Chapter 17:

Additional Aqueous
Equilibria
Chemistry the Central Science,
12
th
ed

Dr. Stacey Gulde
1
Common-Ion Effect
Common ion effect shift in equilibrium caused
by adding an ion involved in the equilibrium
AKA Le Chteliers Principle


If add NaC
2
H
3
O
2
, what happens?
C
2
H
3
O
2
-
causes equilibrium to shift
Thus, [H
+
] decrease & pH becomes more basic

Dissociation of a weak electrolyte (ie. HC
2
H
3
O
2
) decreases
when a strong electrolyte (ie. NaC
2
H
3
O
2
) containing a
common ion (ie. C
2
H
3
O
2
-
) is added
2
) ( ) ( (aq)
2 3 2 2 3 2
aq O H C aq H O H HC
+
+
C
2
H
3
O
2
-

Na
+

breaks up into ions
Sample Problems
1. Calculate the pH of a 0.50M HF solution.
3
) (aq HF
I
C
E
0.50M
0 0
x x -x
0.50 x x x
4
10 8 . 6

= x
] 50 . 0 [
] ][ [
x
x x
K
a

=
] 50 . 0 [
] [
10 8 . 6
2
4
x
x =

M x 018 . 0 =
] [
+
= H
100
] 50 . 0 [
] 018 . 0 [
% x I =
% 6 . 3 % = I
(Assumption OK)
] 018 . 0 log[ = pH
74 . 1 = pH
Check 5% Rule:
Appendix D
Ignore x
(W. Acid)
) ( ) ( aq F aq H
+
+
Sample Problems
2. Calculate the pH of a 0.50M HF solution when 0.10M
NaF is added.
4
4
10 8 . 6

= x
] 50 . 0 [
] 10 . 0 ][ [
x
x x
K
a

+
=
] 50 . 0 [
] 10 . 0 ][ [
10 8 . 6
4
x
x =

M x 0034 . 0 = ] [
+
= H
100
] 50 . 0 [
] 0034 . 0 [
% x I =
% 68 . 0 % = I
] 0034 . 0 log[ = pH
47 . 2 = pH
More basic
) ( ) ( ) ( aq F aq H aq HF
+
+
I
C
E
0.50M
0 0.10M
x x -x
0.50 x 0.10+x x
Ignore x
(W. Acid)
(Common
Ion)
[HF] only:
pH=1.74
Buffer
Solutions
Buffers weak acid/base & conjugate acid/base (salt)
Should have similar concentrations
Sample Prob. #2: 0.50M HF with 0.10M NaF

Natural buffers:
Human blood maintains pH of 7.4
Seawater maintains pH of 8.1-8.3

Calculating pH of a buffer:
Previous sample problem #2 (pH=2.47)
OR use Henderson-Hasselbalch eq. (H-H eq)
5
) ( ) ( ) ( aq F aq H aq HF
+
+
(W. Acid)
(CB)
Henderson-Hasselbalch Eq


Sample Problem #2 Revisited: Calculate pH of a
0.50M HF solution when 0.10M NaF is added.
6
| |
| | acid
base
pK pH
a
log + =
) ( ) ( ) ( aq F aq H aq HF
+
+
K
a
= 6.8x10
-4

4
10 8 . 6 log

= x pH
47 . 2 = pH
| |
| | 50 . 0
10 . 0
log +
70 . 0 17 . 3 =
0.50M
0.10M
Adding Strong Acids/Bases
to a Buffer Solutions
Buffer Purpose: resist pH change when limited
amounts of strong acid or base is added
Lab Exp. 18

How happen:
Added acid or base reacts w/something in the buffer
Added acid or base is limiting

Ex. Buffer:
7
Buffer Demo
HA
A
-

Buffered soln
) ( ) ( ) ( aq A aq H aq HA
+
+
(W. Acid)
(CB)
Adding a substance:
1. H
+
added: REACTS w/ ____ in buffer
Producing more ____




2. OH
-
added: REACTS w/ ____ in buffer
Producing more ____
8
HA
A
-

Buffered soln
) ( ) ( ) ( aq A aq H aq HA
+
+
(W. Acid)
(CB)
H
+
(aq) + A
-
(aq) HA

(aq)
HA
A
-

Buffered soln
OH
-
(aq) + HA

(aq) A
-
(aq)
HA
A
-

HA
A
-

A
-

HA
HA
A
-

+ H
2
O(l)
Adding Strong Acid/Base
to a Buffer Solution
If the added acid/base is strong, it is ALL used up

To calculate pH you use:
a) ICE (must use MOLES!)
b) H-H eq. (must use M)
9
Sample Problems
1. Calculate the pH of a 1.0L solution containing 0.10M NaF &
0.50M HF, when 9.5mL of 2.1M HCl is added.
(assume minimal/no volume change)
HF
(0.50M)
NaF
(0.10M)
&
1.0L Soln
already made
BUFFER!
Buffer:
0.50M 0.10M
H
+
(aq) + F
-
(aq) HF

(aq)
ADD HCl
H
+
(aq)
RXN:
+ F
-
(aq) HF

(aq)
Added: H
+
(aq) reacts w/
W. Acid!
Sample Problems
1. Calculate the pH of a 1.0L solution containing 0.10M NaF &
0.50M HF, when 9.5mL of 2.1M HCl is added.
(assume minimal/no volume change)
+0.020 -0.020
0.08mol 0.52mol
-0.020
0
I
C
E
a) ICE Stoichiometry: (MOLES)
Change by lower reactant value
(0.10M)(1.0L) (2.1M)(0.0095L)
0.10mol 0.020 mol
(0.50M)(1.0L)
0.50mol
1.0L
1.0L
b) H-H: (M)
| |
| | Acid
Base
pK pH
a
log + =
4
10 8 . 6 log

= x pH
81 . 0 17 . 3 = pH
36 . 2 = pH
52 . 0
08 . 0
log +
H
+
(aq) + F
-
(aq) HF

(aq)
RXN:
Sample Problems
2. Calculate the pH of a 1.0L solution containing 0.10M NaF &
0.50M HF, when 9.5mL of 2.1M NaOH is added.
(assume minimal/no volume change)
12
Buffer=
a) ICE Stoich.: (MOLES)
b) H-H eq (M)
0
+0.020 0 -0.020
0.48mol 0.12mol 0
-0.020
0
I
C
E
(0.50M)(1.0L) (2.1M)(0.0095L)
0.50mol 0.020 mol
(0.10M)(1.0L)
0.10mol
1.0L 1.0L
0.50M 0.10M
| |
| | Acid
Base
pK pH
a
log + =
4
10 8 . 6 log

= x pH
48 . 0
12 . 0
log +
60 . 0 17 . 3 = pH
57 . 2 = pH
OH
-
(aq) + HF

(aq)
+ F
-
(aq) H
2
O

(l)
H
+
(aq) + F
-
(aq) HF

(aq)
Added: OH
-
(aq) reacts w/
pH Comparison
0.50M HF: pH = 1.74

Buffer 0.50M HF & 0.10M NaF: pH = 2.47
pH inc. (more basic) due presence of a common ion

Buffer 0.50M HF & 0.10M NaF w/added 9.5mL of
2.1M HCl: pH = 2.35
pH dec. (more acidic) due addition of acid

Buffer 0.50M HF & 0.10M NaF w/added 9.5mL of
2.1M NaOH: pH = 2.59
pH inc. (more basic) due addition of base 13
Sample Problem
(What if Volume changes?)
1. Calculate the pH of a solution formed by mixing 65mL of
0.20M NH
4
Cl with 75mL of 0.15M NH
3
. W. Base!
NH
3

NH
4
Cl
NH
3

NH
4
Cl
and
75mL
0.15M
65mL
0.20M
65mL+75mL
??M
Buffer:
To Find Initial:
Convert original M to moles,
then back to
M using Total Vol
=140.mL
Sample Problem
(What if Volume changes?)
1. Calculate the pH of a solution formed by mixing 65mL of
0.20M NH
4
Cl with 75mL of 0.15M NH
3
.
BUFFER, MUST use ICE table!!
15
) ( NH
4
aq
+
0
-x
0.093+x 0
+x
0.080-x
I
C
E
(0.20M)(065L) (0.15M)(0.075L)
0.013mol 0.01125 mol
0.140L
) ( NH
3
+ aq O(l) H
2
0
0
0.140L
0.080M 0.093M
+x
x
5
10 8 . 1

= x
] 080 . 0 [
] ][ 093 . 0 [
x
x x
K
b

+
=
] 080 . 0 [
] ][ 093 . 0 [
10 8 . 1
5 x
x =

M x x
5
10 5 . 1

=
] [

= OH
W. Base!
) ( OH aq

+
Sample Problem
(What if Volume changes?)
1. Calculate the pH of a solution formed by mixing 65mL of
0.20M NH
4
Cl with 75mL of 0.15M NH
3
.
BUFFER, MUST use ICE table!!
16
) ( NH
4
aq
+
0
-x
0.093+x 0
+x
0.080-x
I
C
E
(0.20M)(065L) (0.15M)(0.075L)
0.013mol 0.01125 mol
0.140L
) ( NH
3
+ aq O(l) H
2
0
0
0.140L
0.080M 0.093M
+x
x
W. Base!
) ( OH aq

+ 100
080 . 0
10 5 . 1
%
5
x
x
I

=
% 019 . 0 % = I
] 10 5 . 1 log[
5
= x pOH
82 . 4 = pOH
82 . 4 00 . 14 = pH
18 . 9 = pH
Sample Problem (Volume changes?)
2. Calculate the pH of a solution formed by mixing 65mL of
0.20M NH
4
Cl with 75mL of 0.15M NH
3
& adding 15.3mL
of 0.17M NaOH.
17
O(l) H ) ( NH
2 3
+ aq
-0.0026 -0.0026
0.01385mol 0mol
+0.0026
0.0104mol
I
C
E
(0.15M)(075L) (0.20M)(0.065L)
0.01125mol 0.013 mol
0.155L
) ( NH
4
+
+
aq
) ( OH
-
aq
0
V
T
=65mL+75mL+15.3mL=155.mL
0.155L
0
0
a) ICE Stoich: (MOLES)
(0.17M)(0.0153L)
0.0026 mol
0.00671M 0.0894M
b) H-H: (M)
| |
| | Acid
Base
pK pH
a
log + =
( )( )
14
10 1

= x K K
b a
( )( )
14 5
10 1 10 8 . 1

= x x K
a
10
10 6 . 5

= x K
a
Try on own
Buffer=
Added: OH
-
(aq) reacts w/
0.15M 0.20M
NH
4
+
(aq) + OH
-
(aq) NH
3
(aq) + H
2
O(aq)
(NH
3
is a base, K
b
= 1.8x10
-5
)
Must solve for K
a
Sample Problem (Volume changes?)
2. Calculate the pH of a solution formed by mixing 65mL of
0.20M NH
4
Cl with 75mL of 0.15M NH
3
& adding 15.3mL
of 0.17M NaOH.
18
O(l) H ) ( NH
2 3
+ aq
-0.0026 -0.0026
0.01385mol 0mol
+0.0026
0.0104mol
I
C
E
(0.15M)(075L) (0.20M)(0.065L)
0.01125mol 0.013 mol
0.155L
) ( NH
4
+
+
aq
) ( OH
-
aq
0
V
T
=65mL+75mL+15.3mL=155.mL
0.155L
0
0
a) ICE Stoich: (MOLES)
(0.17M)(0.0153L)
0.0026 mol
0.00671M 0.0894M
b) H-H: (M)
| |
| | Acid
Base
pK pH
a
log + =
Try on own
Buffer=
Added: OH
-
(aq) reacts w/
0.15M 0.20M
NH
4
+
(aq) + OH
-
(aq) NH
3
(aq) + H
2
O(aq)
125 . 0 25 . 9 + = pH
| |
| | 0671 . 0
0894 . 0
log +
38 . 9 = pH
10
10 6 . 5 log

= x pH
Buffer Capacity
Buffer Capacity amount of acid/base added
before a significant pH change occurs
In demo video: needed to count drops of NaOH added
Took ~30 drops to turn green
Took ~35 drops to turn blue/violet

Depends on conc. of acid/base used to prepare buffer
Which has a greater buffering capacity?
19
1 M HF & 1 M NaF
0.1 M HF & 0.1 M NaF
More initial acid/base
to react with
added acid/base
Buffer Range
Buffer range - pH range where buffer is effective
Want conc. of acid/base & conjugate to be similar
Ex: 0.50M HF & 0.10M NaF

If conc of 1 component in buffer is > 10x the conc of the
other, buffering action is poor

Choose an acid whose pKa is close to the desired pH
20
pKa of unit pH 1 Range =
Questions:
1. Which of the following will have the worst buffering
range?

A. 0.1M HA and 0.1M A
-

B. 0.2M HA and 0.1M A
-

C. 0.1M HA and 1.5M A
-

D. 1.0M HA and 1.0M A
-


21
Difference is
more than 10x
Questions:
2. You wish to make a buffered solution with a pH=7.0,
which acid will be the best to use?

A. HNO
2
: K
a
= 4.5x10
-4
pK
a
= 3.35

B. HClO: K
a
= 3.0x10
-8
pK
a
= 7.52
C. H
3
PO
4
: K
a
= 7.5x10
-3
pK
a
= 2.12
D. H
2
CO
3
: K
a
= 4.3x10
-7
pK
a
= 6.37
E. HBrO: K
a
= 2.5x10
-9
pK
a
= 8.60

22
Acid/Base Titration
Introduced in Chapter 4

Indicators chemicals that change
color when a solution turns from
acidic to basic

Phenolphthalein
Acid = Clear
Base = Pink
23
Acid/Base Titration
Titration Curve pH vs. volume of titrant added
Titrant - liquid in buret



Equivalence Point stoichiometric # of moles of acid =
# mols base reacted

Endpoint where indicator changes color permanently
Just past the equivalence point
24
Titration
Curve
Equiv. pt
Endpt
pH at Various
Titration Points
2 types of titrations
1. Strong/Strong
2. Weak/Strong

What is happening to pH @ 4 different points
A. Initial pH
B. Before equivalence pt
C. @ equivalence pt
D. After equivalence pt
25
pH at Various
Titration Points
1. Strong Acid
&
Strong Base
26
1. Strong Acid - Strong Base:
(NaOH added to HCl)
A. Initial pH: before adding base
No NaOH added, only HCl present
pH = Very acidic
B. Before equivalence pt:
HCl & NaOH react
Base limiting
Acid excess
pH = slowly more basic,
b/c less acid in excess
Raises rapidly near
equivalence pt.
27
) ( l(aq) a ) ( a ) (
2
l O H C N aq OH N aq HCl + +
A
100mL
0.50M
?mL
0.10M
pH=0.30
B
pH=0.44
pH=2.17
C. At equivalence pt: HCl & NaOH react
Moles acid = Moles of base
Completely Neutralized
pH = 7.00

How get pH when only
NaCl & H
2
O present?
- Water dissociates
28
C
H
2
O (l) H
+
(aq) + OH
-
(aq)
14
10 1

= x K
w
M 10 1 ] OH [ ] H [
7 +
= = x
1. Strong Acid-Strong Base:
(NaOH added to HCl)
pH=7.00
) ( l(aq) a ) ( a ) (
2
l O H C N aq OH N aq HCl + +
100mL
0.50M
?mL
0.10M
D. After equivalence pt: HCl & NaOH react
Acid limiting
Completely consumed
Base excess
pH = slowly more basic
29
D
1. Strong Acid-Strong Base:
(NaOH added to HCl)
) ( l(aq) a ) ( a ) (
2
l O H C N aq OH N aq HCl + +
100mL
0.50M
?mL
0.10M
pH=11.82
pH=13.20
mL NaOH pH
0 0.30
10.0 0.44
49.0 2.17
50.0 7.00
51.0 11.82
80.0 13.22

1. Strong Acid - Strong Base
Summary: (NaOH is added to HCl)

Why does pH change drastically near equivalence point ()?
pH dependent on MOLES present AFTER reaction!
At equivalence point:
+
=
OH H
n n
1
2
3
4
MOLES present AFTER reacting
0.050
0.040
0.001
0
0
0
0
0
0
0
0.001
0.030

O H NaCl NaOH HCl
2
+ +
1. Strong Acid - Strong Base
Summary: (NaOH is added to HCl)
Step
mL
NaOH
n H
+
(after rxn)
n OH
-

(after rxn)

1 0
2 10.0
2 49.0
3 50.0
4 51.0
4 80.0
What does a
Strong Base-Strong Acid
Titration Look Like?
Question:
Where is the end point for the following titration
curve?
33
pH at Various
Titration Points
2. Weak Acid
&
Strong Base
34
A. Initial pH: before adding base
No NaOH added, only HC
2
H
3
O
2
present
pH = acidic


35
A
) ( ) ( (aq) (aq)
2 2 3 2 2 3 2
l O H aq O H C OH O H HC + +

2. Weak Acid - Strong Base:

(NaOH added to HC
2
H
3
O
2
)
100mL
0.50M
?mL
0.10M
pH=2.52
B. Before equivalence pt: HC
2
H
3
O
2
& NaOH react
Base limiting
Acid excess
pH = slowly more basic,
b/c less acid in excess
Raises rapidly near
equivalence pt.

A BUFFER soln!
HC
2
H
3
O
2
& conjugate
base (C
2
H
3
O
2
-
) present

36
B
O H O H C OH O H HC
2 2 3 2 2 3 2
+ +

2. Weak Acid - Strong Base:

(NaOH added to HC
2
H
3
O
2
)
100mL
0.50M
?mL
0.10M
pH=5.69
C. At equivalence pt: HC
2
H
3
O
2
& NaOH react
Moles acid = Moles of base

NOT completely neutralized!!
Have conjugate base (C
2
H
3
O
2
-
)

pH > 7
37
C
) ( OH ) ( O H HC O(l) H ) ( O H C
2 3 2 2 2 3 2
aq aq aq

+ +
O H O H C OH O H HC
2 2 3 2 2 3 2
+ +

2. Weak Acid - Strong Base:

(NaOH added to HC
2
H
3
O
2
)
100mL
0.50M
?mL
0.10M
pH=9.25
D. After equivalence pt: HC
2
H
3
O
2
& NaOH react
Acid limiting
Completely consumed
Base excess
pH = gets more basic
D
O H O H C OH O H HC
2 2 3 2 2 3 2
+ +

2. Weak Acid - Strong Base:

(NaOH added to HC
2
H
3
O
2
)
100mL
0.50M
?mL
0.10M
pH=11.82
pH=13.20
0 20 40 60 80 100
0
2
4
6
8
10
12
14
p
H
Volume of NaOH added (mL)
Titration Curve
Comparisons
1. Initial pH:
S/S is lower, more acidic
Dissociates completely
more H
+
in soln

2. After Equivalence:
Curves are the same
Amount of excess
OH
-
is the same
W. acid S. base
S. acid S. base
0 20 40 60 80 100
0
2
4
6
8
10
12
14
p
H
Volume of NaOH added (mL)
Titration Curve
Comparisons
3. @ Equivalence point:
S/S more rapid rise

Volume needed is same


pH different
S/S = 7.00
W/S > 7
- b/c conjugate base
present
V
NaOH
(HAc) = V
NaOH
(HCl)


W. acid S. base
S. acid S. base
0 20 40 60 80 100
0
2
4
6
8
10
12
14
p
H
Volume of NaOH added (mL)
Titration Curve
Comparisons
4. Before Equivalence point:

W/S is a buffered soln!

Acid & conjugate base
present
Titration
Comparison
(extra)
W. acid S. base
S. acid S. base
Titration Curve
Comparisons
Differences more pronounced, the weaker the acid
Weaker acids have more basic equivalence points

Can determine K
a
of a
weak acid from the
titration curve
In a buffered system:



| |
| | Acid
Base
pK pH
a
log + =
0
a
pK pH =
Titration of
Polyprotic Acids
Polyprotic acid contains 1 or more ionizable H
atoms
Ex:
H
3
PO
3
=
H
2
C
4
H
4
O
6
=

Ionization occurs 1 H atom at a time,
thus multiple equivalence pts exist
Ex: H
3
PO
3

43
3H
+

2H
+

H
2
PO
3
-
(aq)
H
2
PO
3
-
(aq) HPO
3
2-
(aq)
(aq) H (aq) PO H
3 3
+
+
(aq) H +
+
Titrating w/Indicators
How do you know what indicator to use?
Ideally it should change at/near the equivalence pt.

Since pH changes so fast here, as long indicator changes
anywhere on rapid rise of titration curve, all is ok
44

Titrating w/Indicators
Are the following good indicators for the titration
shown?
45
1. Phenolphthalein: 2. Methyl Red:
Yes, change color
in rapid rise
No, doesnt change color
in rapid rise
Titrating w/Indicators
What if not given a picture diagram for color change?

Indicators are acids thus have a K
a




Indicators change color when pH of the system equals
their pKa!
Want pKa of Indicator to be as close to pH of
endpoint/equivalence as possible
46
+
+Ind H HInd
Color 1 Color 2
Questions:
1. Which indicators would work for the titration shown?
47
Both,
b/c on rapid decline
Questions:
2. A laboratory worker is titrating an unknown solution of a
weak acid with a strong base. Which indicator should
they choose given the following titration curve?
A. Pentamethoxy red: pKa = 1.8
B. Congo red: pKa = 4.0
C. Azolitmin: pKa = 6.5
D. Phenolphthalein: pKa = 9.0
E. Trinitrobenzoic acid: pKa = 12.7
48
Solubility Equilibria
Some ions when combined form insoluble salts
Precipitation Rxns (Chap 4, solubility Rules)

Saturated solution contains undissolved solute
However, some does dissolve (SLIGHTLY!)


49
PbI
2

Solubility Equilibria
Solubility-Product Constant, K
sp
equilibrium
constant for a slightly soluble (or nearly insoluble)
ionic compound
Degree to which a solid is soluble in water



NO solids or liquids in equilibrium expression!
Appendix D
50
) ( 2I ) ( Pb (s) PbI
2
2
aq aq
+
+
2 2
sp
] ][I [Pb K
+
=
5
10 7 . 1

= x
Sample Problem
If 0.0012 mols PbI
2
(s) dissolves in 1.0 L water, what is
its K
sp
value?
51
2 2
] ][ [
+
= I Pb K
sp
0.0012M 0 0
2(0.0012) 0.0012 -0.0012
0M 0.0012M 0.0024M
2
] 0024 . 0 ][ 0012 . 0 [ =
sp
K
9
10 9 . 6

= x K
sp
I
C
E
) ( 2I ) ( Pb (s) PbI
2
2
aq aq
+
+
52
Solubility vs.
Solubility Product, K
sp

Solubility grams dissolved to form a saturated
solution
Units = grams/L

Molar Solubility moles dissolved to form a
saturated solution
Units = mols/L

K
sp
equilibrium constant for ionic solid & its
saturated solution
53
Sample Problem
If the K
sp
of BaF
2
is 1.7x10
-6
, calculate the molar
solubility.
2 2
] ][ [
+
= F Ba K
sp
) ( 2 ) ( (s)
2
2
aq F aq Ba BaF
+
+
2 6
] 2 ][ [ 10 7 . 1 x x x =

3 6
4 10 7 . 1 x x =

M x x
3
10 5 . 7

=
[Ba
2+
]
1:1 ratio of Ba
2+
:BaF
2
,
molar solubility of BaCl
2
= 7.5x10
-3
M
x 0
0
2(x) +x
-x
0M
x
2x
I
C
E
Factors Affecting Solubility
1. Common Ion Effect Adding a common ion
decreases the solubility of the partially soluble salt
AKA Le Chteliers Principle



Adding BaCl
2
(Ba
2+
) or NaF (F
-
) shifts equilibrium
54
) ( 2 ) ( (s)
2
2
aq F aq Ba BaF
+
+
Sample Problem
What is the molar solubility of BaF
2
in 0.15M NaF?
55
) ( 2 ) ( (s)
2
2
aq F aq Ba BaF
+
+
0 0.15
x 2x
x 0.15+2x
2 2
] ][ [
+
= F Ba K
sp
=
6
10 7 . 1 x
2 6
] 15 . 0 ][ [ 10 7 . 1 x x =

M x x
5
10 56 . 7

=
I
C
E
2
] 2 15 . 0 ][ [ x x +
x
-x
0M
small
Just BaCl
2
= 7.5x10
-3
M
Decreased
Factors Affecting Solubility
2. pH: Almost any ionic compound will dissolve if the
pH of the solution is altered
Solubility increases if acid is added to a basic anion
Ex: Add HNO
3
to BaF
2
:

H
+
from HNO
3
reacts w/F
-
from BaF
2





Adding more acid (H
+
) shifts equilibrium
56
) (aq H
+
) ( aq F

+
) (aq HF 2 2
2
) ( 2 ) ( (aq) 2 ) (
2
2
aq HF aq Ba H s BaF + +
+ +
) ( 2 ) ( (s)
2
2
aq F aq Ba BaF
+
+
Factors Affecting Solubility
Complexes
3. In the presence of suitable Lewis bases, metal ions
can form complexes:
57
(aq) S (aq) Fe FeS(s)
2 2 +
+
( ) | | (aq) CN Fe (aq) 6CN (aq) Fe
- 4
6
2 +
+
K
sp
= 6.31x10
-18
K
f
= 1.00x10
35
( ) | | (aq) S (aq) CN Fe (aq) 6CN FeS(s)
- 2
- 4
6
+ +

K = 6.31x10
17
f for formation (of a complex).
More in Chapter 23, but will use this idea in Experiment 19!
Precipitation &
Separation of Ions
How do you know if a precipitate will form?
Need to compare K
sp
to your actual conditions Q
sp

IF:
Q
sp
= K
sp
: Equilibrium (saturated soln)
Q
sp
> K
sp
: Ppt occurs
Q
sp
< K
sp
: Dissolution occurs
58
Sample Problems
1. [Ca
2+
] in human blood is 0.0025M & Calcium oxalate (CaC
2
O
4
)
makes kidney stones. If K
sp
= 2.3x10
-9
for calcium oxalate,
will it ppt in a patient with [C
2
O
4
-2
] = 1.0x10
-6
?
59
] ][ [
2
4 2
2 +
= O C Ca Q
sp
] 10 0 . 1 ][ 0025 . 0 [
6
= x Q
sp
9
10 5 . 2

= x Q
sp
Q
sp
> K
sp

Not at equilibrium, use Q
sp

Ppt occurs & Kidney stones form (OUCH!!)
Sample exercises (in book)
17.15 & 17.16
very helpful!
) ( ) ( (s)
2
4 2
2
4 2
aq O C aq Ca O CaC

+
+
Sample Problems
2. A solution contains 1.0x10
-2
M Ag
+
& 2.0x10
-2
M Pb
2+
.
When Cl
-
is added, both AgCl (K
sp
=1.8x10
-10
) & PbCl
2

(K
sp
=1.7x10
-5
) can precipitate. Which precipitates first?
60
] ][ [
+
= Cl Ag K
sp
2 2
] ][ [
+
= Cl Pb K
sp
Solve for [Cl
-
]
=
10
10 8 . 1 x
8
10 8 . 1 ] [

= x Cl
2 2 5
] ][ 10 0 . 2 [ 10 7 . 1

= Cl x x
2
10 9 . 2 ] [

= x Cl
Anything above this will ppt
AgCl ppt first, b/c smaller [Cl
-
]
] ][ 10 0 . 1 [
2
Cl x
Anything above this will ppt
Determines presence or
absence of metal ions

No info about amount

5 groups
1. Insoluble Cl
-

2. Insoluble Acid S
-

3. Insoluble Base S
-
&
OH
-

4. Insoluble PO
4
-3

5. Soluble alkali metal
& NH
4
+
ions

61
Qualitative Analysis
(selective precipitation)
(LAB 22)
Sample Question
1. Which ion will precipitate when
phosphate ion is added to a
solution containing all of the
ions below
A. K
+
B. Ba
2+

C. Na
+
D. NH
4
+

62
Summary Chap. 17
1. Common Ion Effect
2. Buffers:
Calculations
a) Ice Table
b) Henderson-Hasselbalch eq.
3. Adding Strong Acid or Base to a buffer
RXN occurs!
ICE table (MOLES)
H-H eq. (M)
4. Acid/Base Titration
S/S
S/W
Compare titration curves
5. Solubility equilibria
6. Qualitative analysis
| |
| | acid
base
pK pH
a
log + =