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7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
Bases
H+(aq)
A-(aq)
Strong:
+
Hydrochloric, HCl
Hydrobromic, HBr
Hydroiodoic, HI
Nitric acid, HNO3
Sulfuric acid, H2SO4
Perchloric acid, HClO4
Weak
Hydrofluoric, HF
Phosphoric acid, H3PO4
Acetic acid, CH3COOH
(or HC2H3O2)
Weak
Ammonia, NH3
accepts proton from water to make
NH4+(aq) and OH-(aq)
H2O(l) + 56 kJ / mol
Calculate moles of
Sulfuric Acid
Divide moles by
volume to get
concentration of
sulfate
Use equation to
calculate H+
concentration
Molarity of SO4- 2 =
1 mole H2SO4
= 1.58 moles H2SO4
98.09 g H2SO4
H3O+(aq) + A-(aq)
H3O+(aq) + NO3-(aq)
H3O+(aq) + A-(aq)
[H3O+][A-]
[HA][H2O]
[A-]
Ka = [H3
[HA] [H2O]
H3O+(aq) + A-(aq)
Therefore:
Ka =
[H3O+] [A-]
[HA]
Stronger acid
higher [H3O+]
larger Ka
The Extent
of
Dissociation
for Strong
and Weak
Acids
pH
What is pH?
How is it important?
The definition of pH
pH = -log10[H3O+] = -log10[H+]
Significant Figures for pH
The number of decimal places in the log is
equal to the number of significant figures in
the original number.
pH in the body
Body Section
pH
Stomach Acid
0.7
Urine
6.0
Brain Fluid
7.3
Blood
7.45
Pancreas
8.1
Mitochondria
7.5
Lyosomes
4.5
K = Ka = Kw = 1.0 x 10-14
Autoionization of Water
H2O(l) + H2O(l)
Ka =
[H3O+][OH-]
[H2O]2
H3O+(aq) + OH-(aq)
= [H+][OH-] = Kw
1000 g/L
18.02 g/mol
= 55.5 M
pOH = -log10[OH-]
pOH = 14.00 pH
pKa = - log10Ka
Ka at 25oC
1.02 x 10-2
pKa
1.991
7.1 x 10-4
3.15
1.8 x 10-5
4.74
2.3 x 10-9
8.64
Phenol (C6H5OH)
1.0 x 10-10
10.00
Complete dissociation:
[H+] = initial concentration
Kw
[H+]
1 x 10-14
= 3.333 x 10-15 M
3.0
Kw
1 x 10-14
[OH-] =
=
[H+]
0.0024
= 4.167 x 10-12 M
[H+] [ClO-]
= 3.5 x 10-8
[HClO]
Concentration (M)
Initial
Change
Equilibrium
Ka =
HClO
H2O
0.125
-x
0.125 - x
----------
(x)(x)
= 3.5 x 10-8
0.125-x
H+
0
+x
x
ClO0
+x
x
x2 = 0.4375 x 10-8
-log10(0.661x10-4)
pH = 4.180
x = 0.661 x 10-4
0.12
-x
0.12 -x
Substituted
----------
0.12
0
+x
+x
0
+x
+x
6.46 x 10-5
6.46 x 10-5
HClO(aq) + H2O(l)
[H3O+] [ClO-]
=
[HClO]
Ka = 3.48 x 10-8
= 3.48 x 10-8
[H+] [NO2-]
(x) (x)
= 4.0 x 10-4 =
[HNO2]
1.00 - x
Assume 1.00 x = 1.00 since left side so tiny.
Ka =
x2
Ka =
[H+] [A-]
[HA]
HCN(aq) + H2O(l)
H3O+
CN-
0
+x
x
0
+x
x
HCN
Initial 1.00 M
Change
-x
Final
1.00 x
Ka =
(x)(x)
Ka = (1.00-x)
x2
1.00
Ka =
[H3O+][CN-]
[HCN]
= 6.20 x 10-10
= 6.2 x 10-10
x = 2.49 x 10-5
% dissociation =
2.49 x 10-5
1.00
x 100% = 0.00249%
HA(aq) + MOH(aq)
Acid
MA(aq) + H2O(l)
Base
Salt
+ Water
(aq)
+2
OH -(aq)
+2
H+
(aq)
+2I
2 OH -(aq) + 2 H+(aq)
Molecular Model
Acid
Base
Conjugate
acid
Conjugate
base
Base
Conjugate Pair
Reaction 1
Reaction 2
HF
H2O
HCOOH +
CN
Reaction 3
NH4+
CO3
Reaction 4
H2PO4
OH
Reaction 5
H2SO4
N2H5+
H3O+
HCOO
NH3
HCN
HCO3
HPO42 +
H2O
HSO4
N2H62+
BASES
Molecular Model
pH of a Base Calculation
Calculate the pH of a 2.0 x 10-3 M solution of NaOH.
Since NaOH is a strong base, it will dissociate 100% in water.
NaOH(aq)
Na+(aq) + OH-(aq)
Kw
=
[OH-]
1.0 x 10-14
2.0 x 10-3
= 5.0 x 10-12 M
B(aq) + H2O(l)
Equilibrium constant:
BH+(aq) + OH-(aq)
BH OH
K Kb
+]
[NH4
[OH-]
[NH3]
Concentration (M)
NH3
Initial
Change
Equilibrium
H2O
1.5
-x
1.5 - x
----------
NH4+
OH-
0
+x
x
0
+x
x
[NH4+] [OH-]
[NH3]
(x)(x)
1.5-x
= 1.8 x 10-5
HA + H2O
H3O+ + A-
Base
A-
+ H2O
HA + OH-
2 H2O
H3O+ + OH-
[H3O+] [A-]
[HA] [OH-]
[A-]
[HA]
Ka
Kb
= [H3O+] [OH-]
=
Kw
Molecular Model
H+(aq) + F-(aq)
HOCl(aq)
H+
H2O(aq)
H+(aq) + OH-(aq)
(aq)
OCl-(aq)
Ka = 7.2 x 10-4
Ka = 3.5 x 10-8
Ka = 1.0 x 10-14
Ka =
[H+] [A-]
= specific value
[HA]
H+(aq) + F-(aq)
Ka = 7.2 x 10-4
HOCl(aq)
H+(aq) + OCl-(aq)
Ka = 3.5 x 10-8
H2O(aq)
H+
Ka = 1.0 x 10-14
(aq)
OH-(aq)
[H+] [F-]
= 7.2 x 10-4
[HF]
Ka =
Equilibrium Concentration
(mol/L)
x mol HF
dissociates
[HF] = 1.00 x
[F-] = x
[H+] = x
[H+] [F-]
(x) (x)
= 7.2 x 10-4 =
[HF]
1.00-x
x2
1.00
x = 2.7 x 10-2
Therefore,
[F- ] = [H+] = x = 2.7 x 10-2 and pH = 1.56
[H+] [OCl-]
= 3.5 x 10-8
[HOCl]
(2.7 x 10-2)( x)
(5.00 - x)
5.00 ( 3.5 x 10-8)
2.7 x 10-2
[HOCl]eqbm = 5.00 - x
Polyprotic Acids
Molecular Model
H2SO4 :
Strong acid
so Ka is huge
(100% dissociated)
Weak acid
Ka = 1.2x10-2
HSO4-(aq)
HSO4-(aq) + H+(aq)
SO4-(aq) + H+(aq)
Ka1 = LARGE
Ka2 = 1.2x10-2
HSO4-(aq)
Ka = 1.2x10-2
x mol/L HSO4dissociates
to reach
equilibrium
[HSO4-] = 0.00300 x
[SO42-] = x
[H+] = 0.00300 + x
[H+][SO42-]
=
[HSO4-]
(0.00300 + x)(x)
(0.00300 x)
x=
-b +-
b2 4ac
2a
x = 2.10 x 10-3
pH = 2.29
Note: Change in [H+] does not violate huge Ka for 1st dissociation: [H2SO4] = 0 still.
H2PO4-(aq) + H3O+(aq)
Ka = 7.5x10-3
H2PO4-(aq) + H2O(l)
HPO42-(aq) + H3O+(aq)
Ka = 6.2x10-8
HPO42-(aq) + H2O(l)
PO43-(aq) + H3O+(aq)
Ka = 4.8x10-13
PO43-(aq) + 3 H3O+(aq)
Molecular Model
H2PO4-(aq) + H3O+(aq)
Ka = 7.5x10-3
H2PO4-(aq) + H2O(l)
HPO42-(aq) + H3O+(aq)
Ka = 6.2x10-8
HPO42-(aq) + H2O(l)
PO43-(aq) + H3O+(aq)
Ka = 4.8x10-13
PO43-(aq) + 3 H3O+(aq)
H+(aq) + H2PO4-(aq)
[H+] [H2PO4-]
[H3PO4]
Equilibrium Concentration (mol/L)
[H3PO4] = 5.0 - x
[H2PO4-] =x
[H+] = x
[H+] [H2PO4-]
[H3PO4] =
(x)(x)
= ~
5.0-x
x2
5.0
[H+] [HPO42-]
[H2PO4-]
Base
Conjugate Pair
Reaction 1
HF
H2O
Reaction 2
HCOOH +
CN
Reaction 3
NH4
CO3
Reaction 4
H2PO4
OH
Reaction 5
H2SO4
N2H5+
H3O+
HCOO
NH3
HCN
H2O
HSO4
N2H62+
HCO3
HPO42 +
Molecular Model
HA + H2O
H3O+ + A-
Base
A- + H2O
HA + OH-
2 H2O
H3O+ + OH-
[H3O+] [A-]
[HA] [OH-]
Ka
= [H3O+] [OH-]
[A-]
[HA]
Kb
Kw
HCN(aq) + OH-(aq)
[OH-]
[HCN]
The value of Kb can be calculated
[CN-]
from Kw and the Ka value for HCN.
1.0 x 10-14
Kw
Kb =
=
= 1.61 x 10-5
Ka (for HCN)
6.2 x 10-10
Kb =
[CN-] = 0.45 x
[HCN] = x
[OH-] = x
[HCN] [OH-]
=
[CN-]
(x)(x)
=
0.45 - x
~x2
0.45
Molecular Model
Al(OH)(H2O)52+(aq) + H+(aq)
[Al(OH)(H2O)52+][H+]
1.4 x 10-5 = Ka =
[Al(H2O)63+]
Initial Concentration (mol/L)
[Al(H2O)63+]0 = 0.010
[Al(OH)(H2O)52+] = 0
[H+]0 =~ 0
x mol/L
3+
Al(H2O)6
dissociates
to reach
equilibrium
[Al(H2O)63+] = 0.010 x
[Al(OH)(H2O)52+] = x
[H+] = x
Ka =
Ka =
(x) (x)
=
0.010 - x
x2
= 1.4x10-5
0.010
x = 3.7 x 10-4
Since the approximation is valid by the 5% rule:
[H+] = x = 3.7 x 10-4 M
and pH = 3.43
Base
Conjugate Pair
Reaction 1
Reaction 2
HF
H2O
HCOOH +
CN
Reaction 3
NH4
CO3
Reaction 4
H2PO4
OH
Reaction 5
H2SO4
N2H5+
H3O+
HCOO
NH3
HCN
HCO3
HPO42 +
H2O
HSO4
N2H62+
HA + H2O
H3O+ + A-
Base
A- + H2O
HA + OH-
2 H2O
H3O+ + OH-
[H3O+] [A-]
[HA] [OH-]
[A-]
[HA]
Ka
Kb
pKa + pKb
= [H3O+] [OH-]
Kw
= 14
= 10-14
General reaction:
NR3(aq) + H2O(l)
+]
Kb = [HNR3
[NR3]
HNR3+(aq) + OH-(aq)
[OH-]
Examples
KCl, KNO3
NaCl, NaNO3
Cation is from
strong base;
anion is from
weak acid
Anion acts as
a base; cation
has no effect
on pH
NaC2H3O2
KCN, NaF
Cation is conjugate
acid of weak base;
anion is from
strong acid
Comment
pH of Soln
Neither acts as
an acid or a
Neutral
base
Basic
Cation acts as
an acid; anion
has no effect
on pH
NH4Cl,
NH4NO3
Acidic
Examples
Comment
Cation is conjugate
acid of weak base
anion is conjugate
base of weak acid
NH4C2H3O2
NH4CN
Cation is highly
charged metal ion;
anion is from
strong acid
Al(NO3)3,
FeCl3
pH of Soln
Cation acts as
an acid; anion
acts as a base
Acidic if :
K a > Kb
Basic if :
K b > Ka
Neutral if :
Ka = Kb
Hydrated cation
acts as an acid;
anion has no
effect on pH
Acidic
HF(aq)
HOCl(aq)
H+
H2O(aq)
H+(aq) + OH-(aq)
(aq)
OCl-(aq)
Ka = 7.2 x 10-4
Ka = 3.5 x 10-8
Ka = 1.0 x 10-14
Ka =
[H+] [F-]
= 7.2 x 10-4
[HF]
- I
We start with the expression for the value of Ka , for the weak acid
HA:
From the conservation of charge equation:
Ka =
[H+] [A-]
[HA]
K
[OH-] = [Hw+]
[H+] = [A-] +
Kw
[H+]
or:
[A-] = [H+] -
[Kw]
[H+]
[A-] = [H+] -
or
Kw
[H+]
Ka =
[H+]2 - Kw
[HA]0 -
[H+]2 - Kw
Kw
)
[H+]
Kw
)
[H+]
Full Equation!
[H+]
When [H+]2 >> Kw (i.e., when [H+] > 10-6), this simplifies to:
[H+]2
Ka = [HA] [H+] , which is the usual eqn.
0
Ka = 3.5 x 10-8 =
[H+]2 10-14
[H+]2 10-14
1.0 x 10-5 [H+]
One equation in
one unknown, so
definitely soluble.
But hard to solve!
Use calculator!
Summary:
(P 233)
Think Chemistry, Focus on the solution components and their reactions. It will almost
always be possible to choose one reaction that is the most important.
Be systematic. Write down all the things you know, including things
like the eqbm.
eqbm. constant equation, list what you can calculate, and list what
whats needed.
Be flexible. Although all acid-base problems are similar in many ways, important
differences do occur. Treat each problem as a separate entity. Do not try to force a given
problem to match any you have solved before. Look for both the similarities and the
differences.
Be patient. The complete solution to a complicated problem cannot be seen immediately
in all its detail. Pick the problem apart into its workable steps.
Be confident. Look within the problem for the solution, and let the problem guide you.
Assume that you can think it out. Do not rely on memorizing solutions to problems.
In fact, memorizing solutions is usually detrimental, because you tend to try to force a
new problem to be the same as one you have seen before. Understand and think; dont
just memorize.