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CHAPTER 13
Acids & Bases
2
Properties of Aqueous Solutions
of Acids & Bases
Acidic properties
taste sour
change the colors of indicators
turn litmus red
react with metals to generate H
2(g)

react with metal oxides and hydroxides to
form salts and water
aqueous solutions conduct electricity
3
Properties of Aqueous Solutions
of Acids & Bases
Basic properties
taste bitter
feel slippery
change colors of indicators
turn litmus blue
react with acids to form salts and water
aqueous solutions conduct electricity
4
Strong Electrolytes
Strong electrolytes ionize or dissociate
completely
Three classes of strong electrolytes
1 Strong Acids
HNO H O H O NO
or
HNO H NO
3 2
100%
3
+
3
3 3
+ +
+
~

+
5
Strong Electrolytes
2 Strong Soluble Bases
K OH K OH
H O 100%
2
+
~
+
+
6
Strong Electrolytes
3 Most Soluble Salts
( )
Ca(NO ) Ca 2 NO
3 2 s
H O 100%
2
3
2
~
+
+
7
Strong Electrolytes
Calculation of concentrations of ions in
solution of strong electrolytes is easy
Example: Calculate the concentrations of ions
in 0.050 M nitric acid, HNO
3
.
8
Strong Electrolytes
Calculation of concentrations of ions in
solution of strong electrolytes is easy
Example: Calculate the concentrations of ions
in 0.050 M nitric acid, HNO
3
.
HNO H O H O NO
0.050 0.050
3 2
100%
3 3
+ +
+
0050 . M M M
9
Arrhenius Theory
Svante Augustus Arrhenius - 1884
acids generate H
+
in aqueous solutions



+

+
+ +
+
+
-
2 3 2 2
-
3 2
HCO O H O H H HCO
Cl O H O H HCl
10
Arrhenius Theory
bases generate OH
-
in aqueous solutions
( ) ( )
( ) ( )
+

+
+
+
+
aq aq 4 2 3(g)
-
aq aq
OH NH O H NH
OH Na NaOH
11
Arrhenius Theory
neutralization - combination of H
+
(or H
3
O
+
)
with OH
-

strong acids - ionize 100% in water
HCl, HBr, HI, H
2
SO
4
, HNO
3
, HClO
4
, HClO
3
strong bases - ionize 100% in water
LiOH, NaOH, KOH, RbOH, CsOH,
Ca(OH)
2
, Sr(OH)
2
, Ba(OH)
2
12
Arrhenius Theory
total ionic equation for strong acid with
strong base


net ionic equation for strong acid with
strong base

( ) ( ) ( ) ( ) ( ) ( ) (l)
O H Cl Na OH Na Cl H
2
-
aq aq
-
aq aq aq aq
+ + + + +
+ + +
( ) ( ) (l)
O H OH H
2
-
aq aq
+
+
13
Bronsted-Lowry Acid-Base
Theory
acids - proton (H
+
) donor
1 2 2 1
-
3 2
base acid base acid
Br O H O H HBr + +
+
14
Bronsted-Lowry Acid-Base
Theory
bases - proton (H
+
) acceptor
2 1 2 1
-
4 2 3
base acid acid base
OH NH O H NH +

+
+
15
Bronsted-Lowry Acid-Base
Theory
acid-base reactions are proton transfer
reactions



note that we are often making coordinate
covalent bonds
1 2 2 1
-
4 3
base acid base acid
Cl NH NH HCl + +
+
16
Bronsted-Lowry Acid-Base
Theory
conjugate acid-base pairs
species that differ by a proton
HNO
3
+ H
2
O H
3
O
+
+ NO
3
-
HNO
3
- acid
1
NO
3
-
- base
1
H
2
O - base
2
H
3
O
+
- acid
2
HF + H
2
O H
3
O
+
+ F
-
HF - acid
1
F
-
- base
1

H
2
O - base
2
H
3
O
+
- acid
2
17
Bronsted-Lowry Acid-Base
Theory
differences between Arrhenius & Bronsted-
Lowry theories
reaction does not have to occur in an
aqueous solution
bases do not have to be hydroxides
for example- ammonia is not a hydroxide
base acid acid base
OH NH O H NH
2 1 2 1
-
4 2 3
+

+
+
18
Bronsted-Lowry Acid-Base
Theory
weak acids have strong conjugate
bases
weak bases have strong conjugate
acids
primary reason they are weak acids or
bases
strong conjugates recombine to form the
original species
19
Bronsted-Lowry Acid-Base
Theory
NH
4
+
must be a strong acid-it gives up H
+

to reform NH
3

NaOH Na
+
(aq) + OH
-
(aq)
Na
+
must be a weak acid or it would
recombine to form NaOH
remember NaOH ionizes 100%
+

+
+ -
4 2 3
OH NH O H NH
20
Bronsted-Lowry Acid-Base
Theory
amines are weak bases that behave like
ammonia
amines have organic groups attached to
-NH
2
group
+

+
+

+
+
+
-
3 3 2 2 3
-
4 2 3
OH NH CH O H NH CH
OH NH O H NH
21
Bronsted-Lowry Acid-Base
Theory
water can be either an acid or base in
Bronsted-Lowry theory
amphoteric - species that can be either
an acid or base
amphiprotic - proton transfer reactions
that species behave as either an acid or
base
2 1 2 1
-
3 2 2
base acid acid base
OH O H O H O H +

+
+
22
The Auto-Ionization of Water
Pure water ionizes very slightly
less than one-millionth molar
H O + H O H O +OH
2 2 3
+ -

23
The Auto-Ionization of Water
Because the activity of pure water is 1, the
equilibrium constant for this reaction is
| || |
K H O OH
c 3
+
=

24
The Auto-Ionization of Water
Experimental measurements have determined
that the concentration of each ion is 1.0 x 10
-7

M at 25
0
C
| || |
( )( )
K H O OH
1.0 x 10 1.0 x 10
1.0 x10
c 3
+
-7 -7
14
=
=
=

25
The Auto-Ionization of Water
This particular equilibrium constant is called the
ion-product for water, K
w
.
| || |
K H O OH
1.0 x10
w 3
+
14
=
=

26
The pH and pOH scales
A convenient way to express acidity and
basicity
pH is defined as
| |
pH = -log H O
3
+
27
The pH and pOH scales
In general, a lower case p before a symbol is
read as negative logarithm of the symbol
| |
| |
pOH = -log OH
pAg = -log Ag
and so forth
-
+
28
The pH and pOH scales
If we know either [H
3
O
+
] or [OH
-
], then we can
calculate pH and pOH.
Example: Calculate the pH of a solution in
which the [H
3
O
+
] =0.030M.
29
The pH and pOH scales
If we know either [H
3
O
+
] or [OH
-
], then we can
calculate pH and pOH.
Example: Calculate the pH of a solution in
which the [H
3
O
+
] =0.030M.
| |
( )
52 . 1 pH
10 0 . 3 log pH
O H -log = pH
2
+
3
=
=

30
The pH and pOH scales
A convenient relationship between pH and
pOH may be derived for all dilute aqueous
solutions at 25
0
C.
14
3
10 0 . 1 ] ][OH O [H
+
=
31
The pH and pOH scales
Remember these two expressions!!
| || |
14.00 pOH pH
10 0 . 1 OH O H
14
3
= +
=
+
32
The pH and pOH scales
The usual range for the pH scale is



and for pOH the scale is
| | | |
14.00 pH 0 pH
10 0 . 1 O H down to 0 . 1 O H
14
3 3
= =
= =
+ +
M M
| | | |
0 pOH 00 . 14 pOH
0 . 1 OH to up 10 0 . 1 OH
14
= =
= =

M M
33
The pH and pOH scales
34
Strengths of Acids
Binary Acids
acid strength increases with decreasing
bond strength
hydrogen halides
bond strength
HF>>HCl>HBr>HI
acid strength
HF<<HCl<HBr<HI
35
Strengths of Acids
36
Strengths of Acids
VIA hydrides
bond strength
H
2
O>> H
2
S> H
2
Se> H
2
Te
acid strength
H
2
O<< H
2
S< H
2
Se< H
2
Te
37
Strengths of Acids
for HBr in water
HBr + H
2
O H
3
O
+
+ Br
-

essentially 100%
can only distinguish acid strength
differences of strong acids in
nonaqueous solutions like acetic acid
38
Strengths of Acids
Acid Conjugate Base
Strongest acid Weakest base
HClO
4
ClO
4
-

H
+
(H
3
O
+
) -H
+
H
2
O
CH
3
CO
2
H CH
3
CO
2
-

H
2
O +H
+
OH
-

NH
3
NH
2
-
Weakest acid Strongest base
39
Strengths of Acids
strongest acid in water is H
3
O
+
HCl + H
2
O H
3
O
+
+ Cl
-

HCl is so strong it forces water to accept H
+
strongest base in water is OH
-
NH
2
-
+ H
2
O NH
3
+ OH
-
NH
2
-
is strong enough to remove H
+
from water
because water is amphiprotic
40
Strengths of Bases
Strong Bases are strong electrolytes
Dissociate completely in solution
Bases do not need to contain OH
-
ion
O
2-
(aq) + H
2
O (l) 2OH
-
(aq)
H
-
(aq) + H
2
O(l) H
2
(g) + OH
-
(aq)
N
3
-
(aq) + H
2
O(l) NH
3
(aq) + 3OH
-
(aq)

41
Ionization Constants for Weak
Monoprotic Acids and Bases
Lets look at the dissolution of acetic acid, a
weak acid, in water as an example.
The equation for the ionization of acetic acid
is:

+
+

COO CH O H O H COOH CH
-
3 3 2 3
42
Ionization Constants for Weak
Monoprotic Acids and Bases
The equilibrium constant for this ionization is
expressed as:
| || |
| || | O H COOH CH
COO CH O H
K
2 3
3 3
c
+
=
43
Ionization Constants for Weak
Monoprotic Acids and Bases
The water concentration in dilute aqueous
solutions is very high.
1 L of water contains 55.5 moles of water.
Thus in dilute aqueous solutions:
| | M 5 . 55 O H
2
~
44
Ionization Constants for Weak
Monoprotic Acids and Bases
The water concentration is many orders of
magnitude greater than the ion
concentrations.
Thus the water concentration is essentially
constant.
| |
| || |
| | COOH CH
COO CH O H
O H K
3
3 3
2 c
+
=
45
Ionization Constants for Weak
Monoprotic Acids and Bases
Since a constant multiplied by a constant is a
new constant - lets give this new constant its
own name and symbol
K
a
= ionization constant
| || |
| |
acid acetic for
10 8 . 1
COOH CH
COO CH O H
K
5
3
3 3
a

+
= =
46
Ionization Constants for Weak
Monoprotic Acids and Bases
In simplified form the equation and
expression are written as:
| || |
| |
5
3
3
a
-
3 3
10 8 . 1
COOH CH
COO CH H
K
COO CH H COOH CH

+
+
= =
+

47
Ionization Constants for Weak
Monoprotic Acids and Bases
Values for several ionization constants
48
Ionization Constants for Weak
Monoprotic Acids and Bases
From the above table we see that the order of
increasing acid strength for these weak acids
is:

The larger K
a
The stronger the acid
If K
a
>> 1 then the acid is completely ionized
and the acid is a strong acid.
HF>HNO >CHCOOH>HClO>HCN
3 3
49
Ionization Constants for Weak
Monoprotic Acids and Bases
The order of increasing base strength of the
anions (conjugate bases) of these acids is:
F < NO < CH COO < ClO < CN
-
3
-
3
- - -
50
Ionization Constants for Weak
Monoprotic Acids and Bases
Using K
a
, the concentration of H
+
(and hence the pH)
can be calculated.
Write the balanced chemical equation clearly showing the
equilibrium.
Write the equilibrium expression. Find the value for K
a
.
Write down the initial and equilibrium concentrations for
everything except pure water. We usually assume that the
change in concentration of H
+
is x.
Substitute into the equilibrium constant expression
and solve. Remember to turn x into pH if necessary.
A sample problem can be found at end of the slides.
51
Ionization Constants for Weak
Monoprotic Acids and Bases
Percent Ionization
HA(aq) + H
2
O(l) H
3
O
+
(aq) + A
-
(aq)

% ionization = [H
+
]
equ
x 100
[HA]

Relates equilibrium H
+
concentration to the
initial HA concentration
52
Ionization Constants for Weak
Monoprotic Acids and Bases
Percent Ionization
The higher the percent ionization
The stronger the acid
For weak acids
Percent ionization decreases as the molarity of
the solution decreases
acetic acid 0.05M 2.0% ionized
0.15 M 1.0% ionized
53
Ionization Constants for Weak
Monoprotic Acids and Bases
54
Polyprotic Acids
Many weak acids contain two or more acidic
hydrogens.
polyprotic acids ionize stepwise
ionization constant for each step
Consider arsenic acid, H
3
AsO
4
, which has
three ionization constants
1 K
1
=2.5 x 10
-4
2 K
2
=5.6 x 10
-8

3 K
3
=3.0 x 10
-13
55
Polyprotic Acids
The first ionization step is
| || |
| |
H AsO H H AsO
K
H H AsO
H AsO
3 4 2 4
1
2 4
3 4

+
= =
+
+

2 5 10
4
.
56
Polyprotic Acids
The second ionization step is
| || |
| |
H AsO H HAsO
K
H HAsO
H AsO
2 4
-
4
2
4
2 4
2-

+
= =
+
+

2
2
8
56 10 .
57
Polyprotic Acids
The third ionization step is
| || |
| |
HAsO H AsO
K
H AsO
HAsO
4
2-
4
3
4
4
2-

+
= =
+
+

3
3
13
30 10 .
58
Polyprotic Acids
Notice that the ionization constants vary in
the following fashion:



This is a general relationship. It is always
easier to remove the first proton.
K K K
1 2 3
> >
59
Polyprotic Acids
60
Weak Bases
Remove protons from substances
Equilibrium established
Weak base + H
2
O Conjugate acid + OH
-


Calculate K
b
base dissociation constant
61
Weak Bases
62
Weak Bases
Generally have lone pair or negative
charge
Neutral weak bases contain N
Anions of weak acids are weak bases
63
Relationship between K
a
and K
b

When two reactions are added to give a
third, the equilibrium constant for the
third reaction is the product of the
equilibrium constants for the first two.

Reaction 1 + Reaction 2 = Reaction 3
K
1
x K
2
= K
3

64
Relationship between K
a
and K
b

For a conjugate acid base pair:
K
a
x K
b
= K
w


pK
a
x pK
b
= pK
w


The larger the K
a
, the smaller the K
b

The stronger the acid, the weaker the
conjugate base.
65
Calculation of Ionization
Constants
Example: In 0.12 M solution, a weak
monoprotic acid, HY, is 5.0% ionized.
Calculate the ionization constant for the weak
acid.
66
Calculation of Ionization
Constants
Example: In 0.12 M solution, a weak
monoprotic acid, HY, is 5.0% ionized.
Calculate the ionization constant for the weak
acid.
| || |
| |
HY H + Y
K
H Y
HY
+ -
a
+ -

=
67
Calculation of Ionization
Constants
Since the weak acid is 5.0% ionized, it is also
95% unionized.
Calculate the concentrations of all species in
solution.
| | | |
| |
H Y
HY
+
= = =
=
= =

0 05 012 0 0060
6 0 10
0 95 012 011
3
. ( . ) .
.
. ( . ) .
M M
M
M M
68
Calculation of Ionization
Constants
Substitute into the ionization constant
expression to get the value of K
a
| || |
| |
( )( )
( )
K
H Y
HY
a
= =

=
+

60 10 60 10
011
33 10
3 3
4
. .
.
.
69
Calculations Based on Ionization
Constants
Example: Calculate the concentrations of the
various species in 0.15 M acetic acid,
CH
3
COOH, solution.
It is always a good idea to write down the
ionization reaction and the ionization constant
expression.
| || |
| |
5
3
-
3 3
a
-
3 3 2 3
10 8 . 1
COOH CH
COO CH O H
K
COO CH O H O H COOH CH

+
+
= =
+

+
70
Calculations Based on Ionization
Constants
Next we combine the basic chemical
concepts with some algebra to solve the
problem
M 0.15 [] Initial
COO CH O H O H COOH CH
-
3 3 2 3
+

+
+
71
Calculations Based on Ionization
Constants
Next we combine the basic chemical
concepts with some algebra to solve the
problem
xM xM xM
M
+ +
+

+
+
- Change
0.15 [] Initial
COO CH O H O H COOH CH
-
3 3 2 3
72
Calculations Based on Ionization
Constants
Next we combine the basic chemical
concepts with some algebra to solve the
problem
xM xM -x)M . (
xM xM xM
M
+ +
+ +
+

+
+
15 0 [] m Equilibriu
- Change
0.15 [] Initial
COO CH O H O H COOH CH
-
3 3 2 3
73
Substitute these algebraic quantities into the
ionization expression.
| || |
| |
( )( )
( )
5
3
3 3
a
10 8 . 1
15 . 0
COOH CH
COO CH O H
K

+
=

=
=
x
x x
Calculations Based on Ionization
Constants
74
Solve the algebraic equation, using
simplifying assumption.
Calculations Based on Ionization
Constants
( )
5 2
5
2
10 8 . 1 15 . 0
10 8 . 1
15 . 0

~
=

x x
x
x
75
Solve the algebraic equation, using
simplifying assumption.
Calculations Based on Ionization
Constants
( )
| |
( )
5 2
3
a
5 2
5
2
10 8 . 1 15 . 0
assumption this make then 10
K
If
10 8 . 1 15 . 0
10 8 . 1
15 . 0

~
s
~
=

x
x x
x
x
76
Complete the algebra and solve for
concentrations.
Calculations Based on Ionization
Constants
| | | |
| | ( ) M M
M x
x
15 . 0 10 6 . 1 15 . 0 COOH CH
COO CH O H 10 6 . 1
10 7 . 2
3
3
3 3
3
6 2
~ =
= = =
~

77
Note that the properly applied simplifying
assumption gives the same result as solving the
quadratic equation does.
Calculations Based on Ionization
Constants
( )( )
( )
2a
4ac b b
c b a
0 10 7 . 2 10 8 . 1
10 8 . 1
15 . 0
2
6 5 2
5

=
= +
=

x
x x
X
x x
78
Calculations Based on Ionization
Constants
( ) ( ) ( )( )
( )
3 - 3
6
2
5 5
10 1.6 - and 10 6 . 1
1 2
10 7 . 2 1 4 10 8 . 1 10 8 . 1
=

=


x
x
79
Synthesis Question
One method of increasing the solubility
and the absorption of a medication is to
convert weakly acidic drugs into sodium
salts before making the pills that will be
ingested. How does this preparation
method enhance the drugs solubility in
the stomach?
80
Synthesis Question
The sodium salt of a weakly acidic
compound is a strong conjugate base.
In the presence of stomach fluids, 1.0 M
HCl, the conjugate base readily reacts
with the HCl generating the active and
soluble form of the medication.
81
Group Question
Medicines that are weakly basic are not
absorbed well into the bloodstream.
One method to increase their absorption
is to take an antacid at the same time
that the medicine is administered. How
does this method increase the
absorption?