Chapter 15

Acids and
Bases
2008, Prentice Hall
Chemistry: A Molecular Approach, 1
st
Ed.
Nivaldo Tro
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
Tro, Chemistry: A Molecular Approach 2
Stomach Acid & Heartburn
the cells that line your stomach produce
hydrochloric acid
to kill unwanted bacteria
to help break down food
to activate enzymes that break down food
if the stomach acid backs up into your esophagus, it
irritates those tissues, resulting in heartburn
acid reflux
GERD = gastroesophageal reflux disease = chronic
leaking of stomach acid into the esophagus
Tro, Chemistry: A Molecular Approach 3
Curing Heartburn
mild cases of heartburn can be cured by
neutralizing the acid in the esophagus
swallowing saliva which contains bicarbonate ion
taking antacids that contain hydroxide ions and/or
carbonate ions
Tro, Chemistry: A Molecular Approach 4
Properties of Acids
sour taste
react with active metals
i.e., Al, Zn, Fe, but not Cu, Ag, or Au
2 Al + 6 HCl 2 AlCl
3
+ 3 H
2

corrosive
react with carbonates, producing CO
2
marble, baking soda, chalk, limestone
CaCO
3
+ 2 HCl CaCl
2
+ CO
2
+ H
2
O
change color of vegetable dyes
blue litmus turns red
react with bases to form ionic salts
Tro, Chemistry: A Molecular Approach 5
Common Acids
Chemical Name Formula Uses Strength
Nitric Acid HNO
3
explosive, fertilizer, dye, glue Strong
Sulfuric Acid H
2
SO
4

explosive, fertilizer, dye, glue,
batteries
Strong
Hydrochloric Acid HCl
metal cleaning, food prep, ore
refining, stomach acid
Strong
Phosphoric Acid H
3
PO
4

fertilizer, plastics & rubber,
food preservation
Moderate
Acetic Acid HC
2
H
3
O
2

plastics & rubber, food
preservation, Vinegar
Weak
Hydrofluoric Acid HF metal cleaning, glass etching Weak
Carbonic Acid H
2
CO
3
soda water Weak
Boric Acid H
3
BO
3
eye wash Weak


Tro, Chemistry: A Molecular Approach 6
Structures of Acids
binary acids have acid hydrogens attached to
a nonmetal atom
HCl, HF

Tro, Chemistry: A Molecular Approach 7
Structure of Acids
oxy acids have acid hydrogens attached to
an oxygen atom
H
2
SO
4
, HNO
3
Tro, Chemistry: A Molecular Approach 8
Structure of Acids
carboxylic acids have
COOH group
HC
2
H
3
O
2
, H
3
C
6
H
5
O
7

only the first H in the
formula is acidic
the H is on the COOH
Tro, Chemistry: A Molecular Approach 9
Properties of Bases
also known as alkalis
taste bitter
alkaloids = plant product that is alkaline
often poisonous
solutions feel slippery
change color of vegetable dyes
different color than acid
red litmus turns blue
react with acids to form ionic salts
neutralization
Tro, Chemistry: A Molecular Approach 10
Common Bases
Chemical
Name
Formula
Common
Name
Uses Strength
sodium
hydroxide
NaOH
lye,
caustic soda
soap, plastic,
petrol refining
Strong
potassium
hydroxide
KOH caustic potash
soap, cotton,
electroplating
Strong
calcium
hydroxide
Ca(OH)
2
slaked lime cement Strong
sodium
bicarbonate
NaHCO
3
baking soda cooking, antacid Weak
magnesium
hydroxide
Mg(OH)
2

milk of
magnesia
antacid Weak
ammonium
hydroxide
NH
4
OH,
{NH
3
(aq)}
ammonia
water
detergent,
fertilizer,
explosives, fibers
Weak


Tro, Chemistry: A Molecular Approach 11
Structure of Bases
most ionic bases contain OH ions
NaOH, Ca(OH)
2

some contain CO
3
2-
ions
CaCO
3
NaHCO
3

molecular bases contain structures
that react with H
+
mostly amine groups

Tro, Chemistry: A Molecular Approach 12
Indicators
chemicals which change color depending on
the acidity/basicity
many vegetable dyes are indicators
anthocyanins
litmus
from Spanish moss
red in acid, blue in base
phenolphthalein
found in laxatives
red in base, colorless in acid
Tro, Chemistry: A Molecular Approach 13
Arrhenius Theory
bases dissociate in water to produce OH
-
ions and
cations
ionic substances dissociate in water
NaOH(aq) Na
+
(aq) + OH

(aq)
acids ionize in water to produce H
+
ions and anions
because molecular acids are not made of ions, they cannot
dissociate
they must be pulled apart, or ionized, by the water
HCl(aq) H
+
(aq) + Cl

(aq)
in formula, ionizable H written in front
HC
2
H
3
O
2
(aq) H
+
(aq) + C
2
H
3
O
2

(aq)

Tro, Chemistry: A Molecular Approach 14
Arrhenius Theory
HCl ionizes in water,
producing H
+
and Cl

ions
NaOH dissociates in water,
producing Na
+
and OH

ions
Tro, Chemistry: A Molecular Approach 15
Hydronium Ion
the H
+
ions produced by the acid are so reactive they
cannot exist in water
H
+
ions are protons!!
instead, they react with a water molecule(s) to produce
complex ions, mainly hydronium ion, H
3
O
+

H
+
+ H
2
O H
3
O
+

there are also minor amounts of H
+
with multiple water
molecules, H(H
2
O)
n
+

Tro, Chemistry: A Molecular Approach 16
Arrhenius Acid-Base Reactions
the H
+
from the acid combines with the OH
-

from the base to make a molecule of H
2
O
it is often helpful to think of H
2
O as H-OH
the cation from the base combines with the
anion from the acid to make a salt
acid + base salt + water
HCl(aq) + NaOH(aq) NaCl(aq) + H
2
O(l)
Tro, Chemistry: A Molecular Approach 17
Problems with Arrhenius Theory
does not explain why molecular substances, like
NH
3
, dissolve in water to form basic solutions
even though they do not contain OH

ions
does not explain how some ionic compounds, like
Na
2
CO
3
or Na
2
O, dissolve in water to form basic
solutions even though they do not contain OH

ions
does not explain why molecular substances, like
CO
2
, dissolve in water to form acidic solutions
even though they do not contain H
+
ions
does not explain acid-base reactions that take place
outside aqueous solution
Tro, Chemistry: A Molecular Approach 18
Brnsted-Lowry Theory
in a Brnsted-Lowry Acid-Base reaction, an
H
+
is transferred
does not have to take place in aqueous solution
broader definition than Arrhenius
acid is H donor, base is H acceptor
base structure must contain an atom with an
unshared pair of electrons
in an acid-base reaction, the acid molecule
gives an H
+
to the base molecule
HA + :B :A

+ HB
+


Tro, Chemistry: A Molecular Approach 19
Brnsted-Lowry Acids
Brnsted-Lowry acids are H
+
donors
any material that has H can potentially be a
Brnsted-Lowry acid
because of the molecular structure, often one H in
the molecule is easier to transfer than others
HCl(aq) is acidic because HCl transfers an H
+
to
H
2
O, forming H
3
O
+
ions
water acts as base, accepting H
+

HCl(aq) + H
2
O(l) Cl

(aq) + H
3
O
+
(aq)
acid base
Tro, Chemistry: A Molecular Approach 20
Brnsted-Lowry Bases
Brnsted-Lowry bases are H
+
acceptors
any material that has atoms with lone pairs can
potentially be a Brnsted-Lowry base
because of the molecular structure, often one atom
in the molecule is more willing to accept H
+
transfer
than others
NH
3
(aq) is basic because NH
3
accepts an H
+

from H
2
O, forming OH

(aq)
water acts as acid, donating H
+
NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH

(aq)
base acid
Tro, Chemistry: A Molecular Approach 21
Amphoteric Substances
amphoteric substances can act as either an
acid or a base
have both transferable H and atom with lone pair
water acts as base, accepting H
+
from HCl
HCl(aq) + H
2
O(l) Cl

(aq) + H
3
O
+
(aq)
water acts as acid, donating H
+
to NH
3

NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH

(aq)
Tro, Chemistry: A Molecular Approach 22
Brnsted-Lowry
Acid-Base Reactions
one of the advantages of Brnsted-Lowry theory
is that it allows reactions to be reversible
HA + :B :A

+ HB
+
the original base has an extra H
+
after the
reaction so it will act as an acid in the reverse
process
and the original acid has a lone pair of electrons
after the reaction so it will act as a base in the
reverse process
:A

+ HB
+
HA + :B

Tro, Chemistry: A Molecular Approach 23
Conjugate Pairs
In a Brnsted-Lowry Acid-Base reaction, the
original base becomes an acid in the reverse
reaction, and the original acid becomes a base in
the reverse process
each reactant and the product it becomes is
called a conjugate pair
the original base becomes the conjugate acid;
and the original acid becomes the conjugate base
Tro, Chemistry: A Molecular Approach 24
Brnsted-Lowry
Acid-Base Reactions
HA + :B :A

+ HB
+
acid base conjugate conjugate
base acid
HCHO
2
+ H
2
O CHO
2

+ H
3
O
+
acid base conjugate conjugate
base acid
H
2
O + NH
3
HO

+ NH
4
+
acid base conjugate conjugate
base acid
Tro, Chemistry: A Molecular Approach 25
Conjugate Pairs
In the reaction H
2
O + NH
3
HO

+
NH
4
+


H
2
O and HO

constitute an
Acid/Conjugate Base pair
NH
3
and NH
4
+
constitute a
Base/Conjugate Acid pair
Tro, Chemistry: A Molecular Approach 26
Ex 15.1a Identify the Brnsted-Lowry Acids and
Bases and Their Conjugates in the Reaction
H
2
SO
4
+ H
2
O HSO
4

+ H
3
O
+
acid base conjugate conjugate
base acid
H
2
SO
4
+ H
2
O HSO
4

+ H
3
O
+

When the H
2
SO
4
becomes HSO
4

, it lost an H
+
so
H
2
SO
4
must be the acid and HSO
4

its conjugate base

When the H
2
O becomes H
3
O
+
, it accepted an H
+
so
H
2
O must be the base and H
3
O
+
its conjugate acid
Tro, Chemistry: A Molecular Approach 27
Ex 15.1b Identify the Brnsted-Lowry Acids and
Bases and Their Conjugates in the Reaction
HCO
3

+ H
2
O H
2
CO
3
+ HO

base acid conjugate conjugate
acid base
HCO
3

+ H
2
O H
2
CO
3
+ HO


When the HCO
3

becomes H
2
CO
3
, it accepted an H
+

so HCO
3

must be the base and H

2
CO
3
its conjugate acid
When the H
2
O becomes OH

, it donated an H
+
so
H
2
O must be the acid and OH

its conjugate base

Tro, Chemistry: A Molecular Approach 28
Practice Write the formula for the
conjugate acid of the following
H
2
O
NH
3
CO
3
2
H
2
PO
4
1
Tro, Chemistry: A Molecular Approach 29
Practice Write the formula for the
conjugate acid of the following
H
2
O H
3
O
+

NH
3
NH
4
+

CO
3
2
HCO
3

H
2
PO
4
1
H
3
PO
4

Tro, Chemistry: A Molecular Approach 30
Practice Write the formula for the
conjugate base of the following
H
2
O
NH
3
CO
3
2
H
2
PO
4
1
Tro, Chemistry: A Molecular Approach 31
Practice Write the formula for the
conjugate base of the following
H
2
O HO

NH
3
NH
2

CO
3
2
since CO
3
2
does not have an H, it
cannot be an acid

H
2
PO
4
1
HPO
4
2
Tro, Chemistry: A Molecular Approach 32
Arrow Conventions
chemists commonly use two kinds
of arrows in reactions to indicate
the degree of completion of the
reactions
a single arrow indicates all the
reactant molecules are converted to
product molecules at the end
a double arrow indicates the
reaction stops when only some of
the reactant molecules have been
converted into products
in these notes
Tro, Chemistry: A Molecular Approach 33
Strong or Weak
a strong acid is a strong electrolyte
practically all the acid molecules ionize,
a strong base is a strong electrolyte
practically all the base molecules form OH

ions,
either through dissociation or reaction with water,
a weak acid is a weak electrolyte
only a small percentage of the molecules ionize,
a weak base is a weak electrolyte
only a small percentage of the base molecules form
OH

ions, either through dissociation or reaction with

water,
Tro, Chemistry: A Molecular Approach 34
Strong Acids
The stronger the acid, the
more willing it is to donate H
use water as the standard base
strong acids donate
practically all their Hs
100% ionized in water
strong electrolyte
[H
3
O
+
] = [strong acid]

HCl H
+
+ Cl
-
HCl + H
2
O H
3
O
+
+ Cl
-
Tro, Chemistry: A Molecular Approach 35
Weak Acids
weak acids donate a small
fraction of their Hs
most of the weak acid
molecules do not donate H
to water
much less than 1% ionized
in water
[H
3
O
+
] << [weak acid]

HF H
+
+ F
-
HF + H
2
O H
3
O
+
+ F
-
Tro, Chemistry: A Molecular Approach 36
Polyprotic Acids
often acid molecules have more than one ionizable H
these are called polyprotic acids
the ionizable Hs may have different acid strengths or be equal
1 H = monoprotic, 2 H = diprotic, 3 H = triprotic
HCl = monoprotic, H
2
SO
4
= diprotic, H
3
PO
4
= triprotic
polyprotic acids ionize in steps
each ionizable H removed sequentially
removing of the first H automatically makes removal of
the second H harder
H
2
SO
4
is a stronger acid than HSO
4

Tro, Chemistry: A Molecular Approach 37
Acids Conjugate Bases
HClO
4
ClO
4
-1

H
2
SO
4
HSO
4
-1

HI I
-1

HBr Br
-1

HCl Cl
-1

HNO
3
NO
3
-1

H
3
O
+1
H
2
O
HSO
4
-1
SO
4
-2

H
2
SO
3
HSO
3
-1

H
3
PO
4
H
2
PO
4
-1

HNO
2
NO
2
-1

HF F
-1

HC
2
H
3
O
2
C
2
H
3
O
2
-1

H
2
CO
3
HCO
3
-1

H
2
S HS
-1

NH
4
+1
NH
3

HCN CN
-1

HCO
3
-1
CO
3
-2

HS
-1
S
-2

H
2
O OH
-1

CH
3
-C(O)-CH
3
CH
3
-C(O)-CH
2
-1
NH
3
NH
2
-1

CH
4
CH
3
-1

OH
-1
O
-2

I
n
c
r
e
a
s
i
n
g

A
c
i
d
i
t
y

I
n
c
r
e
a
s
i
n
g


B
a
s
i
c
i
t
y

Tro, Chemistry: A Molecular Approach 38
Strengths of Acids & Bases
commonly, acid or base strength is measured by
determining the equilibrium constant of a substances
reaction with water
HAcid + H
2
O Acid
-1
+ H
3
O
+1
Base: + H
2
O HBase
+1
+ OH
-1

the farther the equilibrium position lies to the products,
the stronger the acid or base
the position of equilibrium depends on the strength of
attraction between the base form and the H
+

stronger attraction means stronger base or weaker acid
Tro, Chemistry: A Molecular Approach 39
General Trends in Acidity
the stronger an acid is at donating H, the
weaker the conjugate base is at accepting H
higher oxidation number = stronger oxyacid
H
2
SO
4
> H
2
SO
3
; HNO
3
> HNO
2

cation stronger acid than neutral molecule;
neutral stronger acid than anion
H
3
O
+1
> H
2
O > OH
-1
; NH
4
+1
> NH
3
> NH
2
-1
base trend opposite
Tro, Chemistry: A Molecular Approach 40
Acid Ionization Constant, K
a
acid strength measured by the size of the
equilibrium constant when react with H
2
O
HAcid + H
2
O Acid
-1
+ H
3
O
+1

the equilibrium constant is called the acid
ionization constant, K
a

larger K
a
= stronger acid
[HAcid]
] O [H ] [Acid
1
3
1
a
+

= K
41
Name Formula K
a1
K
a2
K
a3

Benzoic C
6
H
5
COOH 6.14 x 10
-5

Propanoic CH
3
CH
2
COOH 1.34 x 10
-5

Formic HCOOH 1.77 x 10
-5

Acetic CH
3
COOH 1.75 x 10
-5

Chloroacetic ClCH
2
COOH 1.36 x 10
-5

Trichloroacetic Cl
3
C-COOH 1.29 x 10
-4

Oxalic HOOC-COOH 5.90 x 10
-2
6.40 x 10
-5

Nitric HNO
3
strong
Nitrous HNO
2
4.6 x 10
-4

Phosphoric H
3
PO
4
7.52 x 10
-3
6.23 x 10
-8
2.2 x 10
-13

Phosphorous H
3
PO
3
1.00 x 10
-2
2.6 x 10
-7

Arsenic H
3
AsO
4
6.0 x 10
-3
1.05 x 10
-7
3.0 x 10
-12

Arsenious H
3
AsO
3
6.0 x 10
-10
3.0 x 10
-14
very small
Perchloric HClO
4
> 10
8

Chloric HClO
3
5 x 10
2

Chlorous HClO
2
1.1 x 10
-2

Hypochlorous HClO 3.0 x 10
-8

Boric H
3
BO
3
5.83 x 10
-10

Carbonic H
2
CO
3
4.45 x 10
-7
4.7 x 10
-11



Tro, Chemistry: A Molecular Approach 43
Autoionization of Water
Water is actually an extremely weak electrolyte
therefore there must be a few ions present
about 1 out of every 10 million water molecules
form ions through a process called
autoionization
H
2
O H
+
+ OH

H
2
O + H
2
O H
3
O
+
+ OH

all aqueous solutions contain both H
3
O
+
and OH

the concentration of H
3
O
+
and OH

are equal in water

[H
3
O
+
] = [OH

] = 10
-7
M @ 25C
Tro, Chemistry: A Molecular Approach 44
Ion Product of Water
the product of the H
3
O
+
and OH

concentrations is always the same number
the number is called the ion product of
water and has the symbol K
w

[H
3
O
+
] x [OH

] = K
w
= 1 x 10
-14
@ 25C

if you measure one of the concentrations, you
can calculate the other
as [H
3
O
+
] increases the [OH

] must
decrease so the product stays constant
inversely proportional
Tro, Chemistry: A Molecular Approach 45
Acidic and Basic Solutions
all aqueous solutions contain both H
3
O
+
and
OH

ions
neutral solutions have equal [H
3
O
+
] and [OH

]
[H
3
O
+
] = [OH

] = 1 x 10
-7

acidic solutions have a larger [H
3
O
+
] than [OH

]
[H
3
O
+
] > 1 x 10
-7
; [OH

] < 1 x 10
-7

basic solutions have a larger [OH

] than [H
3
O
+
]
[H
3
O
+
] < 1 x 10
-7
; [OH

] > 1 x 10
-7


Example 15.2b Calculate the [OH

] at 25C when the

[H
3
O
+
] = 1.5 x 10
-9
M, and determine if the solution is
acidic, basic, or neutral
The units are correct. The fact that the
[H
3
O
+
] < [OH

] means the solution is basic

[H
3
O
+
] = 1.5 x 10
-9
M
[OH

]
Check:
Solution:
Concept Plan:

Relationships:
Given:
Find:
[H
3
O
+
] [OH

]
]
-
][OH O H [
3 w
+
= K
] O H [
]
-
OH [
]
-
OH ][ O H [
3
w
3 w
+
+
=
=
K
K
M 10 7 . 6
10 5 . 1
10 0 . 1
]
-
[OH
6
9
14

=
Tro, Chemistry: A Molecular Approach 47
Complete the Table
[H
+
] vs. [OH
-
]
OH
-
H
+
H
+
H
+
H
+
H
+
OH
-
OH
-
OH
-
OH
-
[OH
-
]
[H
+
] 10
0
10
-1
10
-3
10
-5
10
-7
10
-9
10
-11
10
-13
10
-14
Tro, Chemistry: A Molecular Approach 48
Complete the Table
[H
+
] vs. [OH
-
]
OH
-
H
+
H
+
H
+
H
+
H
+
OH
-
OH
-
OH
-
OH
-
[OH
-
]10
-14
10
-13
10
-11
10
-9
10
-7
10
-5
10
-3
10
-1
10
0
[H
+
] 10
0
10
-1
10
-3
10
-5
10
-7
10
-9
10
-11
10
-13
10
-14
even though it may look like it, neither H
+
nor OH
-
will ever be 0
the sizes of the H
+
and OH
-
are not to scale
because the divisions are powers of 10 rather than units
Acid
Base
Tro, Chemistry: A Molecular Approach 49
pH
the acidity/basicity of a solution is often
expressed as pH
pH = -log[H
3
O
+
], [H
3
O
+
] = 10
-pH
exponent on 10 with a positive sign
pH
water
= -log[10
-7
] = 7
need to know the [H
+
] concentration to find pH
pH < 7 is acidic; pH > 7 is basic, pH = 7 is
neutral
Tro, Chemistry: A Molecular Approach 50
Sig. Figs. & Logs
when you take the log of a number written in scientific
notation, the digit(s) before the decimal point come from
the exponent on 10, and the digits after the decimal
point come from the decimal part of the number
log(2.0 x 10
6
) = log(10
6
) + log(2.0)
= 6 + 0.30303 = 6.30303...
since the part of the scientific notation number that
determines the significant figures is the decimal part,
the sig figs are the digits after the decimal point in
the log
log(2.0 x 10
6
) = 6.30
51
pH
the lower the pH, the more acidic the solution; the
higher the pH, the more basic the solution
1 pH unit corresponds to a factor of 10 difference
in acidity
normal range 0 to 14
pH 0 is [H
+
] = 1 M, pH 14 is [OH

] = 1 M
pH can be negative (very acidic) or larger than 14
(very alkaline)

52
pH of Common Substances
Substance pH
1.0 M HCl 0.0
0.1 M HCl 1.0
stomach acid 1.0 to 3.0
lemons 2.2 to 2.4
soft drinks 2.0 to 4.0
plums 2.8 to 3.0
apples 2.9 to 3.3
cherries 3.2 to 4.0
unpolluted rainwater 5.6
human blood 7.3 to 7.4
egg whites 7.6 to 8.0
milk of magnesia (satd Mg(OH)
2
) 10.5
household ammonia 10.5 to 11.5
1.0 M NaOH 14
Tro, Chemistry: A Molecular Approach 53
Example 15.3b Calculate the pH at 25C when the
[OH

] = 1.3 x 10
-2
M, and determine if the solution is
acidic, basic, or neutral
pH is unitless. The fact that the pH > 7 means the
solution is basic
[OH

] = 1.3 x 10
-2
M
pH
Check:
Solution:
Concept Plan:

Relationships:
Given:
Find:
]
-
][OH O H [
3 w
+
= K
2
14
3
3 w
10 3 . 1
10 0 . 1
] O H [
]
-
OH ][ O H [

+
+

=
= K M 10 7 . 7 ] O [H
13
3
+
=
[H
3
O
+
] [OH

] pH
] O H [ log pH
3
-
+
=
( )
12.11 pH
10 7 . 7 log - pH
13
=
=

Tro, Chemistry: A Molecular Approach 55
pOH
another way of expressing the acidity/basicity of
a solution is pOH
pOH = -log[OH

], [OH

] = 10
-pOH
pOH
water
= -log[10
-7
] = 7
need to know the [OH

] concentration to find pOH

pOH < 7 is basic; pOH > 7 is acidic, pOH = 7 is
neutral
Tro, Chemistry: A Molecular Approach 56
pH and pOH
Complete the Table
OH
-
H
+
H
+
H
+
H
+
H
+
OH
-
OH
-
OH
-
OH
-
[OH
-
]10
-14
10
-13
10
-11
10
-9
10
-7
10
-5
10
-3
10
-1
10
0
[H
+
] 10
0
10
-1
10
-3
10
-5
10
-7
10
-9
10
-11
10
-13
10
-14
pH
pOH
Tro, Chemistry: A Molecular Approach 57
pH and pOH
Complete the Table
OH
-
H
+
H
+
H
+
H
+
H
+
OH
-
OH
-
OH
-
OH
-
[OH
-
]10
-14
10
-13
10
-11
10
-9
10
-7
10
-5
10
-3
10
-1
10
0
[H
+
] 10
0
10
-1
10
-3
10
-5
10
-7
10
-9
10
-11
10
-13
10
-14
pH 0 1 3 5 7 9 11 13 14
pOH 14 13 11 9 7 5 3 1 0
Tro, Chemistry: A Molecular Approach 58
Relationship between pH and pOH
the sum of the pH and pOH of a solution = 14.00
at 25C
can use pOH to find pH of a solution
( ) ( ) ( )
( ) ( ) ( ) ( )
14.00 pOH pH
00 . 14 ]
-
[OH log ] O H [ log
10 0 . 1 log ]
-
][OH O H [ log
10 0 . 1 ]
-
][OH O H [
3
14
3
14
w 3
= +
= +
=
= =
+
+
+
K
Tro, Chemistry: A Molecular Approach 59
pK
a way of expressing the strength of an acid or
base is pK
pK
a
= -log(K
a
), K
a
= 10
-pKa
pK
b
= -log(K
b
), K
b
= 10
-pKb

the stronger the acid, the smaller the pK
a

larger K
a
= smaller pK
a

because it is the log

Tro, Chemistry: A Molecular Approach 60
Finding the pH of a Strong Acid
there are two sources of H
3
O
+
in an aqueous
solution of a strong acid the acid and the water
for the strong acid, the contribution of the water
to the total [H
3
O
+
] is negligible
shifts the K
w
equilibrium to the left so far that
[H
3
O
+
]
water

is too small to be significant
except in very dilute solutions, generally < 1 x 10
-4
M
for a monoprotic strong acid [H
3
O
+
] = [HAcid]
for polyprotic acids, the other ionizations can
generally be ignored
0.10 M HCl has [H
3
O
+
] = 0.10 M and pH = 1.00
Tro, Chemistry: A Molecular Approach 61
Finding the pH of a Weak Acid
there are also two sources of H
3
O
+
in and
aqueous solution of a weak acid the acid and
the water
however, finding the [H
3
O
+
] is complicated by
the fact that the acid only undergoes partial
ionization
calculating the [H
3
O
+
] requires solving an
equilibrium problem for the reaction that defines
the acidity of the acid
HAcid + H
2
O Acid

+ H
3
O
+

Tro, Chemistry: A Molecular Approach 62
[HNO
2
] [NO
2
-
] [H
3
O
+
]
initial
change
equilibrium
Ex 15.6 Find the pH of 0.200 M HNO
2
(aq)
solution @ 25C

Write the reaction for
the acid with water
Construct an ICE
table for the reaction
Enter the initial
concentrations
assuming the [H
3
O
+
]
from water is 0
since no products initially, Q
c
= 0, and the reaction is proceeding forward
HNO
2
+ H
2
O NO
2

+ H
3
O
+
[HNO
2
] [NO
2
-
] [H
3
O
+
]
initial
0.200
0 0
change
equilibrium
Tro, Chemistry: A Molecular Approach 63
[HNO
2
] [NO
2
-
] [H
3
O
+
]
initial
0.200
0 0
change
equilibrium
Ex 15.6 Find the pH of 0.200 M HNO
2
(aq)
solution @ 25C
represent the change
in the concentrations
in terms of x
sum the columns to
find the equilibrium
concentrations in
terms of x
substitute into the
equilibrium constant
expression
+x
+x x
0.200 x
x x
| |
( )( )
( ) x
x x
K

= =

+
1
2
3
-
2
a
10 00 . 2 HNO
] O H ][ [NO
Tro, Chemistry: A Molecular Approach 64
Ex 15.6 Find the pH of 0.200 M HNO
2
(aq)
solution @ 25C
| || |
| |
( )( )
( ) x
x x
K

= =

+
1
2
3
-
2
a
10 00 . 2 HNO
O H NO
determine the value of
K
a
from Table 15.5
since K
a
is very small,
approximate the
[HNO
2
]
eq
= [HNO
2
]
init

and solve for x
| || |
| |
( )( )
( )
1
2
3
-
2
a
10 00 . 2 HNO
O H NO

= =
x x
K
1
2
4
10 00 . 2
10 6 . 4

=
x
( )( )
3
1 4
10 6 . 9
10 00 . 2 10 6 . 4

=
=
x
x
K
a
for HNO
2
= 4.6 x 10
-4

[HNO
2
] [NO
2
-
] [H
3
O
+
]
initial
0.200
0 0
change -x +x +x
equilibrium 0.200 x x 0.200 x
Tro, Chemistry: A Molecular Approach 65
Ex 15.6 Find the pH of 0.200 M HNO
2
(aq)
solution @ 25C
K
a
for HNO
2
= 4.6 x 10
-4

[HNO
2
] [NO
2
-
] [H
3
O
+
]
initial
0.200
0 0
change -x +x +x
equilibrium 0.200
x x
check if the
approximation is
valid by seeing if x
< 5% of [HNO
2
]
init

% 5 % 8 . 4 % 100
10 00 . 2
10 6 . 9
1
3
< =

the approximation is valid

x = 9.6 x 10
-3

Tro, Chemistry: A Molecular Approach 66
Ex 15.6 Find the pH of 0.200 M HNO
2
(aq)
solution @ 25C
K
a
for HNO
2
= 4.6 x 10
-4

[HNO
2
] [NO
2
-
] [H
3
O
+
]
initial
0.200
0 0
change -x +x +x
equilibrium 0.200-x
x x
x = 9.6 x 10
-3

substitute x into the
equilibrium
concentration
definitions and solve
| | ( ) M 190 . 0 10 6 . 9 200 . 0 200 . 0 HNO
3
2
= = =

x
| | | | M 10 6 . 9 O H NO
3
3
-
2
+
= = = x
[HNO
2
] [NO
2
-
] [H
3
O
+
]
initial
0.200
0 0
change -x +x +x
equilibrium 0.190 0.0096 0.0096
Tro, Chemistry: A Molecular Approach 67
Ex 15.6 Find the pH of 0.200 M HNO
2
(aq)
solution @ 25C
K
a
for HNO
2
= 4.6 x 10
-4

substitute [H
3
O
+
]
into the formula for
pH and solve
[HNO
2
] [NO
2
-
] [H
3
O
+
]
initial
0.200
0 0
change -x +x +x
equilibrium 0.190 0.0096 0.0096
( )
( ) 02 . 2 10 6 . 9 log
O H -log pH
3
3
= =
=

+
Tro, Chemistry: A Molecular Approach 68
Ex 15.6 Find the pH of 0.200 M HNO
2
(aq)
solution @ 25C
K
a
for HNO
2
= 4.6 x 10
-4

[HNO
2
] [NO
2
-
] [H
3
O
+
]
initial
0.200
0 0
change -x +x +x
equilibrium 0.190 0.0096 0.0096
check by substituting
the equilibrium
concentrations back into
the equilibrium constant
expression and
comparing the calculated
K
a
to the given K
a

| || |
| |
( )
( )
4
2
3
2
3
-
2
a
10 9 . 4
190 . 0
10 6 . 9
HNO
O H NO

+
=

=
= = K
though not exact,
the answer is
reasonably close
Tro, Chemistry: A Molecular Approach 69
Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC
6
H
4
NO
2
?
(K
a
= 1.4 x 10
-5
@ 25C)
Tro, Chemistry: A Molecular Approach 70
Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC
6
H
4
NO
2
?
Write the reaction for
the acid with water
Construct an ICE
table for the reaction
Enter the initial
concentrations
assuming the [H
3
O
+
]
from water is 0
HC
6
H
4
NO
2
+ H
2
O C
6
H
4
NO
2

+ H
3
O
+
[HA] [A
-
] [H
3
O
+
]
initial
0.012
0 0
change
equilibrium
Tro, Chemistry: A Molecular Approach 71
[HA] [A
-
] [H
3
O
+
]
initial
0.012
0 0
change
equilibrium
Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC
6
H
4
NO
2
?
represent the change
in the concentrations
in terms of x
sum the columns to
find the equilibrium
concentrations in
terms of x
substitute into the
equilibrium constant
expression
+x
+x x
0.012 x
x x
| |
( )( )
( ) x
x x
K

= =

+
2
2 4 6
3
-
2 4 6
a
10 2 . 1 NO H HC
] O H ][ NO H [C
HC
6
H
4
NO
2
+ H
2
O C
6
H
4
NO
2

+ H
3
O
+
Tro, Chemistry: A Molecular Approach 72
| || |
| |
( )( )
( ) x
x x
K

= =

+
2
3
-
a
10 2 . 1 HA
O H A
determine the value of
K
a

since K
a
is very small,
approximate the
[HA]
eq
= [HA]
init
and
solve for x
| || |
| |
( )( )
( )
2
3
-
a
10 2 . 1 HA
O H A

= =
x x
K
2
2
5
10 2 . 1
10 4 . 1

=
x
( )( )
4
2 5
10 1 . 4
10 2 . 1 10 4 . 1

=
=
x
x
[HA] [A
2
-
] [H
3
O
+
]
initial
0.012
0 0
change -x +x +x
equilibrium 0.012 x x 0.012 x
Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC
6
H
4
NO
2
? K
a
= 1.4 x 10
-5
@ 25C
HC
6
H
4
NO
2
+ H
2
O C
6
H
4
NO
2

+ H
3
O
+
Tro, Chemistry: A Molecular Approach 73
Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC
6
H
4
NO
2
? K
a
= 1.4 x 10
-5
@ 25C
K
a
for HC
6
H
4
NO
2
= 1.4 x 10
-5

check if the
approximation is
valid by seeing if
x < 5% of
[HC
6
H
4
NO
2
]
init

% 5 % 4 . 3 % 100
10 2 . 1
10 1 . 4
2
4
< =

the approximation is valid

x = 4.1 x 10
-4

[HA] [A
2
-
] [H
3
O
+
]
initial
0.012
0 0
change -x +x +x
equilibrium 0.012
x x
Tro, Chemistry: A Molecular Approach 74
Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC
6
H
4
NO
2
? K
a
= 1.4 x 10
-5
@ 25C
x = 4.1 x 10
-4

substitute x into the
equilibrium
concentration
definitions and solve
| | ( ) M 012 . 0 10 1 . 4 012 . 0 012 . 0 NO H HC
4
2 4 6
= = =

x
| | | | M 10 1 . 4 O H NO H C
4
3
-
2 4 6
+
= = = x
[HA] [A
2
-
] [H
3
O
+
]
initial
0.012
0 0
change -x +x +x
equilibrium 0.012-x
x x
Tro, Chemistry: A Molecular Approach 75
Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC
6
H
4
NO
2
? K
a
= 1.4 x 10
-5
@ 25C
substitute [H
3
O
+
]
into the formula for
pH and solve
( )
( ) 39 . 3 10 1 . 4 log
O H -log pH
4
3
= =
=

+
[HA] [A
2
-
] [H
3
O
+
]
initial
0.012
0 0
change -x +x +x
equilibrium 0.012 0.00041 0.00041
Tro, Chemistry: A Molecular Approach 76
Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC
6
H
4
NO
2
? K
a
= 1.4 x 10
-5
@ 25C
check by substituting
the equilibrium
concentrations back into
the equilibrium constant
expression and
comparing the calculated
K
a
to the given K
a

the values match
[HA] [A
2
-
] [H
3
O
+
]
initial
0.012
0 0
change -x +x +x
equilibrium 0.012 0.00041 0.00041
| |
( )
( )
5
2
2
4
2 4 6
3
-
2 4 6
a
10 4 . 1
10 2 . 1
10 1 . 4
NO H HC
] O H ][ NO H [C

+
=

=
= K
Tro, Chemistry: A Molecular Approach 77
[HClO
2
] [ClO
2
-
] [H
3
O
+
]
initial
0.100
0 0
change
equilibrium
Ex 15.7 Find the pH of 0.100 M HClO
2
(aq)
solution @ 25C

Write the reaction for
the acid with water
Construct an ICE
table for the reaction
Enter the initial
concentrations
assuming the [H
3
O
+
]
from water is 0
HClO
2
+ H
2
O ClO
2

+ H
3
O
+
Tro, Chemistry: A Molecular Approach 78
Ex 15.7 Find the pH of 0.100 M HClO
2
(aq)
solution @ 25C
represent the change
in the concentrations
in terms of x
sum the columns to
find the equilibrium
concentrations in
terms of x
substitute into the
equilibrium constant
expression
| |
( )( )
( ) x
x x
K

= =

+
1
2
3
-
2
a
10 00 . 1 HClO
] O H ][ [ClO
[HClO
2
] [ClO
2
-
] [H
3
O
+
]
initial
0.100
0 0
change -x +x +x
equilibrium 0.100-x x x
Tro, Chemistry: A Molecular Approach 79
Ex 15.7 Find the pH of 0.100 M HClO
2
(aq)
solution @ 25C
determine the value of
K
a
from Table 15.5
since K
a
is very small,
approximate the
[HClO
2
]
eq
= [HClO
2
]
init

and solve for x
| || |
| |
( )( )
( )
1
2
3
-
2
a
10 00 . 1 HClO
O H ClO

= =
x x
K
1
2
2
10 00 . 1
10 1 . 1

=
x
( )( )
2
1 2
10 3 . 3
10 00 . 1 10 1 . 1

=
=
x
x
K
a
for HClO
2
= 1.1 x 10
-2

[HClO
2
] [ClO
2
-
] [H
3
O
+
]
initial
0.100
0 0
change -x +x +x
equilibrium 0.100-x x x
Tro, Chemistry: A Molecular Approach 80
Ex 15.7 Find the pH of 0.100 M HClO
2
(aq)
solution @ 25C
K
a
for HClO
2
= 1.1 x 10
-2

check if the
approximation is
valid by seeing if x
< 5% of [HNO
2
]
init

% 5 % 33 % 100
10 00 . 1
10 3 . 3
1
2
> =

the approximation is invalid

x = 3.3 x 10
-2

[HClO
2
] [ClO
2
-
] [H
3
O
+
]
initial
0.100
0 0
change -x +x +x
equilibrium 0.100-x x x
Tro, Chemistry: A Molecular Approach 81
Ex 15.7 Find the pH of 0.100 M HClO
2
(aq)
solution @ 25C
| || |
| |
( )( )
( ) x
x x
K

= =

+
1
2
3
-
2
a
10 00 . 1 HClO
O H ClO
( ) x
x

=

1
2
2
10 00 . 1
10 1 . 1
( )
0.039 - or 028 . 0
) 1 ( 2
) 0011 . 0 )( 1 ( 4 011 . 0 011 . 0
0011 . 0 011 . 0 0
2
2
=

=
+ =
x
x
x x
K
a
for HClO
2
= 1.1 x 10
-2

if the approximation
is invalid, solve for x
using the quadratic
formula
Tro, Chemistry: A Molecular Approach 82
Ex 15.7 Find the pH of 0.100 M HClO
2
(aq)
solution @ 25C
K
a
for HClO
2
= 1.1 x 10
-2

x = 0.028
substitute x into the
equilibrium
concentration
definitions and solve
| | ( ) M 072 . 0 028 . 0 100 . 0 100 . 0 HClO
2
= = = x
| | | | M 028 . 0 O H ClO
3
-
2
= = =
+
x
[HClO
2
] [ClO
2
-
] [H
3
O
+
]
initial
0.100
0 0
change -x +x +x
equilibrium 0.100-x x x
[HClO
2
] [ClO
2
-
] [H
3
O
+
]
initial
0.100
0 0
change -x +x +x
equilibrium 0.072 0.028 0.028
Tro, Chemistry: A Molecular Approach 83
Ex 15.7 Find the pH of 0.100 M HClO
2
(aq)
solution @ 25C
K
a
for HClO
2
= 1.1 x 10
-2

substitute [H
3
O
+
]
into the formula for
pH and solve
( )
( ) 55 . 1 028 . 0 log
O H -log pH
3
= =
=
+
[HClO
2
] [ClO
2
-
] [H
3
O
+
]
initial
0.100
0 0
change -x +x +x
equilibrium 0.072 0.028 0.028
Tro, Chemistry: A Molecular Approach 84
Ex 15.7 Find the pH of 0.100 M HClO
2
(aq)
solution @ 25C
K
a
for HClO
2
= 1.1 x 10
-2

check by substituting
the equilibrium
concentrations back into
the equilibrium constant
expression and
comparing the calculated
K
a
to the given K
a

| || |
| |
( )
( )
2
2
2
3
-
2
a
10 1 . 1
072 . 0
028 . 0
HClO
O H ClO

+
= =
= = K
the answer matches
[HClO
2
] [ClO
2
-
] [H
3
O
+
]
initial
0.100
0 0
change -x +x +x
equilibrium 0.072 0.028 0.028
Tro, Chemistry: A Molecular Approach 85
Ex 15.8 - What is the K
a
of a weak acid if a
0.100 M solution has a pH of 4.25?
Use the pH to find the
equilibrium [H
3
O
+
]
Write the reaction for
the acid with water
Construct an ICE table
for the reaction
Enter the initial
concentrations and
[H
3
O
+
]
equil

HA + H
2
O A

+ H
3
O
+
[HA] [A
-
] [H
3
O
+
]
initial
change
equilibrium
M 10 6 . 5 10 10 ] O H [
5 25 . 4 -pH
3
+
= = =
[HA] [A
-
] [H
3
O
+
]
initial
0.100
0 0
change
equilibrium 5.6E-05
Tro, Chemistry: A Molecular Approach 86
[HA] [A
-
] [H
3
O
+
]
initial
0.100
0 0
change
equilibrium
Ex 15.8 - What is the K
a
of a weak acid if a
0.100 M solution has a pH of 4.25?
fill in the rest of the
table using the
[H
3
O
+
] as a guide
if the difference is
insignificant,
[HA]
equil
= [HA]
initial

substitute into the K
a

expression and
compute K
a

+5.6E-05 +5.6E-05 5.6E-05
0.100
5.6E-05
5.6E-05 5.6E-05
| |
( )( )
( )
8
a
5 5
3
-
a
10 1 . 3
100 . 0
10 6 . 5 10 6 . 5
HA
] O H ][ [A

+
=

= =
K
K
HA + H
2
O A

+ H
3
O
+
0.100
Tro, Chemistry: A Molecular Approach 87
Percent Ionization
another way to measure the strength of an acid is
to determine the percentage of acid molecules that
ionize when dissolved in water this is called the
percent ionization
the higher the percent ionization, the stronger the acid
since [ionized acid]
equil
= [H
3
O
+
]
equil
% 100
acid of molarity initial
acid ionized of molarity
Ionization Percent =
% 100
[HA]
] O [H
Ionization Percent
init
equil 3
=
+
Tro, Chemistry: A Molecular Approach 88
Ex 15.9 - What is the percent ionization of a
2.5 M HNO
2
solution?
Write the reaction for
the acid with water
Construct an ICE table
for the reaction
Enter the Initial
Concentrations
Define the Change in
Concentration in
terms of x
Sum the columns to
define the Equilibrium
Concentrations
HNO
2
+ H
2
O NO
2

+ H
3
O
+
[HNO
2
] [NO
2
-
] [H
3
O
+
]
initial
change
equilibrium
[HNO
2
] [NO
2
-
] [H
3
O
+
]
initial
2.5
0 0
change
equilibrium
+x
+x x
2.5 x x x
Tro, Chemistry: A Molecular Approach 89
determine the value of
K
a
from Table 15.5
since K
a
is very small,
approximate the
[HNO
2
]
eq
= [HNO
2
]
init

and solve for x
| || |
| |
( )( )
( ) 5 . 2 HNO
O H NO
2
3
-
2
a
x x
K = =
+
5 . 2
10 6 . 4
2
4
x
=

( )( )
2
4
10 4 . 3
5 . 2 10 6 . 4

=
=
x
x
K
a
for HNO
2
= 4.6 x 10
-4

[HNO
2
] [NO
2
-
] [H
3
O
+
]
initial
2.5
0 0
change -x +x +x
equilibrium 2.5-x 2.5 x x
Ex 15.9 - What is the percent ionization of a
2.5 M HNO
2
solution?
Tro, Chemistry: A Molecular Approach 90
Ex 15.9 - What is the percent ionization of a
2.5 M HNO
2
solution?
HNO
2
+ H
2
O NO
2

+ H
3
O
+
[HNO
2
] [NO
2
-
] [H
3
O
+
]
initial
2.5
0 0
change -x +x +x
equilibrium 2.5 0.034 0.034 2.5 x x x
substitute x into the
Equilibrium
Concentration
definitions and solve
| | ( ) M 5 . 2 034 . 0 5 . 2 5 . 2 HNO
2
= = = x
| | | | M 034 . 0 O H NO
3
-
2
= = =
+
x
x = 3.4 x 10
-2

Tro, Chemistry: A Molecular Approach 91
Ex 15.9 - What is the percent ionization of a
2.5 M HNO
2
solution?
HNO
2
+ H
2
O NO
2

+ H
3
O
+
[HNO
2
] [NO
2
-
] [H
3
O
+
]
initial
2.5
0 0
change -x +x +x
equilibrium 2.5 0.034 0.034
Apply the Definition
and Compute the
Percent Ionization
% 4 . 1 % 100
5 . 2
10 4 . 3
% 100
] [HNO
] O [H
Ionization Percent
2
init 2
equil 3
=

=
=

+ since the percent

ionization is < 5%,
the x is small
approximation is
valid
Tro, Chemistry: A Molecular Approach 92
Relationship Between
[H
3
O
+
]
equilibrium
& [HA]
initial

increasing the initial concentration
of acid results in increased H
3
O
+

concentration at equilibrium
increasing the initial concentration
of acid results in decreased percent
ionization
this means that the increase in H
3
O
+

concentration is slower than the
increase in acid concentration
% 100
[HA]
] O [H
Ionization Percent
init
equil 3
=
+
93
Why doesnt the increase in H
3
O
+

keep up with the increase in HA?
the reaction for ionization of a weak acid is:
HA
(aq)
+ H
2
O
(l)
A

(aq)
+ H
3
O
+
(aq)

according to Le Chteliers Principle, if we reduce the
concentrations of all the (aq) components, the equilibrium
should shift to the right to increase the total number of
dissolved particles
we can reduce the (aq) concentrations by using a more dilute
initial acid concentration
the result will be a larger [H
3
O
+
] in the dilute solution
compared to the initial acid concentration
this will result in a larger percent ionization
Tro, Chemistry: A Molecular Approach 94
Finding the pH of Mixtures of Acids
generally, you can ignore the contribution of the
weaker acid to the [H
3
O
+
]
equil

for a mixture of a strong acid with a weak acid, the
complete ionization of the strong acid provides more
than enough [H
3
O
+
] to shift the weak acid equilibrium
to the left so far that the weak acids added [H
3
O
+
] is
negligible
for mixtures of weak acids, generally only need to
consider the stronger for the same reasons
as long as one is significantly stronger than the other, and
their concentrations are similar
Tro, Chemistry: A Molecular Approach 95
Ex 15.10 Find the pH of a mixture of 0.150 M
HF(aq) solution and 0.100 M HClO
2
(aq)
Write the reactions for
the acids with water
and determine their K
a
s
If the K
a
s are
sufficiently different,
use the strongest acid to
construct an ICE table
for the reaction
Enter the initial
concentrations
assuming the [H
3
O
+
]
from water is 0
HF + H
2
O F

+ H
3
O
+
K
a
= 3.5 x 10
-4
[HF] [F
-
] [H
3
O
+
]
initial
0.150
0 0
change
equilibrium
HClO + H
2
O ClO

+ H
3
O
+
K
a
= 2.9 x 10
-8
H
2
O + H
2
O OH

+ H
3
O
+
K
w
= 1.0 x 10
-14
Tro, Chemistry: A Molecular Approach 96
[HF] [F
-
] [H
3
O
+
]
initial
0.150
0 0
change
equilibrium
Ex 15.10 Find the pH of a mixture of 0.150 M
HF(aq) solution and 0.100 M HClO
2
(aq)
represent the change
in the concentrations
in terms of x
sum the columns to
find the equilibrium
concentrations in
terms of x
substitute into the
equilibrium constant
expression
+x
+x x
0.150 x
x x
| |
( )( )
( ) x
x x
K

= =

+
1
3
-
a
10 50 . 1 HF
] O H ][ [F
Tro, Chemistry: A Molecular Approach 97
Ex 15.10 Find the pH of a mixture of 0.150 M
HF(aq) solution and 0.100 M HClO
2
(aq)
| || |
| |
( )( )
( ) x
x x
K

= =
+
150 . 0 HF
O H F
3
-
a
determine the value of
K
a
for HF
since K
a
is very small,
approximate the
[HF]
eq
= [HF]
init
and
solve for x
| || |
| |
( )( )
( ) 150 . 0 HF
O H F
3
-
a
x x
K = =
+
1
2
4
10 50 . 1
10 5 . 3

=
x
( )( )
3
1 4
10 2 . 7
10 50 . 1 10 5 . 3

=
=
x
x
K
a
for HF = 3.5 x 10
-4

[HF] [F
-
] [H
3
O
+
]
initial
0.150
0 0
change -x +x +x
equilibrium 0.150 x x 0.150 x
Tro, Chemistry: A Molecular Approach 98
Ex 15.10 Find the pH of a mixture of 0.150 M
HF(aq) solution and 0.100 M HClO
2
(aq)
K
a
for HF = 3.5 x 10
-4

[HF] [F
-
] [H
3
O
+
]
initial
0.150
0 0
change -x +x +x
equilibrium 0.150
x x
check if the
approximation is
valid by seeing if x
< 5% of [HF]
init

% 5 % 8 . 4 % 100
10 50 . 1
10 2 . 7
1
3
< =

the approximation is valid

x = 7.2 x 10
-3

Tro, Chemistry: A Molecular Approach 99
Ex 15.10 Find the pH of a mixture of 0.150 M
HF(aq) solution and 0.100 M HClO
2
(aq)
K
a
for HF = 3.5 x 10
-4

[HF] [F
-
] [H
3
O
+
]
initial
0.150
0 0
change -x +x +x
equilibrium 0.150-x
x x
x = 7.2 x 10
-3

substitute x into the
equilibrium
concentration
definitions and solve
| | ( ) M 143 . 0 10 2 . 7 150 . 0 150 . 0 HF
3
= = =

x
| | | | M 10 2 . 7 O H F
3
3
- +
= = = x
[HF] [F
-
] [H
3
O
+
]
initial
0.150
0 0
change -x +x +x
equilibrium 0.143 0.0072 0.0072
Tro, Chemistry: A Molecular Approach 100
Ex 15.10 Find the pH of a mixture of 0.150 M
HF(aq) solution and 0.100 M HClO
2
(aq)
K
a
for HF = 3.5 x 10
-4

substitute [H
3
O
+
]
into the formula for
pH and solve
( )
( ) 14 . 2 10 2 . 7 log
O H -log pH
3
3
= =
=

+
[HF] [F
-
] [H
3
O
+
]
initial
0.150
0 0
change -x +x +x
equilibrium 0.143 0.0072 0.0072
Tro, Chemistry: A Molecular Approach 101
Ex 15.10 Find the pH of a mixture of 0.150 M
HF(aq) solution and 0.100 M HClO
2
(aq)
K
a
for HF = 3.5 x 10
-4

check by substituting
the equilibrium
concentrations back into
the equilibrium constant
expression and
comparing the calculated
K
a
to the given K
a

| || |
| |
( )
( )
4
2
3
3
-
a
10 6 . 3
143 . 0
10 2 . 7
HF
O H F

+
=

=
= = K
though not exact,
the answer is
reasonably close
[HF] [F
-
] [H
3
O
+
]
initial
0.150
0 0
change -x +x +x
equilibrium 0.143 0.0072 0.0072
Tro, Chemistry: A Molecular Approach 102
NaOH Na
+
+ OH
-
Strong Bases
the stronger the base, the more
willing it is to accept H
use water as the standard acid
for strong bases, practically all
molecules are dissociated into
OH

or accept Hs
strong electrolyte
multi-OH strong bases
completely dissociated
[HO

] = [strong base] x (# OH)

Example 15.11b Calculate the pH at 25C of a 0.0015 M
Sr(OH)
2
solution and determine if the solution is acidic,
basic, or neutral
pH is unitless. The fact that the pH > 7 means the
solution is basic
[Sr(OH)
2
] = 1.5 x 10
-3
M
pH
Check:
Solution:
Concept Plan:
Relationships:
Given:
Find:
]
-
][OH O H [
3 w
+
= K
3
14
3
3 w
10 0 . 3
10 0 . 1
] O H [
]
-
OH ][ O H [

+
+

=
= K
M 10 3 . 3 ] O [H
12
3
+
=
] O H [ log pH
3
-
+
=
( )
11.48 pH
10 3 . 3 log - pH
12
=
=

[H
3
O
+
] [OH

] pH [Sr(OH)
2
]
[OH

]=2[Sr(OH)
2
]
[OH

]
= 2(0.0015)
= 0.0030 M
Tro, Chemistry: A Molecular Approach 105
Practice - Calculate the pH of a 0.0010 M
Ba(OH)
2
solution and determine if it is
acidic, basic, or neutral
Tro, Chemistry: A Molecular Approach 106
Practice - Calculate the pH of a 0.0010 M
Ba(OH)
2
solution and determine if it is
acidic, basic, or neutral
[H
3
O
+
] =
1.00 x 10
-14

2.0 x 10
-3
= 5.0 x 10
-12
M
pH > 7 therefore basic
Ba(OH)
2
= Ba
2+
+ 2 OH
-
therefore
[OH
-
] = 2 x 0.0010 = 0.0020 = 2.0 x 10
-3
M
pH = -log [H
3
O
+
] = -log (5.0 x 10
-12
)
pH = 11.30
K
w
= [H
3
O
+
][OH

]
Tro, Chemistry: A Molecular Approach 107
Weak Bases
in weak bases, only a small
fraction of molecules accept Hs
weak electrolyte
most of the weak base molecules
do not take H from water
much less than 1% ionization in
water
[HO

] << [weak base]

finding the pH of a weak base
solution is similar to finding the
pH of a weak acid

NH
3
+ H
2
O NH
4
+
+ OH
-
Tro, Chemistry: A Molecular Approach 108
Tro, Chemistry: A Molecular Approach 109
Structure of Amines
Tro, Chemistry: A Molecular Approach 110
[NH
3
] [NH
4
+
] [OH

]
initial
change
equilibrium
Ex 15.12 Find the pH of 0.100 M NH
3
(aq) solution

Write the reaction for
the base with water
Construct an ICE
table for the reaction
Enter the initial
concentrations
assuming the [OH

]
from water is 0
since no products initially, Q
c
= 0, and the reaction is proceeding forward
NH
3
+ H
2
O NH
4
+
+ OH

[NH
3
] [NH
4
+
] [OH

]
initial
0.100
0 0
change
equilibrium
Tro, Chemistry: A Molecular Approach 111
[NH
3
] [NH
4
+
] [OH

]
initial
0.100
0 0
change
equilibrium
Ex 15.12 Find the pH of 0.100 M NH
3
(aq) solution
represent the change
in the concentrations
in terms of x
sum the columns to
find the equilibrium
concentrations in
terms of x
substitute into the
equilibrium constant
expression
+x
+x x
0.100 x
x x
| |
( )( )
( ) x
x x
K

= =

+
1
3
4
b
10 00 . 1 NH
] OH ][ [NH
Tro, Chemistry: A Molecular Approach 112
Ex 15.12 Find the pH of 0.100 M NH
3
(aq) solution
| || |
| |
( )( )
( ) x
x x
K

= =

+
1
3
4
b
10 00 . 1 NH
OH NH
determine the value of
K
b
from Table 15.8
since K
b
is very small,
approximate the
[NH
3
]
eq
= [NH
3
]
init

and solve for x
| || |
| |
( )( )
( )
1
3
4
b
10 00 . 1 NH
OH NH

= =
x x
K
1
2
5
10 00 . 1
10 76 . 1

=
x
( )( )
3
1 5
10 33 . 1
10 00 . 1 10 76 . 1

=
=
x
x
K
b
for NH
3
= 1.76 x 10
-5

[NH
3
] [NH
4
+
] [OH

]
initial
0.100
0 0
change -x +x +x
equilibrium 0.100 x x 0.100 x
Tro, Chemistry: A Molecular Approach 113
Ex 15.12 Find the pH of 0.100 M NH
3
(aq) solution
K
b
for NH
3
= 1.76 x 10
-5

[NH
3
] [NH
4
+
] [OH

]
initial
0.100
0 0
change -x +x +x
equilibrium 0.100
x x
check if the
approximation is
valid by seeing if x
< 5% of [NH
3
]
init

% 5 % 33 . 1 % 100
10 00 . 1
10 33 . 1
1
3
< =

the approximation is valid

x = 1.33 x 10
-3

Tro, Chemistry: A Molecular Approach 114
Ex 15.12 Find the pH of 0.100 M NH
3
(aq) solution
substitute x into the
equilibrium
concentration
definitions and solve
| | ( ) M 099 . 0 10 33 . 1 100 . 0 100 . 0 NH
3
3
= = =

x
M 10 33 . 1 ] [OH ] NH [
3 -
4
+
= = = x
K
b
for NH
3
= 1.76 x 10
-5

[NH
3
] [NH
4
+
] [OH

]
initial
0.100
0 0
change -x +x +x
equilibrium 0.100 x
x x
x = 1.33 x 10
-3

[NH
3
] [NH
4
+
] [OH

]
initial
0.100
0 0
change -x +x +x
equilibrium 0.099 1.33E-3 1.33E-3
Tro, Chemistry: A Molecular Approach 115
Ex 15.12 Find the pH of 0.100 M NH
3
(aq) solution
use the [OH
-
] to find
the [H
3
O
+
] using K
w

substitute [H
3
O
+
]
into the formula for
pH and solve
( )
( ) 124 . 11 10 52 . 7 log
O H -log pH
12
3
= =
=

+
K
b
for NH
3
= 1.76 x 10
-5

[NH
3
] [NH
4
+
] [OH

]
initial
0.100
0 0
change -x +x +x
equilibrium 0.099 1.33E-3 1.33E-3
12 -
3
3 -
14 -
3
-
3 w
10 7.52 ] O [H
10 1.33
10 1.00
] O [H
] ][OH O [H
=

=
=
+
+
+
K
Tro, Chemistry: A Molecular Approach 117
Ex 15.12 Find the pH of 0.100 M NH
3
(aq) solution
K
b
for NH
3
= 1.76 x 10
-5

[NH
3
] [NH
4
+
] [OH

]
initial
0.100
0 0
change -x +x +x
equilibrium 0.099 1.33E-3 1.33E-3
check by substituting
the equilibrium
concentrations back into
the equilibrium constant
expression and
comparing the calculated
K
b
to the given K
b

| || |
| |
( )
( )
5
2
3
3
4
b
10 8 . 1
099 . 0
10 33 . 1
NH
OH NH

+
=

=
= K
though not exact,
the answer is
reasonably close
Tro, Chemistry: A Molecular Approach 118
Practice Find the pH of a 0.0015 M morphine
solution, K
b
= 1.6 x 10
-6

Tro, Chemistry: A Molecular Approach 119
Practice Find the pH of a 0.0015 M morphine solution
Write the reaction for
the base with water
Construct an ICE
table for the reaction
Enter the initial
concentrations
assuming the [OH

]
from water is 0
since no products initially, Q
c
= 0, and the reaction is proceeding forward
B + H
2
O BH
+
+ OH

[B] [BH
+
] [OH

]
initial
0.0015
0 0
change
equilibrium
Tro, Chemistry: A Molecular Approach 120
[B] [BH
+
] [OH

]
initial
0.0015
0 0
change
equilibrium
Practice Find the pH of a 0.0015 M morphine solution
represent the change
in the concentrations
in terms of x
sum the columns to
find the equilibrium
concentrations in
terms of x
substitute into the
equilibrium constant
expression
+x
+x x
0.0015 x
x x
| |
( )( )
( ) x
x x
K

= =

+
3
b
10 5 . 1 B
] OH ][ [BH
Tro, Chemistry: A Molecular Approach 121
Practice Find the pH of a 0.0015 M morphine solution
| || |
| |
( )( )
( ) x
x x
K

= =

+
3
b
10 5 . 1 B
OH BH
determine the value of
K
b

since K
b
is very small,
approximate the
[B]
eq
= [B]
init
and
solve for x
| || |
| |
( )( )
( )
3
b
10 5 . 1 B
OH BH

= =
x x
K
1
2
6
10 5 . 1
10 6 . 1

=
x
( )( )
5
3 6
10 9 . 4
10 5 . 1 10 6 . 1

=
=
x
x
K
b
for Morphine = 1.6 x 10
-6

[B] [BH
+
] [OH

]
initial
0.0015
0 0
change -x +x +x
equilibrium 0.0015 x x 0.0015 x
Tro, Chemistry: A Molecular Approach 122
Practice Find the pH of a 0.0015 M morphine solution
check if the
approximation is
valid by seeing if x
< 5% of [B]
init

% 5 % 3 . 3 % 100
10 5 . 1
10 9 . 4
3
5
< =

the approximation is valid

x = 4.9 x 10
-5

K
b
for Morphine = 1.6 x 10
-6

[B] [BH
+
] [OH

]
initial
0.0015
0 0
change -x +x +x
equilibrium 0.0015
x x
Tro, Chemistry: A Molecular Approach 123
Practice Find the pH of a 0.0015 M morphine solution
substitute x into the
equilibrium
concentration
definitions and solve
| | ( ) M 0015 . 0 10 9 . 4 0015 . 0 0015 . 0 Morphine
5
= = =

x
M 10 9 . 4 ] [OH ] BH [
5 - +
= = = x
x = 4.9 x 10
-5

K
b
for Morphine = 1.6 x 10
-6

[B] [BH
+
] [OH

]
initial
0.0015
0 0
change -x +x +x
equilibrium 0.0015 x
x x
[B] [BH
+
] [OH

]
initial
0.0015
0 0
change -x +x +x
equilibrium 0.0015 4.9E-5 4.9E-5
Tro, Chemistry: A Molecular Approach 124
Practice Find the pH of a 0.0015 M morphine solution
use the [OH
-
] to find
the [H
3
O
+
] using K
w

substitute [H
3
O
+
]
into the formula for
pH and solve
( )
( ) 69 . 9 10 0 . 2 log
O H -log pH
10
3
= =
=

+
10 -
3
5 -
14 -
3
-
3 w
10 0 . 2 ] O [H
10 9 . 4
10 1.00
] O [H
] ][OH O [H
=

=
=
+
+
+
K
K
b
for Morphine = 1.6 x 10
-6

[B] [BH
+
] [OH

]
initial
0.0015
0 0
change -x +x +x
equilibrium 0.0015 4.9E-5 4.9E-5
Tro, Chemistry: A Molecular Approach 126
Practice Find the pH of a 0.0015 M morphine solution
check by substituting
the equilibrium
concentrations back into
the equilibrium constant
expression and
comparing the calculated
K
b
to the given K
b

| || |
| |
( )
( )
6
2
5
b
10 6 . 1
0015 . 0
10 9 . 4
B
OH BH

+
=

=
= K
the answer
matches the
given K
b

K
b
for Morphine = 1.6 x 10
-6

[B] [BH
+
] [OH

]
initial
0.0015
0 0
change -x +x +x
equilibrium 0.0015 4.9E-5 4.9E-5
Tro, Chemistry: A Molecular Approach 127
Acid-Base Properties of Salts
salts are water soluble ionic compounds
salts that contain the cation of a strong base and an
anion that is the conjugate base of a weak acid are
basic
NaHCO
3
solutions are basic
Na
+
is the cation of the strong base NaOH
HCO
3

is the conjugate base of the weak acid H

2
CO
3

salts that contain cations that are the conjugate acid of a
weak base and an anion of a strong acid are acidic
NH
4
Cl solutions are acidic
NH
4
+
is the conjugate acid of the weak base NH
3

Cl

is the anion of the strong acid HCl

Tro, Chemistry: A Molecular Approach 128
Anions as Weak Bases
every anion can be thought of as the conjugate base of an
acid
therefore, every anion can potentially be a base
A

(aq) + H
2
O(l) HA(aq) + OH

(aq)
the stronger the acid is, the weaker the conjugate base is
an anion that is the conjugate base of a strong acid is pH neutral
Cl

(aq) + H
2
O(l) HCl(aq) + OH

(aq)
since HCl is a strong acid, this equilibrium lies practically completely to the
left
an anion that is the conjugate base of a weak acid is basic
F

(aq) + H
2
O(l) HF(aq) + OH

(aq)
since HF is a weak acid, the position of this equilibrium favors the right

Tro, Chemistry: A Molecular Approach 129
Ex 15.13 - Use the Table to Determine
if the Given Anion Is Basic or Neutral
a) NO
3

the conjugate base of a
strong acid, therefore
neutral
b) NO
2

the conjugate base of a
weak acid, therefore
basic
130
Relationship between K
a
of an Acid and
K
b
of Its Conjugate Base
many reference books only give tables of K
a
values
because K
b
values can be found from them
] [A
] O HA][H [
) ( OH ) HA( ) O( H ) ( A
[HA]
] O ][H A [
) ( O H ) ( A ) O( H ) HA(
3
b 2
3
a 3 2

+

+
+
= + +
= + +
K aq aq l aq
K aq aq l aq
when you add
equations,
you multiply
the Ks
) ( OH ) ( O H ) O( H 2
3 2
aq aq l
+
+
w 3 b a
3
b a
] OH ][ O H [
] A [
] OH ][ HA [
] HA [
] O H ][ A [
K K K
K K
= =
=
+

+
Tro, Chemistry: A Molecular Approach 131
Ex 15.14 Find the pH of 0.100 M
NaCHO
2
(aq) solution

Na
+
is the cation of a
strong base pH
neutral. The CHO
2

is the anion of a
weak acid pH basic
Write the reaction for
the anion with water
Construct an ICE
table for the reaction
Enter the initial
concentrations
assuming the [OH

]
from water is 0
CHO
2

+ H
2
O HCHO
2
+ OH

[CHO
2

] [HCHO
2
] [OH

]
initial
0.100 0 0
change
equilibrium
132
0.100 x
Ex 15.14 Find the pH of 0.100 M NaCHO
2
(aq) solution
represent the change
in the concentrations
in terms of x
sum the columns to
find the equilibrium
concentrations in
terms of x
Calculate the value
of K
b
from the value
of K
a
of the weak
acid from Table 15.5
substitute into the
equilibrium constant
expression
+x +x x
x x
| |
( )( )
( ) x
x x
K

= =

1
2
2
b
10 00 . 1 CHO
] OH ][ [HCHO
[CHO
2

] [HCHO
2
] [OH

]
initial
0.100 0 0
change
equilibrium
11
4
14
b
w b a
10 6 . 5
10 8 . 1
10 0 . 1

=
=
K
K K K
Tro, Chemistry: A Molecular Approach 133
Ex 15.14 Find the pH of 0.100 M NaCHO
2
(aq) solution
since K
b
is very small,
approximate the
[CHO
2

]
eq
= [CHO
2

]
init

and solve for x
1
2
11
10 00 . 1
10 6 . 5

=
x
( )( )
6
1 11
10 4 . 2
10 00 . 1 10 6 . 5

=
=
x
x
K
b
for CHO
2

= 5.6 x 10
-11

[CHO
2

] [HCHO
2
] [OH

]
initial
0.100 0 0
change -x +x +x
equilibrium 0.100 x x 0.100 x
| |
( )( )
( ) x
x x
K

= =

1
2
2
b
10 00 . 1 CHO
] OH ][ [HCHO
| |
( )( )
( )
1
2
2
b
10 00 . 1 CHO
] OH ][ [HCHO

= =
x x
K
Tro, Chemistry: A Molecular Approach 134
Ex 15.14 Find the pH of 0.100 M NaCHO
2
(aq) solution
check if the
approximation is
valid by seeing if x
< 5% of [CHO
2

]
init

% 5 % 0024 . 0 % 100
10 00 . 1
10 4 . 2
1
6
< =

the approximation is valid

x = 2.4 x 10
-6

K
b
for CHO
2

= 5.6 x 10
-11

[CHO
2

] [HCHO
2
] [OH

]
initial
0.100 0 0
change -x +x +x
equilibrium 0.100
x x
Tro, Chemistry: A Molecular Approach 135
Ex 15.14 Find the pH of 0.100 M NaCHO
2
(aq) solution
substitute x into the
equilibrium
concentration
definitions and solve
| | ( ) M 100 . 0 10 4 . 2 100 . 0 100 . 0 CHO
6
2
= = =

x
M 10 4 . 2 ] [OH ] HCHO [
6 -
2

= = = x
x = 2.4 x 10
-6

K
b
for CHO
2

= 5.6 x 10
-11

[CHO
2

] [HCHO
2
] [OH

]
initial
0.100 0 0
change -x +x +x
equilibrium 0.100 x
x x
[CHO
2

] [HCHO
2
] [OH

]
initial
0.100 0 0
change -x +x +x
equilibrium 0.100 2.4E-6 2.4E-6
Tro, Chemistry: A Molecular Approach 136
Ex 15.14 Find the pH of 0.100 M NaCHO
2
(aq) solution
use the [OH
-
] to find
the [H
3
O
+
] using K
w

substitute [H
3
O
+
]
into the formula for
pH and solve
( )
( ) 38 . 8 10 2 . 4 log
O H -log pH
9
3
= =
=

+
9 -
3
6 -
14 -
3
-
3 w
10 2 . 4 ] O [H
10 4 . 2
10 1.00
] O [H
] ][OH O [H
=

=
=
+
+
+
K
K
b
for CHO
2

= 5.6 x 10
-11

[CHO
2

] [HCHO
2
] [OH

]
initial
0.100 0 0
change -x +x +x
equilibrium 0.100 2.4E-6 2.4E-6
Tro, Chemistry: A Molecular Approach 138
Ex 15.14 Find the pH of 0.100 M NaCHO
2
(aq) solution
check by substituting
the equilibrium
concentrations back into
the equilibrium constant
expression and
comparing the calculated
K
b
to the given K
b

| || |
| |
( )
( )
11
2
6
2
2
b
10 8 . 5
100 . 0
10 4 . 2
CHO
OH HCHO

=
= K
though not exact,
the answer is
reasonably close
K
b
for CHO
2

= 5.6 x 10
-11

[CHO
2

] [HCHO
2
] [OH

]
initial
0.100 0 0
change -x +x +x
equilibrium 0.100 2.4E-6 2.4E-6
Tro, Chemistry: A Molecular Approach 139
Polyatomic Cations as Weak Acids
some cations can be thought of as the conjugate acid
of a base
others are the counterions of a strong base
therefore, some cation can potentially be an acid
MH
+
(aq) + H
2
O(l) MOH(aq) + H
3
O
+
(aq)
the stronger the base is, the weaker the
conjugate acid is
a cation that is the counterion of a strong base is pH
neutral
a cation that is the conjugate acid of a weak base is acidic
NH
4
+
(aq) + H
2
O(l) NH
3
(aq) + H
3
O
+
(aq)
since NH
3
is a weak base, the position of this equilibrium favors
the right

Tro, Chemistry: A Molecular Approach 140
Metal Cations as Weak Acids
cations of small, highly charged metals are weakly
acidic
alkali metal cations and alkali earth metal cations pH neutral
cations are hydrated
Al(H
2
O)
6
3+
(aq) + H
2
O(l) Al(H
2
O)
5
(OH)
2+

(aq) + H
3
O
+
(aq)
Tro, Chemistry: A Molecular Approach 141
Ex 15.15 - Determine if the Given
Cation Is Acidic or Neutral
a) C
5
N
5
NH
2
+

the conjugate acid of a weak base, therefore
acidic
b) Ca
2+

the counterion of a strong base, therefore neutral
c) Cr
3+

a highly charged metal ion, therefore acidic
Tro, Chemistry: A Molecular Approach 142
Classifying Salt Solutions as
Acidic, Basic, or Neutral
if the salt cation is the counterion of a strong
base and the anion is the conjugate base of a
strong acid, it will form a neutral solution
NaCl Ca(NO
3
)
2
KBr
if the salt cation is the counterion of a strong
base and the anion is the conjugate base of a
weak acid, it will form a basic solution
NaF Ca(C
2
H
3
O
2
)
2
KNO
2

Tro, Chemistry: A Molecular Approach 143
Classifying Salt Solutions as
Acidic, Basic, or Neutral
if the salt cation is the conjugate acid of a weak
base and the anion is the conjugate base of a
strong acid, it will form an acidic solution
NH
4
Cl
if the salt cation is a highly charged metal ion
and the anion is the conjugate base of a strong
acid, it will form an acidic solution
Al(NO
3
)
3

Tro, Chemistry: A Molecular Approach 144
Classifying Salt Solutions as
Acidic, Basic, or Neutral
if the salt cation is the conjugate acid of a weak
base and the anion is the conjugate base of a
weak acid, the pH of the solution depends on the
relative strengths of the acid and base
NH
4
F since HF is a stronger acid than NH
4
+
, K
a
of
NH
4
+
is larger than K
b
of the F

; therefore the
solution will be acidic

Tro, Chemistry: A Molecular Approach 145
Ex 15.16 - Determine whether a solution of the
following salts is acidic, basic, or neutral
a) SrCl
2

Sr
2+
is the counterion of a strong base, pH neutral
Cl

is the conjugate base of a strong acid, pH neutral

solution will be pH neutral
b) AlBr
3

Al
3+
is a small, highly charged metal ion, weak acid
Cl

is the conjugate base of a strong acid, pH neutral

solution will be acidic
c) CH
3
NH
3
NO
3

CH
3
NH
3
+
is the conjugate acid of a weak base, acidic
NO
3

is the conjugate base of a strong acid, pH neutral

solution will be acidic
Tro, Chemistry: A Molecular Approach 146
Ex 15.16 - Determine whether a solution of the
following salts is acidic, basic, or neutral
d) NaCHO
2

Na
+
is the counterion of a strong base, pH neutral
CHO
2

is the conjugate base of a weak acid, basic

solution will be basic
e) NH
4
F
NH
4
+
is the conjugate acid of a weak base, acidic
F

is the conjugate base of a weak acid, basic

K
a
(NH
4
+
) > K
b
(F

); solution will be acidic

Tro, Chemistry: A Molecular Approach 147
Polyprotic Acids
since polyprotic acids ionize in steps, each H has a
separate K
a

K
a1
> K
a2
> K
a3

generally, the difference in K
a
values is great enough so
that the second ionization does not happen to a large
enough extent to affect the pH
most pH problems just do first ionization
except H
2
SO
4
use [H
2
SO
4
] as the [H
3
O
+
] for the second
ionization
[A
2-
] = K
a2

as long as the second ionization is negligible
148
Tro, Chemistry: A Molecular Approach 149
[HSO
4

] [SO
4
2
] [H
3
O
+
]
initial
0.0100
0 0.0100
change
equilibrium
Ex 15.18 Find the pH of 0.0100 M H
2
SO
4
(aq)
solution @ 25C

Write the reactions
for the acid with
water
Construct an ICE
table for the reaction
Enter the initial
concentrations
assuming the
[HSO
4

] and [H
3
O
+
]
is [H
2
SO
4
]
HSO
4

+ H
2
O SO
4
2
+ H
3
O
+
H
2
SO
4
+ H
2
O HSO
4

+ H
3
O
+
Tro, Chemistry: A Molecular Approach 150
Ex 15.18 Find the pH of 0.0100 M H
2
SO
4
(aq)
solution @ 25C
represent the change
in the concentrations
in terms of x
sum the columns to
find the equilibrium
concentrations in
terms of x
substitute into the
equilibrium constant
expression
( )( )
( ) x
x x
K

+
= =
+
0100 . 0
0100 . 0
] HSO [
] O H ][ [SO
-
4
3
- 2
4
a
[HSO
4

] [SO
4
2
] [H
3
O
+
]
initial
0.0100 0 0.0100
change x +x +x
equilibrium 0.0100 x x 0.0100 x
Tro, Chemistry: A Molecular Approach 151
Ex 15.18 Find the pH of 0.0100 M H
2
SO
4
(aq)
solution @ 25C
( )
( )
00012 . 0 022 . 0 0
10 00 . 1 10 2 . 1 10 2 . 1
0100 . 0
0100 . 0
012 . 0
2
2 2 2 4
+ =
+ =

+
=

x x
x x x
x
x x
( )
0.0045 or 027 . 0
) 1 ( 2
) 00012 . 0 )( 1 ( 4 022 . 0 022 . 0
2
=

=
x
x
K
a
for HSO
4

= 0.012
expand and solve for
x using the quadratic
formula
( )( )
( ) x
x x
K

+
= =
+
0100 . 0
0100 . 0
] HSO [
] O H ][ [SO
-
4
3
- 2
4
a
Tro, Chemistry: A Molecular Approach 152
Ex 15.18 Find the pH of 0.0100 M H
2
SO
4
(aq)
solution @ 25C
x = 0.0045
substitute x into the
equilibrium
concentration
definitions and solve
( ) M 0055 . 0 0045 . 0 0100 . 0 0100 . 0 ] HSO [
4
= = =

x
( ) M 0145 . 0 0100 . 0 ] O H [
3
= + =
+
x
[HSO
4

] [SO
4
2
] [H
3
O
+
]
initial
0.0100 0 0.0100
change x +x +x
equilibrium 0.0100 x x 0.0100 x
K
a
for HSO
4

= 0.012
[HSO
4

] [SO
4
2
] [H
3
O
+
]
initial
0.0100 0 0.0100
change x +x +x
equilibrium 0.0055 0.0045 0.0145
M 0045 . 0 ] SO [
- 2
4
= = x
Tro, Chemistry: A Molecular Approach 153
Ex 15.18 Find the pH of 0.0100 M H
2
SO
4
(aq)
solution @ 25C
substitute [H
3
O
+
]
into the formula for
pH and solve
( )
( ) 839 . 1 0145 . 0 log
O H -log pH
3
= =
=
+
K
a
for HSO
4

= 0.012
[HSO
4

] [SO
4
2
] [H
3
O
+
]
initial
0.0100 0 0.0100
change x +x +x
equilibrium 0.0055 0.0045 0.0145
Tro, Chemistry: A Molecular Approach 154
Ex 15.7 Find the pH of 0.100 M HClO
2
(aq)
solution @ 25C
check by substituting
the equilibrium
concentrations back
into the equilibrium
constant expression
and comparing the
calculated K
a
to the
given K
a

| || |
| |
( )( )
( )
2
-
4
3
- 2
4
a
10 2 . 1
0055 . 0
0145 . 0 0045 . 0
HSO
O H SO

+
= =
= = K
the answer matches
K
a
for HSO
4

= 0.012
[HSO
4

] [SO
4
2
] [H
3
O
+
]
initial
0.0100 0 0.0100
change x +x +x
equilibrium 0.0055 0.0045 0.0145
Tro, Chemistry: A Molecular Approach 155
Strengths of Binary Acids
the more o+ H-X o- polarized the
bond, the more acidic the bond
the stronger the H-X bond, the
weaker the acid
binary acid strength increases to the
right across a period
H-C < H-N < H-O < H-F
binary acid strength increases down
the column
H-F < H-Cl < H-Br < H-I
Tro, Chemistry: A Molecular Approach 156
Strengths of Oxyacids, H-O-Y
the more electronegative the Y atom, the
stronger the acid
helps weakens the H-O bond
the more oxygens attached to Y, the stronger the
acid
further weakens and polarizes the H-O bond
Tro, Chemistry: A Molecular Approach 157
Lewis Acid - Base Theory
electron sharing
electron donor = Lewis Base = nucleophile
must have a lone pair of electrons
electron acceptor = Lewis Acid = electrophile
electron deficient
when Lewis Base gives electrons from lone
pair to Lewis Acid, a covalent bond forms
between the molecules
Nucleophile: + Electrophile Nucleophile:Electrophile
product called an adduct
other acid-base reactions also Lewis
Tro, Chemistry: A Molecular Approach 158
Example - Complete the Following
Lewis Acid-Base Reactions
Label the Nucleophile and Electrophile
OH

H C H



+ OH
-1

OH

H C H

OH
OH

H C H



+ OH
-1

Electrophile
Nucleophile




Tro, Chemistry: A Molecular Approach 159
Practice - Complete the Following
Lewis Acid-Base Reactions
Label the Nucleophile and Electrophile
BF
3
+ HF
CaO + SO
3

KI + I
2

Tro, Chemistry: A Molecular Approach 160
Practice - Complete the Following
Lewis Acid-Base Reactions
Label the Nucleophile and Electrophile
BF
3
+ HF H
+1
BF
4
-1

CaO + SO
3
Ca
+2
SO
4
-2

KI + I
2
KI
3

F

B F

F
H F

+
F

B F

F
F
-1
H
+1
Nuc Ele
c
O

S O

O


Ca
+2
O
-2

+
O

S O

O
O
-2
Ca
+2
Elec Nuc
I I K
+1
I
-1

+
Elec Nuc
K
+1
I I I
-1
Tro, Chemistry: A Molecular Approach 161
What Is Acid Rain?
natural rain water has a pH of 5.6
naturally slightly acidic due mainly to CO
2

rain water with a pH lower than 5.6 is called
acid rain
acid rain is linked to damage in ecosystems and
structures
Tro, Chemistry: A Molecular Approach 162
What Causes Acid Rain?
many natural and pollutant gases dissolved in the air
are nonmetal oxides
CO
2
, SO
2
, NO
2

nonmetal oxides are acidic
CO
2
+ H
2
O H
2
CO
3
2 SO
2
+ O
2
+ 2 H
2
O 2 H
2
SO
4
processes that produce nonmetal oxide gases as waste
increase the acidity of the rain
natural volcanoes and some bacterial action
man-made combustion of fuel
weather patterns may cause rain to be acidic in regions
other than where the nonmetal oxide is produced
pH of Rain in Different Regions
Sources of SO
2
from Utilities
Tro, Chemistry: A Molecular Approach 165
Damage from Acid Rain
acids react with metals, and materials that contain
carbonates
acid rain damages bridges, cars, and other metallic
structures
acid rain damages buildings and other structures made
of limestone or cement
acidifying lakes affecting aquatic life
dissolving and leaching more minerals from soil
making it difficult for trees
Tro, Chemistry: A Molecular Approach 166
Acid Rain Legislation
1990 Clean Air Act attacks acid rain
force utilities to reduce SO
2

result is acid rain in northeast stabilized and
beginning to be reduced
167
Damage from Acid Rain