Acid-Base Equilibria

Chapter 16
The common ion effect is the shift in equilibrium caused by the
addition of a compound having an ion in common with the
dissolved substance.

The presence of a common ion suppresses

the ionization of a weak acid or a weak base.

Consider mixture of CH3COONa (strong electrolyte) and

CH3COOH (weak acid).
CH3COONa (s) Na+ (aq) + CH3COO- (aq)
common
ion
CH3COOH (aq) H+ (aq) + CH3COO- (aq)
16.2
 What is the pH of a solution containing 0.30 M HCOOH
and 0.52 M HCOOK?

Mixture of weak acid and conjugate base!

HCOOH (aq) H+ (aq) + HCOO- (aq)

Initial (M) 0.30 0.00 0.52
Change (M) -x +x +x
Equilibrium (M) 0.30 - x x 0.52 + x

Ka for HCOOH = 1.8 x 10 -4

x = 1.038 X 10 -4
[H+] [HCOO-]
Ka = pH = 3.98
[HCOOH]
16.2
 OR Use the Henderson-Hasselbach equation
Consider mixture of salt NaA and weak acid HA.
NaA (s) Na+ (aq) + A- (aq) [H+][A-] pK = -log K
Ka = a a
HA (aq) H+ (aq) + A- (aq) [HA]

Ka [HA]
[H ] =
+
[A-] Henderson-Hasselbach
[HA] equation
-log [H+] = -log Ka - log
[A-] [conjugate base]
- pH = pKa + log
-log [H ] = -log Ka + log
+ [A ] [acid]
[HA]
-
pH = pKa + log [A ]
[HA]

16.2
 What is the pH of a solution containing 0.30 M HCOOH
and 0.52 M HCOOK?

Mixture of weak acid and conjugate base!

HCOOH (aq) H+ (aq) + HCOO- (aq)

Initial (M) 0.30 0.00 0.52
Change (M) -x +x +x
Equilibrium (M) 0.30 - x x 0.52 + x
-
Common ion effect pH = pKa + log [HCOO ]
[HCOOH]
0.30 x 0.30
[0.52]
0.52 + x 0.52 pH = 3.77 + log = 4.01
[0.30]
HCOOH pKa = 3.77
16.2
A buffer solution is a solution of:
1. A weak acid or a weak base and
2. The salt of the weak acid or weak base
Both must be present!

A buffer solution has the ability to resist changes in pH upon

the addition of small amounts of either acid or base.

Consider an equal molar mixture of CH3COOH and CH3COONa

CH3COOH (aq) H+ (aq) + CH3COO- (aq)

Adding more acid creates a shift left IF

enough acetate ions are present
16.3
 HCl H+ + Cl-
HCl + CH3COO- CH3COOH + Cl-

16.3
 Which of the following are buffer systems? (a) KF/HF
(b) KCl/HCl, (c) Na2CO3/NaHCO3

(a) KF is a weak acid and F- is its conjugate base

buffer solution
(b) HCl is a strong acid
not a buffer solution
(c) CO32- is a weak base and HCO3- is it conjugate acid
buffer solution

16.3
 Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer
system. What is the pH after the addition of 20.0 mL of
0.050 M NaOH to 80.0 mL of the buffer solution?
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)
[NH4+] [OH-]
Kb = = 1.8 X 10-5
[NH3]
Initial 0.30 0.36 0
Change -x +x +x
End 0.30 - x 0.36 + x x
(.36 + x)(x)
1.8 X 10-5 =
(.30 x)
0.36x
1.8 X 10
-5
x = 1.5 X 10-5 pOH = 4.82 pH= 9.18
0.30
16.3
 Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer
system. What is the pH after the addition of 20.0 mL of
0.050 M NaOH to 80.0 mL of the buffer solution?
final volume = 80.0 mL + 20.0 mL = 100 mL
NH4+ 0.36 M x 0.080 L = 0.029 mol / .1 L = 0.29 M
OH- 0.050 x 0.020 L = 0.001 mol / .1 L = 0.01M
NH3 0.30 M x 0.080 = 0.024 mol / .1 L = 0.24M
start (M) 0.29 0.01 0.24
NH4+ (aq) + OH- (aq) H2O (l) + NH3 (aq)
end (M) 0.28 0.0 0.25

[H+] [NH3]
Ka= = 5.6 X 10 -10
[NH4+] [H+] = 6.27 X 10 -10
[H+] 0.25 pH = 9.20
= 5.6 X 10 -10

0.28 16.3
 Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer
system. What is the pH after the addition of 20.0 mL of
0.050 M NaOH to 80.0 mL of the buffer solution?

NH4+ (aq) H+ (aq) + NH3 (aq)

[NH3] [0.30]
pH = pKa + log pKa = 9.25 pH = 9.25 + log = 9.17
[NH4+] [0.36]
final volume = 80.0 mL + 20.0 mL = 100 mL

start (M) 0.29 0.01 0.24

NH4+ (aq) + OH- (aq) H2O (l) + NH3 (aq)
end (M) 0.28 0.0 0.25

[0.25]
pH = 9.25 + log = 9.20
[0.28]
16.3
Chemistry In Action: Maintaining the pH of Blood

16.3
 Titrations
In a titration a solution of accurately known concentration is
added gradually added to another solution of unknown
concentration until the chemical reaction between the two
solutions is complete.

Equivalence point the point at which the reaction is complete

Indicator substance that changes color at the

endpoint (hopefully close to the equivalence point)

Slowly add base

to unknown acid
UNTIL
The indicator
changes color
(pink) 4.7
Strong Acid-Strong Base Titrations
100%
NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq) ionization!
OH- (aq) + H+ (aq) H2O (l) No equilibrium

16.4
Weak Acid-Strong Base Titrations
CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)
CH3COOH (aq) + OH- (aq) CH3COO- (aq) + H2O (l)
At equivalence point (pH > 7):
CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq)

16.4
Strong Acid-Weak Base Titrations
HCl (aq) + NH3 (aq) NH4Cl (aq)
H+ (aq) + NH3 (aq) NH4Cl (aq)
At equivalence point (pH < 7):
NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)

16.4
Acid-Base Indicators

16.5
pH
16.5
The titration curve of a strong acid with a strong base.

16.5
 Which indicator(s) would you use for a titration of HNO 2
with KOH ?

Weak acid titrated with strong base.

At equivalence point, will have conjugate base of weak acid.
At equivalence point, pH > 7
Use cresol red or phenolphthalein

16.5
 Finding the Equivalence Point
(calculation method)
Strong Acid vs. Strong Base
100 % ionized! pH = 7 No equilibrium!
Weak Acid vs. Strong Base
Acid is neutralized; Need Kb for conjugate base
equilibrium
Strong Acid vs. Weak Base
Base is neutralized; Need Ka for conjugate acid
equilibrium
Weak Acid vs. Weak Base
Depends on the strength of both; could be
conjugate acid, conjugate base, or pH 7
 Exactly 100 mL of 0.10 M HNO2 are titrated with 100 mL of
a 0.10 M NaOH solution. What is the pH at the
equivalence point ?
start (moles) 0.01 0.01
HNO2 (aq) + OH- (aq) NO2- (aq) + H2O (l)
end (moles) 0.0 0.0 0.01
0.01
Final volume = 200 mL [NO2 ] = 0.200 = 0.05 M
-

NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)

Initial (M) 0.05 0.00 0.00
Change (M) -x +x +x
Equilibrium (M) 0.05 - x x x
[OH-][HNO2] x2
Kb = = = 2.2 x 10 -11 pOH = 5.98
[NO2-] 0.05-x
0.05 x 0.05 x 1.05 x 10-6 = [OH-] pH = 14 pOH = 8.02
 Complex Ion Equilibria and Solubility
A complex ion is an ion containing a central metal cation
bonded to one or more molecules or ions.
Co2+ (aq) + 4Cl- (aq) CoCl42-(aq)

Co(H2O)62+ CoCl2-
4

16.10
16.10
 Complex Ion Formation
These are usually formed from a transition
metal surrounded by ligands (polar
molecules or negative ions).
As a "rule of thumb" you place twice the
number of ligands around an ion as the
charge on the ion... example: the dark
blue Cu(NH3)42+ (ammonia is used as a
test for Cu2+ ions), and Ag(NH3)2+.
Memorize the common ligands.
 Common Ligands
Ligands Names used in the ion
H2O aqua
NH3 ammine
OH- hydroxy
Cl- chloro
Br- bromo
CN- cyano
SCN- thiocyanato (bonded through
sulphur)
isothiocyanato (bonded through
nitrogen)
 Names
Names: ligand first, then cation
Examples:
tetraamminecopper(II) ion: Cu(NH3)42+
diamminesilver(I) ion: Ag(NH3)2+.
tetrahydroxyzinc(II) ion: Zn(OH)4 2-
The charge is the sum of the parts
(2+) + 4(-1)= -2.
 When Complexes Form
Aluminum also forms complex ions as do some post transitions
metals. Ex: Al(H2O)63+
Transitional metals, such as Iron, Zinc and Chromium, can form
complex ions.
The odd complex ion, FeSCN2+, shows up once in a while
Acid-base reactions may change NH3 into NH4+ (or vice versa)
which will alter its ability to act as a ligand.
Visually, a precipitate may go back into solution as a complex
ion is formed. For example, Cu 2+ + a little NH4OH will form the
light blue precipitate, Cu(OH) 2. With excess ammonia, the
complex, Cu(NH3)42+, forms.
Keywords such as "excess" and "concentrated" of any
solution may indicate complex ions. AgNO3 + HCl forms the
white precipitate, AgCl. With excess, concentrated HCl, the
complex ion, AgCl2-, forms and the solution clears.
 Coordination Number
Total number of bonds from the ligands
to the metal atom.
Coordination numbers generally range
between 2 and 12, with 4
(tetracoordinate) and 6 (hexacoordinate)
being the most common.
 Some Coordination Complexes
molecular Lewis Lewis acid donor coordination
formula base/ligand atom number

Ag(NH3)2+ NH3 Ag+ N 2

[Zn(CN)4]2- CN- Zn2+ C 4

[Ni(CN)4]2- CN- Ni2+ C 4

[PtCl6] 2- Cl- Pt4+ Cl 6

[Ni(NH3)6]2+ NH3 Ni2+ N 6