44
0.10
0.10
0.018
4.74
0.10
0.15
0.012
4.92
* % Dissociation =
[CH3COOH]dissoc
[CH3COOH]initial
19-4
% Dissociation*
x 100
Figure19.3
How a buffer works.
Buffer after addition of H3O+
Buffer with equal

concentrations of
conjugate base and acid
H3O+
H2O + CH3COOH
19-5
H3O+ + CH3COO-
Buffer after addition of OH-
OH-
CH3COOH + OH-
H2O + CH3COO-
Sample Problem 19.1

PROBLEM:
Calculating the Effect of Added H3O+ or OHon Buffer pH

Calculate the pH:
(a) of a buffer solution consisting of 0.50M CH3COOH and 0.50M CH3COONa

(b) after adding 0.020mol of solid NaOH to 1.0L of the buffer solution in part (a)
(c) after adding 0.020mol of HCl to 1.0L of the buffer solution in part (a)
Ka of CH3COOH = 1.8x10-5. (Assume the additions cause negligible volume
changes.
PLAN: We know Ka and can find initial concentrations of conjugate acid and
base. Make assumptions about the amount of acid dissociating relative to its
initial concentration. Proceed step-wise through changes in the system.
SOLUTION: (a)
Concentration (M)
Initial
Change
Equilibrium
19-6
CH3COOH(aq) + H2O(l)
CH3COO-(aq) + H3O+(aq)
0.50
-x
0.50
+x
0
+x
0.50-x
0.50 +x
Sample Problem 19.1
Calculating the Effect of Added H3O+ and OHon Buffer pH
continued (2 of 4)
[H3O+] = x
Ka =
[CH3COOH]equil 0.50M
[H3O+][CH3COO-]
[CH3COOH]
Check the assumption:

(b)
[OH-]added =
Concentration (M)
Before addition
Addition
After addition
19-7
[H3O+] = x = Ka
[CH3COO-]initial 0.50M
[CH3COOH]
[CH3COO ]
-
= 1.8x10-5M
1.8x10-5/0.50 X 100 = 3.6x10-3 %
0.020 mol
1.0L soln
= 0.020M NaOH
CH3COOH(aq) + OH-(aq)
0.50
0.48
0.020
0
CH3COO-(aq) + H2O (l)

0.50
0.52
Sample Problem 19.1
continued (3 of 4)
Concentration (M)
Set up a reaction table with the new values.
Initial
Change
Equilibrium
[H3O+] = 1.8x10-5
(c)
[H3O+]added =
0.48
0.48
-x
0.52
+x
0
+x
0.48 -x
0.52 +x
= 1.7x10-5
0.52
0.020 mol
1.0L soln
pH = 4.77
= 0.020M H3O+
Concentration (M) CH3COO-(aq) + H3O+(aq)

Before addition
Addition
After addition
19-8
CH3COOH(aq) + H2O (l)
0.50
-
0.020
0.50
-
0.48
0.52
Sample Problem 19.1

continued (4 of 4)
Concentration (M)
Equilibrium
19-9
Set up a reaction table with the new values.
Initial
Change
[H3O+] = 1.8x10-5
0.52
0.48
0.52
-x
0.48
+x
0
+x
0.52 -x
0.48 +x
= 2.0x10-5
pH = 4.70
The Henderson-Hasselbalch Equation

HA + H2O
Ka =
H3O+ + A[H3O+] [A-]

[HA]
[H3O+] =
Ka [HA]
[A-]
- log[H3O+] = - log Ka + log
pH = pKa + log
19-10
[A-]
[HA]
[base]
[acid]
Buffer Capacity and Buffer Range

Buffer capacity is the ability to resist pH change.
The more concentrated the components of a buffer, the greater
the buffer capacity.
The pH of a buffer is distinct from its buffer capacity.
A buffer has the highest capacity when the component
concentrations are equal.
Buffer range is the pH range over which the buffer acts effectively.
Buffers have a usable range within 1 pH unit of the pKa of
its acid component.
19-11
Figure19.4
19-12
The relation between buffer capacity and pH change.
Preparing a Buffer
1. Choose the conjugate acid-base pair.
2. Calculate the ratio of buffer component concentrations.
3. Determine the buffer concentration.
4. Mix the solution and adjust the pH.
19-13
Sample Problem 19.2

PROBLEM:
Preparing a Buffer
An environmental chemist needs a carbonate buffer of pH 10.00

to study the effects of the acid rain on limsetone-rich soils. How
many grams of Na2CO3 must she add to 1.5L of freshly prepared
0.20M NaHCO3 to make the buffer? Ka of HCO3- is 4.7x10-11.
PLAN:
We know the Ka and the conjugate acid-base pair. Convert pH to

[H3O+], find the number of moles of carbonate and convert to mass.
SOLUTION:
[CO32-][H3O+]
HCO3-(aq) + H2O(l)
CO32-(aq) + H3O+(aq) Ka =
[HCO3-]
pH = 10.00; [H3O+] = 1.0x10-10
4.7x10-11 =
[CO32-](0.20)
1.0x10-10
moles of Na2CO3 = (1.5L)(0.094mols/L) = 0.14

0.14 moles
19-14
105.99g
mol
= 15 g Na2CO3
[CO32-] = 0.094M
Figure19.5
Colors and approximate pH range of some

common acid-base indicators.
pH
19-15
Figure19.6 The color change of the indicator bromthymol blue.
basic
acidic
19-16
change occurs
over ~2pH units
Figure19.7
19-17
Curve for a strong acid-strong base

titration.
Figure19.8
Titration of 40.00mL of 0.1000M HPr

with 0.1000M NaOH
Curve for a
weak acidstrong base
titration.
pKa of HPr =
4.89
pH = 8.80 at
equivalence point
[HPr] = [Pr-]
19-18
methylred
Sample Problem 19.3
Calculating the pH During a Weak AcidStrong Base Titration
PROBLEM:
Calculate the pH during the titration of 40.00 mL of 0.1000M

propanoic acid (HPr; Ka = 1.3x10-5) after adding the following
volumes of 0.1000M NaOH:
(a) 0.00mL
(b) 30.00mL (c) 40.00mL (d) 50.00mL
PLAN: The amounts of HPr and Pr- will be changing during the titration.
Remember to adjust the total volume of solution after each addition.
SOLUTION: (a) Find the starting pH using the methods of Chapter 18.
Ka = [Pr-][H3O+]/[HPr]
[Pr-] = x = [H3O+]
x (1.3x105)(0.10)
(b)
19-19
[Pr-] = x = [H3O+]
x = 1.1x10-3 ; pH = 2.96
Amount (mol)
HPr(aq) + OH-(aq)
Before addition
Addition
0.04000
0.03000
After addition
0.01000
Pr-(aq) + H2O (l)

0
0.03000
Sample Problem 19.3
Calculating the pH During a Weak AcidStrong Base Titration
continued
[H3O+] = 1.3x10-5
0.001000 mol
0.003000 mol
= 4.3x10-6M
pH = 5.37
(c) When 40.00mL of NaOH are added, all of the HPr will be reacted and the [Pr -]
will be
(0.004000 mol)
= 0.05000M
(0.004000L) + (0.004000L)
Ka x Kb = Kw
[H3O+] = Kw /
Kb = Kw/Ka = 1.0x10-14/1.3x10-5 = 7.7x10-10

K bx[Pr=] 1.6x10-9M
pH = 8.80
(d) 50.00mL of NaOH will produce an excess of OH-.

mol XS base = (0.1000M)(0.05000L - 0.04000L) = 0.00100mol
[H3O+] = 1.0x10-14/0.01111 = 9.0x10-11M
pH = 12.05
19-20
M = (0.00100)
(0.0900L)
M = 0.01111
Figure19.9
Titration of 40.00mL of 0.1000M NH3

with 0.1000M HCl
pKa of NH4+ =
9.25
Curve for a
weak basestrong acid
titration.
19-21
pH = 5.27 at
equivalence
point
Ion-Product Expression (Qsp)

and Solubility Product Constant (Ksp)
For the hypothetical compound, MpXq
At equilibrium
19-22
Qsp = [Mn+]p [Xz-]q = Ksp
Sample Problem 19.4
Writing Ion-Product Expressions for Slightly

Soluble Ionic Compounds
PROBLEM: Write the ion-product expression for each of the following:

(a) Magnesium carbonate
(c) Calcium phosphate
(b) Iron (II) hydroxide

(d) Silver sulfide
PLAN: Write an equation which describes a saturated solution. Take

note of the sulfide ion produced in part (d).
SOLUTION:
(a) MgCO3(s)
Mg2+(aq) + CO32-(aq)
(b) Fe(OH)2(s)
Fe2+(aq) + 2OH- (aq)
(c) Ca3(PO4)2(s)
(d) Ag2S(s)
3Ca2+(aq) + 2PO43-(aq)
Ksp = [Fe2+][OH-] 2
Ksp = [Ca2+]3[PO43-]2
2Ag+(aq) + S2-(aq)
S2-(aq) + H2O(l)
Ag2S(s) + H2O(l)
19-23
Ksp = [Mg2+][CO32-]
HS-(aq) + OH-(aq)
Ksp = [Ag+]2[HS-][OH-]
2Ag+(aq) + HS-(aq) + OH-(aq)
Table 19.2 Solubility-Product Constants (Ksp) of Selected Ionic

Compounds at 250C
Name, Formula
19-24
Ksp
Aluminum hydroxide, Al(OH)3
3 x 10-34
Cobalt (II) carbonate, CoCO3
1.0 x 10-10
Iron (II) hydroxide, Fe(OH)2
4.1 x 10-15
Lead (II) fluoride, PbF2
3.6 x 10-8
Lead (II) sulfate, PbSO4
1.6 x 10-8
Mercury (I) iodide, Hg2I2
4.7 x 10-29
Silver sulfide, Ag2S
8 x 10-48
Zinc iodate, Zn(IO3)2
3.9 x 10-6
Sample Problem 19.5
Determining Ksp from Solubility
PROBLEM: (a) Lead (II) sulfate is a key component in lead-acid car batteries.
Its solubility in water at 250C is 4.25x10-3g/100mL solution. What is
the Ksp of PbSO4?
(b) When lead (II) fluoride (PbF2) is shaken with pure water at 250C,
the solubility is found to be 0.64g/L. Calculate the Ksp of PbF2.
PLAN:
Write the dissolution equation; find moles of dissociated ions;

convert solubility to M and substitute values into solubility product
constant expression.
SOLUTION: (a) PbSO4(s)
Pb2+(aq) + SO42-(aq)
4.25x10-3g
1000mL
mol PbSO4
100mL soln
303.3g PbSO4
Ksp = [Pb2+][SO42-] = (1.40x10-4)2 =
19-25
Ksp = [Pb2+][SO42-]
= 1.40x10-4M PbSO4
1.96x10-8
Sample Problem 19.5
Determining Ksp from Solubility
continued
(b) PbF2(s)
0.64g
L soln
Pb2+(aq) + 2F-(aq)
mol PbF2
245.2g PbF2
= 2.6x10-3 M
Ksp = (2.6x10-3)(5.2x10-3)2 =
19-26
7.0x10-8
Ksp = [Pb2+][F-]2
Sample Problem 19.6
Determining Solubility from Ksp
PROBLEM: Calcium hydroxide (slaked lime) is a major component of mortar,

plaster, and cement, and solutions of Ca(OH)2 are used in
industry as a cheap, strong base. Calculate the solubility of
Ca(OH)2 in water if the Ksp is 6.5x10-6.
PLAN:
Write out a dissociation equation and Ksp expression; Find the molar
solubility (S) using a table.
SOLUTION:
Ca(OH)2(s)
Concentration (M)
Ca2+(aq) + 2OH-(aq)
Ca(OH)2(s)
Ksp = [Ca2+][OH-]2
Ca2+(aq) + 2OH-(aq)
Initial
Change
+S
+ 2S
Equilibrium
2S
Ksp = (S)(2S)2
S=
6
3 6.5x10
19-27
= 1.2x10x-2M
Table 19.3 Relationship Between Ksp and Solubility at 250C

No. of Ions
19-28
Formula
Cation:Anion
Ksp
Solubility (M)
MgCO3
1:1
3.5 x 10-8
1.9 x 10-4
PbSO4
1:1
1.6 x 10-8
1.3 x 10-4
BaCrO4
1:1
2.1 x 10-10
1.4 x 10-5
Ca(OH)2
1:2
5.5 x 10-6
1.2 x 10-2
BaF2
1:2
1.5 x 10-6
7.2 x 10-3
CaF2
1:2
3.2 x 10-11
2.0 x 10-4
Ag2CrO4
2:1
2.6 x 10-12
8.7 x 10-5
Figure19.10
The effect of a common ion on solubility.
CrO42- added
PbCrO4(s)
19-29
Pb2+(aq) + CrO42-(aq)
PbCrO4(s)
Pb2+(aq) + CrO42-(aq)
Sample Problem 19.7
Calculating the Effect of a Common Ion on

Solubility
PROBLEM: In Sample Problem 19.6, we calculated the solubility of Ca(OH)2

in water. What is its solubility in 0.10M Ca(NO3)2? Ksp of
Ca(OH)2 is 6.5x10-6.
PLAN: Set up a reaction equation and table for the dissolution of Ca(OH)2.
The Ca(NO3)2 will supply extra [Ca2+] and will relate to the molar
solubility of the ions involved.
SOLUTION:
Concentration(M)
Ca(OH)2(s)
Initial
0.10
Change
+S
+2S
Equilibrium
0.10 + S
2S
Ksp = 6.5x10-6 = (0.10 + S)(2S)2 = (0.10)(2S)2

S=
19-30
Ca2+(aq) + 2OH-(aq)
6.5x106
4
= 4.0x10-3
S << 0.10
Check the assumption:

4.0x10-3
0.10M
x 100 = 4.0%
Figure19.11
19-31
Test for the presence of a carbonate.
Sample Problem 19.8
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 these ionic compounds:
(a) Lead (II) bromide
(b) Copper (II) hydroxide
(c) Iron (II) sulfide
PLAN: Write dissolution equations and consider how strong acid would affect
the anion component.
SOLUTION: (a) PbBr2(s)
Pb2+(aq) + 2Br-(aq) Br- is the anion of a strong acid.

No effect.
(b) Cu(OH)2(s)
Cu2+(aq) + 2OH-(aq)
OH- is the anion of water, which is a weak acid. Therefore it will shift the
solubility equation to the right and increase solubility.
(c) FeS(s)
Fe2+(aq) + S2-(aq)
FeS(s) + H2O(l)
S2- is the anion of a weak acid and will

react with water to produce OH-.
Fe2+(aq) + HS-(aq) + OH-(aq)
Both weak acids serve to increase the solubility of FeS.
19-32
Sample Problem 19.9

PROBLEM:
PLAN:
Predicting Whether a Precipitate Will Form
A common laboratory method for preparing a precipitate is to mix

solutions of the component ions. Does a precipitate form when
0.100L of 0.30M Ca(NO3)2 is mixed with 0.200L of 0.060M NaF?
Write out a reaction equation to see which salt would be formed. Look
up the Ksp valus in a table. Treat this as a reaction quotient, Q,
problem and calculate whether the concentrations of ions are > or <
Ksp. Remember to consider the final diluted solution when calculating
concentrations.
SOLUTION:
CaF2(s)
Ca2+(aq) + 2F-(aq)
Ksp = 3.2x10-11
mol Ca2+ = 0.100L(0.30mol/L) = 0.030mol
[Ca2+] = 0.030mol/0.300L = 0.10M
mol F- = 0.200L(0.060mol/L) = 0.012mol
[F-] = 0.012mol/0.300L = 0.040M
Q = [Ca2+][F-]2 =
(0.10)(0.040)2 = 1.6x10-4
Q is >> Ksp and the CaF2 WILL precipitate.
19-33
Figure19.12
19-34
Formation of acidic precipitation.
Figure19.13
19-35
Cr(NH3)63+, a typical complex ion.
Figure19.14
The stepwise exchange of NH3 for H2O in M(H2O)42+.
NH3
M(H2O)42+
3NH3
M(H2O)3(NH3)2+
M(NH3)42+
19-36
Sample Problem 19.10
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), through formation of the complex ion
Ag(S2O3)23-. Calculate the solubility of AgBr in (a) H2O; (b) 1.0M
hypo. Kf of Ag(S2O3)23- is 4.7x1013 and Ksp AgBr is 5.0x10-13.
PLAN: Write equations for the reactions involved. Use Ksp to find S, the molar
solubility. Consider the shifts in equilibria upon the addition of the
complexing agent.
SOLUTION:
AgBr(s)
Ag+(aq) + Br-(aq)
(a) S = [AgBr]dissolved = [Ag+] = [Br-]

(b)
19-37
AgBr(s)
Ksp = [Ag+][Br-] = 5.0x10-13
Ksp = S2 = 5.0x10-13 ; S = 7.1x10-7M

Ag+(aq) + Br-(aq)
Ag+(aq) + 2S2O32-(aq)
Ag(S2O3)23-(aq)
AgBr(s) + 2S2O32-(aq)
Br -(aq) + Ag(S2O3)23-(aq)
Sample Problem 19.10
Calculating the Effect of Complex-Ion Formation

on Solubility
continued
Koverall = Ksp x Kf =
Concentration(M)
[Br-][Ag(S2O3]23[AgBr][S2O32-]2
AgBr(s) + 2S2O32-(aq)
Br-(aq) + Ag(S2O3)23-(aq)
Initial
1.0
Change
-2S
+S
+S
Equilibrium
1.0-2S
Koverall =
S2
(1.0-2S)2
= 24
1.0-2S
S = [Ag(S2O3)23-] = 0.45M
19-38
= (5.0x10-13)(4.7x1013) = 24
= (24)1/2

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Ionic Equilibria in Aqueous Systems

19.1 Equilibria of Acid-Base Buffer Systems

19.2 Acid-Base Titration Curves

19.3 Equilibria of Slightly Soluble Ionic Compounds

19.4 Equilibria Involving Complex Ions

The effect of addition of acid or base to

How a buffer works.

Buffer after addition of H3O+

Buffer with equal

Buffer after addition of OH-

Sample Problem 19.1

Calculating the Effect of Added H3O+ or OHon Buffer pH

(a) of a buffer solution consisting of 0.50M CH3COOH and 0.50M CH3COONa

Sample Problem 19.1

Calculating the Effect of Added H3O+ and OHon Buffer pH

Check the assumption:

1.8x10-5/0.50 X 100 = 3.6x10-3 %

CH3COO-(aq) + H2O (l)

Sample Problem 19.1

Calculating the Effect of Added H3O+ and OHon Buffer pH

Set up a reaction table with the new values.

Concentration (M) CH3COO-(aq) + H3O+(aq)

CH3COOH(aq) + H2O (l)

Sample Problem 19.1

Set up a reaction table with the new values.

Calculating the Effect of Added H3O+ and OHon Buffer pH

The Henderson-Hasselbalch Equation

H3O+ + A[H3O+] [A-]

- log[H3O+] = - log Ka + log

Buffer Capacity and Buffer Range

The relation between buffer capacity and pH change.

1. Choose the conjugate acid-base pair.

2. Calculate the ratio of buffer component concentrations.

3. Determine the buffer concentration.

4. Mix the solution and adjust the pH.

Sample Problem 19.2

An environmental chemist needs a carbonate buffer of pH 10.00

We know the Ka and the conjugate acid-base pair. Convert pH to

moles of Na2CO3 = (1.5L)(0.094mols/L) = 0.14

Colors and approximate pH range of some

Figure19.6 The color change of the indicator bromthymol blue.

Curve for a strong acid-strong base

Titration of 40.00mL of 0.1000M HPr

Sample Problem 19.3

Calculating the pH During a Weak AcidStrong Base Titration

Calculate the pH during the titration of 40.00 mL of 0.1000M

Pr-(aq) + H2O (l)

Sample Problem 19.3

Calculating the pH During a Weak AcidStrong Base Titration

Kb = Kw/Ka = 1.0x10-14/1.3x10-5 = 7.7x10-10

(d) 50.00mL of NaOH will produce an excess of OH-.

Titration of 40.00mL of 0.1000M NH3

Ion-Product Expression (Qsp)

Qsp = [Mn+]p [Xz-]q = Ksp

Sample Problem 19.4

Writing Ion-Product Expressions for Slightly

PROBLEM: Write the ion-product expression for each of the following:

(b) Iron (II) hydroxide

PLAN: Write an equation which describes a saturated solution. Take

Fe2+(aq) + 2OH- (aq)

2Ag+(aq) + HS-(aq) + OH-(aq)

Table 19.2 Solubility-Product Constants (Ksp) of Selected Ionic