Chapter 15

Chemistry: A Molecular Approach, 2nd Ed.
Nivaldo Tro
Chapter 15
Acids and
Bases
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
Copyright 2011 Pearson Education, Inc.
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
Tro, Chemistry: A Molecular Approach, 2/e 2 Copyright 2011 Pearson Education, Inc.
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
GERD
Chronic heartburn is a problem for some people
GERD (gastroesophageal reflux disease) is chronic
leaking of stomach acid into the esophagus
In people with GERD, the muscles separating the
stomach from the esophagus do not close tightly,
allowing stomach acid to leak into the esophagus
Physicians diagnose GERD by attaching a pH
sensor to the esophagus to measure the acidity
levels of the fluids over time
Properties of Acids
Sour taste
React with active metals
i.e., Al, Zn, Fe, but not Cu, Ag, or Au
2 Al + 6 HCl AlCl3 + 3 H2
corrosive
React with carbonates, producing CO2
marble, baking soda, chalk, limestone
CaCO3 + 2 HCl CaCl2 + CO2 + H2O
Change color of vegetable dyes
blue litmus turns red
React with bases to form ionic salts
Common Acids
Structures of Acids
Binary acids have acid hydrogens attached

to a nonmetal atom
HCl, HF
Structure of Acids
Oxy acids have acid hydrogens attached to
an oxygen atom
H2SO4, HNO3
Structure of Acids
Carboxylic acids
have COOH group
HC2H3O2, H3C6H5O7
Only the first H in the
formula is acidic
the H is on the
COOH
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
Common Bases
Structure of Bases
Most ionic bases contain OH ions

NaOH, Ca(OH)2
Some contain CO32 ions
CaCO3 NaHCO3
Molecular bases contain structures
that react with H+
mostly amine groups
Indicators
Chemicals that change color depending on
the solutions acidity or 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
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
HC2H3O2(aq) H+(aq) + C2H3O2(aq)
Arrhenius Theory
HCl ionizes in water, NaOH dissociates in water,

producing H+ and Cl ions producing Na+ and OH ions
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 water molecules to produce
complex ions, mainly hydronium ion, H3O+
H+ + H2O H3O+
there are also minor amounts of H+ with multiple water
molecules, H(H2O)n+
Arrhenius AcidBase Reactions
The H+ from the acid combines with the OH

from the base to make a molecule of H2O
it is often helpful to think of H2O 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) + H2O(l)
Problems with Arrhenius Theory
Does not explain why molecular substances, such as
NH3, dissolve in water to form basic solutions even
though they do not contain OH ions
Does not explain how some ionic compounds, such
as Na2CO3 or Na2O, dissolve in water to form basic
solutions even though they do not contain OH ions
Does not explain why molecular substances, such as
CO2, dissolve in water to form acidic solutions even
though they do not contain H+ ions
Does not explain acidbase reactions that take place
outside aqueous solution
Another Definition:
Brnsted-Lowry Acid-Base Theory
Brnsted and Lowry redefined acids and bases
based on what happens in a reaction.
Any reaction that involves H+ being transferred from
one molecule to another is an acidbase reaction
regardless of whether it occurs in aqueous solution, or if
there is OH present
All reactions that fit the Arrhenius definition also fit
the Brnsted-Lowry definition, but many more do
as well
Brnsted-Lowry Theory
In a Brnsted-Lowry acidbase reaction, an H+

is transferred
The acid is an H donor
The base is an H acceptor
base structure must contain an atom with an
unshared pair of electrons
In a Brnsted-Lowry acid-base reaction, the
acid molecule gives an H+ to the base molecule
HA + :B:A + HB+
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
When HCl dissolves in water, the HCl is the
acid because HCl transfers an H+ to H2O,
forming H3O+ ions
water acts as base, accepting H +
HCl(aq) + H2O(l) Cl(aq) + H3O+(aq)
acid base
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
When NH3 dissolves in water, the NH3(aq) is the
base because NH3 accepts an H+ from H2O,
forming OH(aq)
water acts as acid, donating H+
NH3(aq) + H2O(l) NH4+(aq) + OH(aq)
base acid
A Warning!
Because chemists know common bonding
patterns, we often do not draw lone pair
electrons on our structures. You need to be
able to recognize when an atom in a molecule
has lone pair electrons and when it doesnt!
Practice Draw structures of the
following that include lone pairs of
electrons
HClO
HCO3
Amphoteric Substances
Amphoteric substances can act as either an
acid or a base
because they have both a transferable H and an
atom with lone pair electrons
Water acts as base, accepting H+ from HCl
HCl(aq) + H2O(l) Cl(aq) + H3O+(aq)
Water acts as acid, donating H+ to NH3
NH3(aq) + H2O(l) NH4+(aq) + OH(aq)
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
Conjugate Pairs
In a Brnsted-Lowry acidbase 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 its conjugate acid;
and the original acid becomes its conjugate base
Brnsted-Lowry
AcidBase Reactions
HA + :B :A + HB+
acid base conjugate conjugate
base acid
HCHO2 + H2O CHO2 + H3O+
base acid
H2O + NH3 HO + NH4+
base acid
Conjugate Pairs
In the reaction H2O + NH3 HO + NH4+
H2O and HO constitute an
acid/conjugate base pair
NH3 and NH4+ constitute

a base/conjugate acid
pair
Practice Write the formula for the
conjugate acid of the following
H2O H3O+
NH3 NH4+
CO32 HCO3
H2PO41 H3PO4
Practice Write the formula for the
conjugate base of the following
H2O HO
NH3 NH2
CO32 because CO32 does not have an H, it

cannot be an acid
H2PO41
H2PO41 HPO42
Example 15.1a: Identify the Brnsted-Lowry acids
and bases, and their conjugates, in the reaction
H2SO4 + H2O HSO4 + H3O+

When the H2SO4 becomes HSO4, it loses an H+ so
H2SO4 must be the acid and HSO4 its conjugate base
When the H2O becomes H3O+, it accepts an H+ so H2O
must be the base and H3O+ its conjugate acid
H2SO4 + H2O HSO4 + H3O+
base acid
Example 15.1b: Identify the Brnsted-Lowry acids
and bases and their conjugates in the reaction
HCO3 + H2O H2CO3 + HO

When the HCO3 becomes H2CO3, it accepts an H+ so
HCO3 must be the base and H2CO3 its conjugate acid
When the H2O becomes OH, it donats an H+ so H2O must
be the acid and OH its conjugate base
HCO3 + H2O H2CO3 + HO
base acid conjugate conjugate
acid base
Practice Identify the Brnsted-Lowry acid,
base, conjugate acid, and conjugate base in
the following reaction
HSO4(aq) + HCO3(aq) SO42(aq) + H2CO3(aq)
Acid Base Conjugate Conjugate

Base Acid
PracticeWrite the equations for the following
reacting with water and acting as a monoprotic
acid & label the conjugate acid and base
HBr HBr + H2O Br + H3O+

Acid Base Conj. Conj.
base acid
HSO4 HSO4 + H2O SO42 + H3O+

Acid Base Conj. Conj.
base acid
PracticeWrite the equations for the following
reacting with water and acting as a
monoprotic-accepting base and label the
conjugate acid and base
I I + H2O HI + OH
Base Acid Conj. Conj.
acid base
CO32 + H2O HCO3 + OH

CO32
Base Acid Conj. Conj.
acid base
Comparing Arrhenius Theory and
Brnsted-Lowry Theory
Arrhenius theory BrnstedLowry theory
HCl(aq) H+ HCl(aq) + H2O(l) Cl
(aq) + Cl(aq) (aq) + H3O+(aq)
HF(aq) H+(aq) HF(aq) + H2O(l) F
+ F(aq)
(aq) + H3O+(aq)
NaOH(aq) Na+
(aq) + OH(aq) NaOH(aq) Na+
(aq) + OH(aq)
NH4OH(aq) NH4+
NH3(aq) + H2O(l) NH4+
(aq) + OH(aq)
(aq) + OH(aq)
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
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,
Strong Acids
The stronger the acid, the
more willing it is to donate H HCl H+ + Cl
we use water as the standard HCl + H2O H3O+ + Cl
base to donate H to
Strong acids donate
practically all their Hs
100% ionized in water
strong electrolyte
[H3O+] = [strong acid]
[X] means the molarity of X
0.10 M HCl = 0.10 M H3O+
Weak Acids
Weak acids donate a small

HF H+ + F
fraction of their Hs
HF + H2O H3O+ + F
most of the weak acid
molecules do not donate H
to water
much less than 1% ionized
in water
[H3O+] << [weak acid]
0.10 M HF 0.10 M H3O+
Strong & Weak Acids
Tro, Chemistry: A Molecular Approach, 2/e Copyright 2011 Pearson Education, Inc.
Strengths of Acids & Bases
Commonly, acid or base strength is measured by
determining the equilibrium constant of a
substances reaction with water
HAcid + H2O Acid + H3O+
Base: + H2O HBase+ + OH
The farther the equilibrium position lies toward 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
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
H2SO4 > H2SO3; HNO3 > HNO2
Cation stronger acid than neutral molecule;
neutral stronger acid than anion
H3O+ > H2O > OH; NH4+ > NH3 > NH2
trend in base strength opposite
Acid Ionization Constant, Ka
Acid strength measured by the size of the
equilibrium constant when reacts with H2O
The equilibrium constant for this reaction is
called the acid ionization constant, Ka
larger Ka = stronger acid

Ka

Autoionization of Water
Water is actually an extremely weak electrolyte
therefore there must be a few ions present
About 2 out of every 1 billion water molecules
form ions through a process called
autoionization
H2O H+ + OH
H2O + H2O H3O+ + OH
All aqueous solutions contain both H3O+ and OH
the concentration of H3O+ and OH are equal in water
[H3O+] = [OH] = 107M @ 25 C
Ion Product of Water
The product of the H3O+ and OH concentrations is
always the same number
The number is called the Ion Product of Water
and has the symbol Kw
aka the Dissociation Constant of Water
[H3O+] x [OH] = Kw = 1.00 x 1014 @ 25 C
if you measure one of the concentrations, you can
calculate the other
As [H3O+] increases the [OH] must decrease so
the product stays constant
inversely proportional
Acidic and Basic Solutions
All aqueous solutions contain both H3O+ and OH
ions
Neutral solutions have equal [H3O+] and [OH]
[H3O+] = [OH] = 1.00 x 107
Acidic solutions have a larger [H3O+] than [OH]
[H3O+] > 1.00 x 107; [OH] < 1.00 x 107
Basic solutions have a larger [OH] than [H3O+]
[H3O+] < 1.00 x 107; [OH] > 1.00 x 107
Practice Complete the table
[H+] vs. [OH]
[H+] 100 101 103 105 107 109 1011 1013 1014
H+
H +
+ H
H H
+
+
OH OH OH OH OH
[OH]
[H+] vs. [OH]
Acid Base
[H+] 100 101 103 105 107 109 1011 1013 1014
H+
H +
H H
H
+
+ +
OH OH
OH OH OH
[OH]1014 1013 1011 109 107 105 103 101 100
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
Example 15.2b: Calculate the [OH] at 25 C when
the [H3O+] = 1.5 x 109 M, and determine if the
solution is acidic, basic, or neutral
Given: [H3O+] = 1.5 x 109 M
Find: [OH]
Conceptual
Plan: [H3O+] [OH]
Relationships:
Solution:
Check: the units are correct; the fact that the

[H3O+] < [OH] means the solution is basic
Practice Determine the [H3O+] when the
[OH] = 2.5 x 109 M
Practice Determine the [H3O+] when the
[OH] = 2.5 x 109 M
Given: [OH] = 2.5 x 109 M
Find: [H3O+]
Conceptual
Plan: [OH] [H3O+]
Relationships:
Solution:
Check: the units are correct; the fact that the

[H3O+] > [OH] means the solution is acidic
Measuring Acidity:
pH
The acidity or basicity of a solution is
often expressed as pH
pH = log[H3O+]
exponent on 10 with a positive sign
pHwater = log[107] = 7
need to know the [H3O+] concentration to find
pH
pH < 7 is acidic; pH > 7 is basic, pH = 7
is neutral
[H3O+] = 10pH
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 106) = log(106) + log(2.0)
= 6 + 0.30303 = 6.30303...
Because 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 106) = 6.30
What Does the pH Number Imply?
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 of pH is 0 to 14
pH 0 is [H3O+] = 1 M, pH 14 is [OH] = 1 M
pH can be negative (very acidic) or larger than 14
(very alkaline)
Example 15.3b: Calculate the pH at 25 C when the
[OH] = 1.3 x 102 M, and determine if the solution is
acidic, basic, or neutral
Given: [OH] = 1.3 x 102 M
Find: pH
Conceptual
Plan: [OH] [H3O+] pH
Relationships:
Solution:
Check: pH is unitless; the fact that the pH > 7 means

the solution is basic
Practice Determine the pH @ 25 C of a
solution that has [OH] = 2.5 x 109 M
Practice Determine the pH @ 25 C of a solution
that has [OH] = 2.5 x 109 M
Given: [OH] = 2.5 x 109 M
Find: pH
Conceptual
Plan: [OH] [H3O+] pH
Relationships:
Solution:
Check: pH is unitless; the fact that the pH < 7 means

the solution is acidic
Practice Determine the [OH] of a solution
with a pH of 5.40
Practice Determine the [OH] of a solution with a
pH of 5.40
Given: pH = 5.40
Find: [OH], M
Conceptual
Plan: pH [H3O+] [OH]
Relationships:
Solution:
Check: because the pH < 7, [OH] should be less

than 1 x 107; and it is
pOH
Another way of expressing the acidity/basicity of
a solution is pOH
pOH = log[OH], [OH] = 10pOH
pOHwater = log[107] = 7
need to know the [OH] concentration to find pOH
pOH < 7 is basic; pOH > 7 is acidic, pOH = 7 is
neutral
pH + pOH = 14.0
pH and pOH
pH
[H+] 100 101 103 105 107 109 1011 1013 1014
H+
H +
H H
H
+
+ +
OH OH
OH OH OH
[OH]1014 1013 1011 109 107 105 103 101 100
pOH
pH and pOH
Acid Base
pH 0 1 3 5 7 9 11 13 14
[H+] 100 101 103 105 107 109 1011 1013 1014
H+
H +
H H
H
+
+ +
OH OH
OH OH OH
[OH]1014 1013 1011 109 107 105 103 101 100
pOH 14 13 11 9 7 5 3 1 0
Relationship between pH and pOH
pH + pOH = 14.00
at 25 C
you can use pOH to find pH of a solution
[H3O

Example: Calculate the pH at 25 C when the [OH]
= 1.3 x 102 M, and determine if the solution is acidic,
basic, or neutral
Given: [OH] = 1.3 x 102 M
Find: pH
Conceptual
Plan: [OH] pOH pH
Relationships:
Solution:

Practice Determine the pOH @ 25 C of a
solution that has [H3O+] = 2.5 x 109 M
Practice Determine the pOH @ 25 C of a solution
that has [H3O+] = 2.5 x 109 M
Given: [H3O+] = 2.5 x 109 M

Find: pOH
Conceptual
Plan: [H3O+] pH pOH
Relationships:
Solution:

pK
A way of expressing the strength of an acid or base is
pK
pKa = log(Ka), Ka = 10pKa
pKb = log(Kb), Kb = 10pKb
The stronger the acid, the smaller the pKa
larger Ka = smaller pKa
because it is the log
The stronger the base, the smaller the pKb
larger Kb = smaller pKb
[H3O+] and [OH] in a
Strong Acid or Strong Base Solution
There are two sources of H3O+ in an aqueous
solution of a strong acid the acid and the water
There are two sources of OH in an aqueous
solution of a strong acid the base and the water
For a strong acid or base, the contribution of the
water to the total [H3O+] or [OH] is negligible
the [H3O+]acid shifts the Kw equilibrium so far that
[H3O+]water is too small to be significant
except in very dilute solutions, generally < 1 x 104 M
Finding pH of a Strong Acid or
Strong Base Solution
For a monoprotic strong acid [H3O+] = [HAcid]
for polyprotic acids, the other ionizations can generally be
ignored
for H2SO4, the second ionization cannot be ignored
0.10 M HCl has [H3O+] = 0.10 M and pH = 1.00
For a strong ionic base, [OH] = (number OH)x[Base]
for molecular bases with multiple lone pairs available, only
one lone pair accepts an H, the other reactions can generally
be ignored
0.10 M Ca(OH)2 has [OH] = 0.20 M and pH = 13.30
Finding the pH of a Weak Acid
There are also two sources of H3O+ in an
aqueous solution of a weak acid the acid and
the water
However, finding the [H3O+] is complicated by the
fact that the acid only undergoes partial ionization
Calculating the [H3O+] requires solving an
equilibrium problem for the reaction that defines
the acidity of the acid
Example 15.6: Find the pH of 0.200 M
HNO2(aq) solution @ 25 C
write the reaction for HNO2 + H2O NO2 + H3O+
the acid with water
construct an ICE
[HNO2] [NO2] [H3O+]
table for the reaction initial 0.200 0 0
enter the initial change
concentrations
equilibrium
assuming the [H3O+]
from water is 0
because no products initially, Qc = 0, and the reaction is proceeding

forward
represent the [HNO2] [NO2] [H3O+]
change in the
concentrations in initial 0.200 0 0
terms of x change x +x +x
sum the columns to equilibrium 0.200 x x x
find the equilibrium
concentrations in HNO2 + H2O(l) NO2(aq) + H3O+(aq)
terms of x
substitute into the
equilibrium constant
expression
Ka for HNO2 = 4.6 x 104
determine the value [HNO2] [NO2] [H3O+]
of Ka from Table 15.5
initial 0.200 0 0
because Ka is very
small, approximate change x +x +x
the [HNO2]eq = 0.200x
equilibrium 0.200 x x
[HNO2]init and solve
for x
Ka for HNO2 = 4.6 x 104
check if the [HNO2] [NO2] [H3O+]
approximation is
valid by seeing if initial 0.200 0 0
x < 5% of [HNO2]init change x +x +x
x = 9.6 x 103
the approximation is valid

Ka for HNO2 = 4.6 x 104
substitute x into [HNO2] [NO2] [H3O+]
the equilibrium
concentration initial 0.200 0 0
definitions and change x +x +x
solve
equilibrium 0.200x x
0.190 0.0096 x
0.0096
x = 9.6 x 103
Ka for HNO2 = 4.6 x 104
substitute [H3O+] [HNO2] [NO2] [H3O+]
into the formula for
pH and solve initial 0.200 0 0
change x +x +x
equilibrium 0.190 0.0096 0.0096
Ka for HNO2 = 4.6 x 104
check by substituting [HNO2] [NO2] [H3O+]
the equilibrium
concentrations back initial 0.200 0 0
into the equilibrium change x +x +x
constant expression
and comparing the equilibrium 0.190 0.0096 0.0096
calculated Ka to the
given Ka
though not exact,

the answer is
reasonably close
Practice What is the pH of a 0.012 M
solution of nicotinic acid, HC6H4NO2?
(Ka = 1.4 x 105 @ 25 C)
write the reaction HC6H4NO2 + H2O C6H4NO2 + H3O+

for the acid with
water
[HA] [A] [H3O+]
construct an ICE
table for the initial 0.012 0 0
reaction change
enter the initial equilibrium
concentrations
assuming the
[H3O+] from water
is 0
represent the HC6H4NO2 + H2O C6H4NO2 + H3O+
change in the
concentrations in [HA] [A] [H3O+]
terms of x
initial 0.012 0 0
sum the columns x +x
change +x
to find the
equilibrium equilibrium 0.012 x x x
concentrations in
terms of x
substitute into the
equilibrium
constant
expression
Practice What is the pH of a 0.012 M solution of
nicotinic acid, HC6H4NO2? Ka = 1.4 x 105 @ 25 C
determine the HC6H4NO2 + H2O C6H4NO2 + H3O+
value of Ka
[HA] [A] [H3O+]
because Ka is very
small, approximate
initial 0.012 0 0
the [HA]eq = [HA]init change x +x +x
and solve for x equilibrium 0.012
0.012x x x
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Ka for HC6H4NO2 = 1.4 x 105
check if the [HA] [A] [H3O+]
approximation is
x < 5% of change x +x +x
[HC6H4NO2]init
x = 4.1 x 104

substitute x into the [HA] [A] [H3O+]

equilibrium
solve
equilibrium 0.012x x x
x = 4.1 x 104
substitute [H3O+] [HA] [A] [H3O+]

change x +x +x
equilibrium 0.012 0.00041 0.00041
check by substituting [HA] [A] [H3O+]

the equilibrium
constant expression
given Ka
the values match
HClO2(aq) solution @ 25 C
write the reaction
for the acid with HClO2 + H2O ClO2 + H3O+
water
[HClO2] [ClO2] [H3O+]
construct an ICE
reaction change
concentrations
assuming the
[H3O+] from water
is 0
represent the [HClO2] [ClO2] [H3O+]
change in the
sum the columns equilibrium 0.100x x x
to find the
equilibrium
concentrations in
terms of x
substitute into the
equilibrium
constant
expression
determine the value Ka for HClO2 = 1.1 x 102
of Ka from Table 15.5
[HClO2] [ClO2] [H3O+]
because Ka is very
initial 0.100 0 0
small, approximate
the [HClO2]eq = change x +x +x
[HClO2]init and solve equilibrium 0.100x x x
for x
Ka for HClO2 = 1.1 x 102
check if the [HClO2] [ClO2] [H3O+]
approximation is
valid by seeing if x initial 0.100 0 0
< 5% of [HNO2]init change x +x +x
x = 3.3 x 102
the approximation is invalid

if the
approximation is
invalid, solve for x
using the quadratic
formula
substitute x into [HClO2] [ClO2] [H3O+]
the equilibrium
solve
equilibrium 0.100x
0.072 0.028
x 0.028
x
x = 0.028
substitute [H3O+] [HClO2] [ClO2] [H3O+]
into the formula
for pH and solve initial 0.100 0 0
change x +x +x
equilibrium 0.072 0.028 0.028
HClO2(aq) solution @ 25C
check by substituting Ka for HClO2 = 1.1 x 102
the equilibrium
concentrations back
[HClO2] [ClO2-] [H3O+]
into the equilibrium initial 0.100 0 0
constant expression
and comparing the change x +x +x
calculated Ka to the equilibrium 0.072 0.028 0.028
given Ka
the answer matches
Example 15.8: What is the Ka of a weak acid if
a 0.100 M solution has a pH of 4.25?
use the pH to find
the equilibrium
[H3O+] HA + H2O A + H3O+
write the reaction [HA] [A] [H3O+]
for the acid with
water
initial 0.100 0 0
construct an ICE change

table for the equilibrium 5.6E-05
reaction
enter the initial
concentrations and
[H3O+]equil
Example 15.8: What is the Ka of a weak acid if
a 0.100 M solution has a pH of 4.25?
fill in the rest of the HA + H2O A + H3O+
table using the
[H3O+] as a guide [HA] [A] [H3O+]
if the difference is initial 0.100 0 0
insignificant, change 5.6E-05 +5.6E-05 +5.6E-05
[HA]equil = [HA]initial
0.100
equilibrium 0.100 5.6E-05 5.6E-05
substitute into the 5.6E-05
Ka expression and
compute Ka
Practice What is the Ka of nicotinic
acid, HC6H4NO2, if a 0.012 M solution
of nicotinic acid has a pH of 3.40?
Practice What is the Ka of nicotinic acid,
HC6H4NO2, if a 0.012 M solution of nicotinic
acid has a pH of 3.40?
use the pH to find the
equilibrium [H3O+]
HA + H2O A + H3O+
write the reaction for
the acid with water [HA] [A] [H3O+]
construct an ICE initial 0.012 0 0
table for the reaction change
enter the initial equilibrium 4.0E-04
concentrations and
[H3O+]equil
Practice What is the Ka of nicotinic acid,
HC6H4NO2, if a 0.012 M solution of nicotinic
acid has a pH of 3.40?
fill in the rest of the HA + H2O A + H3O+
table using the
[H3O+] as a guide [HA] [A] [H3O+]
if the difference is initial 0.012 0 0
insignificant, 4.0E-04 +4.0E-04 +4.0E-04
[HA]equil = [HA]initial
change
0.012 4.0E-04 4.0E-04
substitute into the equilibrium 4.0E-04
0.012
Ka expression and
compute Ka
Polyprotic Acids
Acid molecules often 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, H2SO4 = diprotic, H3PO4 = triprotic
Polyprotic acids ionize in steps
each ionizable H is removed sequentially
Removing of the first H automatically makes removal of
the second H harder
H2SO4 is a stronger acid than HSO4
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
Because [ionized acid]equil = [H3O+]equil
Example 15.9: What is the percent ionization
of a 2.5 M HNO2 solution?
write the reaction for
HNO2 + H2O NO2 + H3O+
the acid with water
construct an ICE [HNO2] [NO2] [H3O+]
enter the Initial change x +x +x
Concentrations
equilibrium 2.5 x x x
define the change in
concentration in
terms of x
sum the columns to
define the
equilibrium
concentrations
determine the value Ka for HNO2 = 4.6 x 104
of Ka from Table 15.5 [HNO2] [NO2] [H3O+]
because Ka is very initial 2.5 0 0
small, approximate
the [HNO2]eq =
change x +x +x
[HNO2]init and solve equilibrium 2.5x 2.5 x x
for x
substitute x into [HNO2] [NO2] [H3O+]
the equilibrium
solve
equilibrium 2.5 x
2.5 x
0.034 x
0.034
x = 3.4 x 102
apply the definition [HNO2] [NO2] [H3O+]
and compute the
percent ionization initial 2.5 0 0
change x +x +x
equilibrium 2.5 0.034 0.034
because the percent
ionization is < 5%,
the x is small
approximation is
valid
Practice What is the percent ionization of a
0.012 M solution of nicotinic acid, HC 6H4NO2?
(Ka = 1.4 x 105 @ 25 C)
write the reaction for HC6H4NO2 + H2O C6H4NO2 + H3O+
the acid with water
construct an ICE [HA] [A] [H3O+]
concentrations
equilibrium
assuming the [H3O+]
from water is 0
represent the HC6H4NO2 + H2O C6H4NO2 + H3O+
change in the
terms of x initial 0.012 0 0
sum the columns change x +x +x
to find the
concentrations in
terms of x
substitute into the
equilibrium
constant
expression
Practice What is the percent ionization of a 0.012 M
solution of nicotinic acid, HC6H4NO2? Ka = 1.4 x 105
HC6H4NO2 + H2O C6H4NO2 + H3O+
determine the value
of Ka [HA] [A] [H3O+]
because Ka is very initial 0.012 0 0
the [HA]eq = [HA]init
0.012x x x
Practice What is the percent ionization of a 0.012 M
substitute x into [HA] [A] [H3O+]
the equilibrium
solve
x = 4.1 x 104
apply the definition [HA] [A] [H3O+]
and compute the
percent ionization initial 0.012 0 0
change x +x +x
because the equilibrium 0.012 4.1E-04 4.1E-04
percent ionization
is < 5%, the
x is small
approximation is
valid
Relationship Between
[H3O+]equilibrium & [HA]initial
Increasing the initial
concentration of acid results in
increased [H3O+] at equilibrium
Increasing the initial
concentration of acid results in
decreased percent ionization
This means that the increase in
[H3O+] concentration is slower
than the increase in acid
concentration
Why doesnt the increase in H3O+ keep
up with the increase in HA?
The reaction for ionization of a weak acid is
HA(aq) + H2O(l) A(aq) + H3O+(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 [H3O+] in the dilute solution compared to
the initial acid concentration
This will result in a larger percent ionization
Finding the pH of Mixtures of Acids
Generally, you can ignore the contribution of the
weaker acid to the [H3O+]equil
For a mixture of a strong acid with a weak acid,
the complete ionization of the strong acid provides
more than enough [H3O+] to shift the weak acid
equilibrium to the left so far that the weak acids
added [H3O+] 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
Example 15.10: Find the pH of a mixture of
0.150 M HF(aq) solution and 0.100 M HClO2(aq)
write the reactions for HF + H2O F + H3O+ Ka = 3.5 x 104
the acids with water
and determine their Kas HClO + H2O ClO + H3O+ Ka = 2.9 x 108
if the Kas are H2O + H2O OH + H3O+ Kw = 1.0 x 1014
sufficiently different,
use the strongest acid
to construct an ICE [HF] [F] [H3O+]
table for the reaction
initial 0.150 0 0
enter the initial
concentrations change
assuming the [H3O+]
from water is 0 equilibrium
Example 15.10: Find the pH of a mixture of 0.150
M HF(aq) solution and 0.100 M HClO2(aq)
represent the [HF] [F-] [H3O+]
change in the
term of x
change x +x +x
sum the columns to
find the equilibrium equilibrium 0.150 x x x
concentrations in
terms of x
substitute into the

expression
Ka for HF = 3.5 x 104
because Ka is very [HF] [F-] [H3O+]
small, approximate
the [HF]eq = [HF]init initial 0.150 0 0
and solve for x change x +x +x
equilibrium 0.150
0.150 x x x
Ka for HF = 3.5 x 104
check if the [HF] [F-] [H3O+]
approximation is
x < 5% of [HF]init change x +x +x
x = 7.2 x 103

Ka for HF = 3.5 x 104
substitute x into [HF] [F-] [H3O+]
the equilibrium
solve
equilibrium 0.150-x x
0.143 0.0072 x
0.0072
x = 7.2 x 103
Ka for HF = 3.5 x 104
substitute [H3O+] [HF] [F-] [H3O+]
into the formula
for pH and solve initial 0.150 0 0
change x +x +x
equilibrium 0.143 0.0072 0.0072
Ka for HF = 3.5 x 104
check by substituting [HF] [F-] [H3O+]
the equilibrium
constant expression
given Ka
though not exact,

the answer is
reasonably close
Practice Determine the pH @ 25 C of a
solution that is a mixture of 0.045 M HCl and
0.15 M HF
Practice Determine the pH @ 25 C of a solution
that is a mixture of 0.045 M HCl and 0.15 M HF
Given: [HCl] = 4.5 x 102 M, [HF] = 0.15 M
Find: pH
Conceptual Because HCl is a strong acid and HF is a weak acid,
Plan: [H3O+] = [HCl]
[HCl] [H3O+] pH
Relationships:
Solution:

Strong Bases
The stronger the base, the
more willing it is to accept H NaOH Na+ + OH
use water as the standard acid
For ionic bases, practically all
units are dissociated into OH
or accept Hs
strong electrolyte
multi-OH strong bases
completely dissociated
[HO] = [strong base] x (# OH)
Example 15.11: Calculate the pH at 25 C of a 0.0015
M Sr(OH)2 solution and determine if the solution is
acidic, basic, or neutral
Given: [Sr(OH)2] = 1.5 x 103 M
Find: pH
Conceptual [Sr(OH)2] [OH] [H3O+] pH
Plan:
[OH]=2[Sr(OH)2]
Relationships:
Solution:
[OH]
= 2(0.0015)
= 0.0030 M

Practice Calculate the pH of the
following strong acid or base solutions
0.0020 M HCl
[H3O+] = [HCl] = 2.0 x 103 M
pH = log(2.0 x 103) = 2.70
0.0015 M Ca(OH)2
[OH] = 2 x [Ca(OH)2] = 3.0 x 103 M
pOH = log(3.0 x 103) = 2.52
pH = 14.00 pOH = 14.00 2.52
pH = 11.48
Weak Bases
In weak bases, only a small
fraction of molecules accept Hs
weak electrolyte
NH3 + H2O NH4+ + OH
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
Base Ionization Constant, Kb
Base strength measured by the size of the
equilibrium constant when react with H2O
:Base + H2O OH + H:Base+
The equilibrium constant is called the base
ionization constant, Kb
larger Kb = stronger base
Structure of Amines
Example 15.12:Find the pH of 0.100 M NH 3(aq)
write the reaction NH3 + H2O NH4+ + OH

for the base with
water [NH3] [NH4+] [OH]
table for the change
reaction
equilibrium
enter the initial
concentrations
assuming the because no products initially, Qc = 0,
[OH] from water and the reaction is proceeding forward
is 0
Example 15.12: Find the pH of 0.100 M NH 3(aq)
represent the [NH3] [NH4+] [OH]
change in the
sum the columns to equilibrium 0.100 x x x
concentrations in
terms of x
substitute into the
equilibrium
constant
expression
determine the value Kb for NH3 = 1.76 x 105
of Kb from Table
15.8 [NH3] [NH4+] [OH]
because Kb is very initial 0.100 0 0
the [NH3]eq = [NH3]init
and solve for x 0.100x
Kb for NH3 = 1.76 x 105
check if the [NH3] [NH4+] [OH]
approximation is
x < 5% of [NH3]init change x +x +x
x = 1.33 x 103

Kb for NH3 = 1.76 x 105
substitute x into [NH3] [NH4+] [OH]
the equilibrium
definitions and change -x +x +x
solve
equilibrium 0.100
0.099x 1.33E-3
x x
1.33E-3
x = 1.33 x 103
Kb for NH3 = 1.76 x 105
use the [OH] to [NH3] [NH4+] [OH]
find the [H3O+]
using Kw initial 0.100 0 0
substitute [H3O+] change x +x +x

into the formula equilibrium 0.099 1.33E3 1.33E3
for pH and solve
Kb for NH3 = 1.76 x 105
check by
substituting the [NH3] [NH4+] [OH]
equilibrium
constant expression
and comparing the equilibrium 0.099 1.33E3 1.33E3
calculated Kb to the
given Kb
though not exact,

the answer is
reasonably close
Practice Find the pH of a 0.0015 M
morphine solution, Kb = 1.6 x 106
Practice Find the pH of a 0.0015 M morphine solution
write the reaction

for the base with B + H2O BH+ + OH
water [B] [BH+] [OH]
table for the
reaction change
concentrations
assuming the
because no products initially, Qc = 0,
[OH] from water
is 0 and the reaction is proceeding forward
represent the B + H2O BH+ + OH

change in the
concentrations in [B] [BH+] [OH]
terms of x
initial 0.0015 0 0
sum the columns
to find the change x +x +x
concentrations in
terms of x
substitute into
the equilibrium
constant
expression
determine the Kb for morphine = 1.6 x 106

value of Kb
[B] [BH+] [OH]
because Kb is very initial 0.0015 0 0
small, approximate
the [B]eq = [B]init change x +x +x
0.0015 x x x
Kb for morphine = 1.6 x 106
check if the [B] [BH+] [OH]
approximation is
x < 5% of [B]init change x +x +x
x = 4.9 x 105

substitute x into [B] [BH++] [OH
[OH]]
the equilibrium
+x
solve
equilibrium 0.0015 x
0.0015x 4.9E5 x
4.9E5
x = 4.9 x 105
use the [OH] to [B] [BH+] [OH]
find the [H3O+]
using Kw
initial 0.0015 0 0
change x +x +x
substitute [H3O+]
into the formula equilibrium 0.0015 4.9E5 4.9E5
for pH and solve
check by
substituting the [B] [BH+] [OH]
equilibrium
concentrations back
initial 0.0015 0 0
constant expression
and comparing the equilibrium 0.0015 4.9E5 4.9E5
calculated Kb to the
given Kb
the answer
matches the
given Kb
AcidBase 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
NaHCO3 solutions are basic
Na+ is the cation of the strong base NaOH
HCO3 is the conjugate base of the weak acid H 2CO3
Salts that contain cations that are the conjugate acid of
a weak base and an anion of a strong acid are acidic
NH4Cl solutions are acidic
NH4+ is the conjugate acid of the weak base NH 3
Cl is the anion of the strong acid HCl
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) + H2O(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) + H2O(l) HCl(aq) + OH(aq)
An anion that is the conjugate base of a weak acid
is basic
F(aq) + H2O(l) HF(aq) + OH(aq)
Example 15.13: Use the table to determine
if the given anion is basic or neutral
a) NO3
the conjugate base of
a strong acid,
therefore neutral
b) NO2
the conjugate base of
a weak acid, therefore
basic
Relationship between Ka of an Acid and
Kb of Its Conjugate Base
Many reference books only give tables of Ka

values because Kb values can be found from them
when you add
equations, you
multiply the Ks
Na+ is the cation
of a strong base Example 15.14: Find the pH of
pH neutral. The 0.100 M NaCHO2(aq) solution
CHO2 is the
anion of a weak
acid pH basic CHO2 + H2O HCHO2 + OH
write the reaction [CHO2] [HCHO2] [OH]
for the anion with initial 0.100 0 0
water
change
construct an ICE
table for the equilibrium
reaction
enter the initial
concentrations
assuming the
[OH] from water
is 0
Copyright 2011 Pearson Education, Inc.
Example 15.14: Find the pH of 0.100
M NaCHO2(aq) solution
represent the
change in the [CHO2] [HCHO2] [OH]
concentrations in
terms of x initial 0.100 0 0
sum the columns to change x +x +x
concentrations in equilibrium 0.100 x x x
terms of x
Calculate the value

of Kb from the value
of Ka of the weak
acid from Table 15.5
substitute into the
expression
Example 15.14: Find the pH of 0.100 M NaCHO2(aq)
Kb for CHO2 = 5.6 x 1011
because Kb is very [CHO2] [HCHO2] [OH]
small, approximate
the [CHO2]eq =
initial 0.100 0 0
[CHO2]init and solve change x +x +x
for x equilibrium 0.100
0.100x x x
Kb for CHO2 = 5.6 x 1011
check if the [CHO2] [HCHO2] [OH]
approximation is
[CHO2]init
x = 2.4 x 106

Kb for CHO2 = 5.6 x 1011
substitute x into [CHO2] [HCHO2] [OH]
the equilibrium
solve
equilibrium 0.100
0.100x x
2.4E-6 x
2.4E-6
x = 2.4 x 106
Kb for CHO2 = 5.6 x 1011

use the [OH] to
find the [H3O+] [CHO2] [HCHO2] [OH]
using Kw initial 0.100 0 0
substitute [H3O+] change x +x +x
into the formula
equilibrium 0.100 2.4E-6 2.4E-6
for pH and solve
check by Kb for CHO2 = 5.6 x 1011
substituting the [CHO2] [HCHO2] [OH]
equilibrium
concentrations initial 0.100 0 0
back into the
equilibrium
change x +x +x
constant equilibrium 0.100 2.4E6 2.4E6
expression and
comparing the
calculated Kb to
the given Kb
though not exact,

the answer is
reasonably close
Practice If a 0.15 M NaA solution has a pOH
of 5.45, what is the Ka of HA?
Na+ is the cation
of a strong base If a 0.0015 M NaA solution has a pOH
pOH neutral. of 5.45, what is the Ka of HA?
Because pOH is <
7, the solutinon is
basic. A is basic.
A
+ H 2O HA + OH
write the reaction [A] [HA] [OH]

for the anion with initial 0.100 0 0
water
change
construct an ICE
table for the equilibrium
reaction
enter the initial
concentrations
assuming the
[OH] from water
is 0
165 Copyright 2011 Pearson Education, Inc.
Practice If a 0.15 M NaA solution has a
pOH of 5.45, what is the Ka of HA?
use the pOH to [A] [HA] [OH]
find the [OH]
initial 0.15 0 0
use [OH] to fill
in other items
change 3.6E6 +3.6E6 +3.6E6
calculate the [A] [HA] [OH]
value of Kb of A
initial 0.15 0 0
change 3.6E6 +3.6E6 +3.6E6
use Kb of A to [A] [HA] [OH]
find Ka of HA
initial 0.15 0 0
change 3.6E6 +3.6E6 +3.6E6

K b
Polyatomic Cations as
Weak Acids
Some cations can be thought of as the conjugate acid
of a weak base
others are the counter-ions of a strong base
Therefore, some cations can potentially be acidic
MH+(aq) + H2O(l) MOH(aq) + H3O+(aq)
The stronger the base is, the weaker the
conjugate acid is
a cation that is the counter-ion of a strong base is pH neutral
a cation that is the conjugate acid of a weak base is acidic
NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)
because NH3 is a weak base, the position of this equilibrium favors
the right
Metal Cations as Weak Acids
Cations of small, highly charged metals are weakly
acidic
alkali metal cations and alkali earth metal cations are pH
neutral
cations are hydrated
Al(H2O)63+(aq) + H2O(l) Al(H2O)5(OH)2+ (aq) + H3O+(aq)
Example 15.15: Determine if the given
cation Is acidic or neutral
a) C5N5NH2+
the conjugate acid of the weak base pyridine,
therefore acidic
b) Ca2+
the counter-ion of the strong base Ca(OH)2,
therefore neutral
a) Cr3+
a highly charged metal ion, therefore acidic
Classifying Salt Solutions as
Acidic, Basic, or Neutral
If the salt cation is the counter-ion of a strong
base and the anion is the conjugate base of a
strong acid, it will form a neutral solution
NaCl Ca(NO3)2 KBr
If the salt cation is the counter-ion of a strong
weak acid, it will form a basic solution
NaF Ca(C2H3O2)2 KNO2
If the salt cation is the conjugate acid of a weak
strong acid, it will form an acidic solution
NH4Cl
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(NO3)3
If the salt cation is the conjugate acid of a weak
weak acid, the pH of the solution depends on
the relative strengths of the acid and base
NH4F because HF is a stronger acid than NH4+, Ka
of NH4+ is larger than Kb of the F; therefore the
solution will be acidic
Example 15.16: Determine whether a solution
of the following salts is acidic, basic, or neutral
a) SrCl2
Sr2+ is the counter-ion of a strong base, pH neutral
Cl is the conjugate base of a strong acid, pH neutral
solution will be pH neutral
b) AlBr3
Al3+ is a small, highly charged metal ion, weak acid
Cl is the conjugate base of a strong acid, pH neutral
b) CH3NH3NO3
CH3NH3+ is the conjugate acid of a weak base, acidic
NO3 is the conjugate base of a strong acid, pH neutral
Example 15.16: Determine whether a solution
of the following salts is acidic, basic, or neutral
d) NaCHO2
Na+ is the counter-ion of a strong base, pH neutral
CHO2 is the conjugate base of a weak acid, basic
solution will be basic
d) NH4F
NH4+ is the conjugate acid of a weak base, acidic
F is the conjugate base of a weak acid, basic
Ka(NH4+) > Kb(F); solution will be acidic
Practice Determine whether a solution of
the following salts is acidic, basic, or neutral
K+ is the counter-ion of a strong base, pH neutral
KNO3 NO is the counter-ion of a strong acid, pH neutral
3
the
Co3+solution is pH
is a highly neutralcation, pH acidic
charged
CoCl3 Cl is the counter-ion of a strong acid, pH neutral
the
2+ solution is pH acidic
Ba is the counter-ion of a strong base, pH neutral
the solution is pH basic
Ba(HCO3)2
CH NH + isis the
HCO the conjugate
conjugate of
of aa weak
weak acid,
base,pH
pHbasic

3
3 3 acidic
the solution is pH acidic
CH3NH3NO3
NO3 is the counter-ion of a strong acid, pH neutral
Ionization in Polyprotic Acids
Because polyprotic acids ionize in steps, each H has a
separate Ka
Ka1 > Ka2 > Ka3
Generally, the difference in Ka 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 H2SO4 use [H2SO4] as the [H3O+] for the second
ionization
[A2] = Ka2 as long as the second ionization is negligible
Practice What is the pH of a 0.12 M solution
of carbonic acid, H2CO3?
(Ka1 = 4.3 x 107, Ka2 = 5.6 x 1011)
H2CO3 + H2O HCO3 + H3O+
write the reactions
for the acid with HCO3 + H2O CO32 + H3O+
water one H at a
time
[HA] [A] [H3O+]
construct an ICE
reaction change
concentrations
assuming the
second ionization
is negligible
represent the H2CO3 + H2O HCO3 + H3O+
change in the
terms of x
initial 0.12 0 0
sum the columns x +x
change +x
to find the
concentrations in
terms of x
substitute into the
equilibrium
constant
expression
carbonic acid, H2CO3?
determine the Ka1 = 4.3 x 107, Ka2 = 5.6 x 1011
value of Ka1
[HA] [A] [H3O+]
because Ka1 is very
small, approximate
initial 0.12 0 0
the [HA]eq = [HA]init change x +x +x
and solve for x equilibrium 0.12 x
0.012 x x
Ka1 for H2CO3 = 4.3 x 107
check if the [HA] [A] [H3O+]
approximation is
[H2CO3]init
x = 2.27 x 104

substitute x into the [HA] [A] [H3O+]

equilibrium
solve
x = 2.3 x 104
substitute [H3O+] [HA] [A] [H3O+]

change x +x +x
equilibrium 0.12 0.00023 0.00023
check by substituting Ka1 for H2CO3 = 4.3 x 107

the equilibrium [HA] [A] [H3O+]
concentrations back
into the equilibrium initial 0.12 0 0
constant expression change x +x +x
and comparing the
calculated Ka to the equilibrium 0.12 0.00023 0.00023
given Ka
the values match

within sig figs
Practice What is the [CO32] in a 0.12 M
solution of carbonic acid, H2CO3?
(Ka1 = 4.3 x 107, Ka2 = 5.6 x 1011)
write the reactions
for the acid with H2CO3 + H2O HCO3 + H3O+
water one H at a HCO3 + H2O CO32 + H3O+
time
construct an ICE [HCO3] [CO32] [H3O+]
table for the
reaction
initial 0.00023 0 0.00023

concentrations for equilibrium
the second
ionization using the
equilibrium
concentrations
from first ionization
represent the HCO3 + H2O CO32 + H3O+
change in the
concentrations in [HCO3] [CO32] [H3O+]
terms of x initial 0.00023 0 0.00023
sum the columns change x +x +x
to find the
equilibrium equilibrium 2.3E4 x x 2.3E4 +x
concentrations in
terms of x
substitute into the
equilibrium
constant
expression
Practice What is the [CO32] in a 0.12 M solution of
determine the Ka1 = 4.3 x 107, Ka2 = 5.6 x 1011
value of Ka2 [HCO3] [CO32] [H3O+]
because Ka2 is very initial 0.00023 0 0.00023
the [HA]eq = [HA]init,
[H3O+]eq = [H3O+]init, equilibrium 2.3E4 xx 2.3E4
x +x
and solve for x
using this
approximation, it is
seen that x = Ka2.
Therefore [CO32]
= Ka2
Ionization in H2SO4
The ionization constants for H2SO4 are

H2SO4 + H2O HSO4 + H3O+ strong
HSO4 + H2O SO42 + H3O+ Ka2 = 1.2 x 102
For most sulfuric acid solutions, the second
ionization is significant and must be accounted
for
Because the first ionization is complete, use
the given [H2SO4] = [HSO4]initial = [H3O+]initial
H2SO4(aq) solution @ 25 C
write the reactions H2SO4 + H2O HSO4 + H3O+
for the acid with
water HSO4 + H2O SO42 + H3O+
construct an ICE
table for the
[HSO4 ] [SO42 ] [H3O+]
second ionization initial 0.0100 0 0.0100
reaction
change
enter the initial
concentrations equilibrium
assuming the
[HSO4] and [H3O+]
is [H2SO4]
represent the
[HSO4 ] [SO42 ] [H3O+]
change in the
concentrations in initial 0.0100 0 0.0100
terms of x
change x +x +x
sum the columns
to find the
equilibrium 0.0100
x
0.0100
x x
equilibrium
concentrations in
terms of x
substitute into the
equilibrium
constant
expression
Ka for HSO4 = 0.012
expand and solve
for x using the
quadratic formula
Ka for HSO4 = 0.012
substitute x into [HSO4 ] [SO42 ] [H3O+]
the equilibrium initial 0.0100 0 0.0100
concentration
solve equilibrium 0.0100
0.0055x 0.0045
x 0.0100
0.0145x
x = 0.0045
Ka for HSO4 = 0.012
substitute [H3O+] [HSO4 ] [SO42 ] [H3O+]
into the formula initial 0.0100 0 0.0100
for pH and solve
change x +x +x
equilibrium 0.0055 0.0045 0.0145
Ka for HSO4 = 0.012
check by [HSO4 ] [SO42 ] [H3O+]
substituting the initial 0.0100 0 0.0100
equilibrium
concentrations back change x +x +x
into the equilibrium equilibrium 0.0055 0.0045 0.0145
constant expression
and comparing the
given Ka
the answer
matches
Strengths of Binary Acids
The more + HX polarized
the bond, the more acidic the
bond
The stronger the HX bond, the
weaker the acid
Binary acid strength increases to
the right across a period
acidity: HC < HN < HO < HF
Binary acid strength increases
down the column
acidity: HF < HCl < HBr < HI
Relationship between Bond Strength
and Acidity
Bond
Energy Type of
Acid
Acid
kJ/mol
HF 565 weak
HCl 431 strong
HBr 364 strong

Strengths of Oxyacids, HOY
The more electronegative the Y atom, the stronger the
oxyacid
HClO > HIO
acidity of oxyacids decreases down a group
same trend as binary acids
helps weakens the HO bond
The larger the oxidation number of the central atom, the
stronger the oxyacid
H2CO3 > H3BO3
acidity of oxyacids increases to the right across a period
opposite trend of binary acids
The more oxygens attached to Y, the stronger the oxyacid
further weakens and polarizes the HO bond
HClO3 > HClO2
Relationship Between
Electronegativity and Acidity
Acid Electronegativity Ka
HOY of Y
HOCl 3.0 2.9 x 108
HOBr 2.8 2.0 x 109
HOI 2.5 2.3 x 1011
Relationship Between Number of Oxygens
on the Central Atom and Acidity
Practice Order the Following
By Acidity (Least to Most)

H3PO4 HNO3H3PO3 H3AsO3

HCl HBr H2S HS
By Basicity (Least to Most)

CO32 NO3 HCO3 BO33
Practice Order the Following
H3PO4 HNO3H3PO3 H3AsO3
H3AsO3 < H3PO3 < H3PO4 < HNO3
HCl HBr H2S HS
HS < H2S < HCl < HBr
By Basicity (Least to Most)
CO32 NO3 HCO3 BO33
NO3 < HCO3 < CO32 < BO33
Lewis AcidBase Theory
Lewis AcidBase theory focuses on transferring
an electron pair
lone pair bond
bond lone pair
Does NOT require H atoms
The electron donor is called the Lewis Base
electron rich, therefore nucleophile
The electron acceptor is called the Lewis Acid
electron deficient, therefore electrophile
Lewis Bases
Lewis Base has electrons it is willing to give
away to or share with another atom
Lewis Base must have lone pair of electrons on
it that it can donate
Anions are better Lewis Bases than neutral
atoms or molecules
N: < N:
Generally, the more electronegative an atom, the
less willing it is to be a Lewis Base
O: < S:
Lewis Acids
Electron deficient, either from
being attached to electronegative atom(s)
not having an octet
Must have empty orbital willing to accept the electron
pair
H+ has empty 1s orbital
B in BF3 has empty 2p orbital and an incomplete octet
Many small, highly charged metal cations have empty
orbitals they can use to accept electrons
Atoms that are attached to highly electronegative
atoms and have multiple bonds can be Lewis Acids
Lewis AcidBase Reactions
The base donates a pair of electrons to the

acid
Generally results in a covalent bond forming
H3N: + BF3 H3NBF3
The product that forms is called an adduct
Arrhenius and Brnsted-Lowry acidbase
reactions are also Lewis
Examples of Lewis AcidBase Reactions
Examples of Lewis AcidBase Reactions
Ag+(aq) + 2 :NH3(aq) Ag(NH3)2+(aq)

Lewis Lewis Adduct
Acid Base
Practice Identify the Lewis Acid and
Lewis Base in Each Reaction
Lewis
Base Lewis
Acid
Lewis Lewis
Base Acid
U.S. Fuel Consumption
Over 85% of the energy use in the United States
comes from the combustion of fossil fuels
oil, natural gas, coal
Combustion of fossil fuels produces CO2
CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g)
Natural fossil fuels also contain small amounts of S
that burn to produce SO2(g)
S(s) + O2(g) SO2(g)
The high temperatures of combustion allow N2(g) in
the air to combine with O2(g) to form oxides of nitrogen
N2(g) + 2 O2(g) 2 NO2(g)
What Is Acid Rain?
Natural rain water has a pH of 5.6

naturally slightly acidic due mainly to CO2
Rain water with a pH lower than 5.6 is called
acid rain
Acid rain is linked to damage in ecosystems
and structures
What Causes Acid Rain?
Many natural and pollutant gases dissolved in the
air are nonmetal oxides
CO2, SO2, NO2
Nonmetal oxides are acidic
CO2(g) + H2O(l) H2CO3(aq)
2 SO2(g) + O2(g) + 2 H2O(l) 2 H2SO4(aq)
4 NO2(g) + O2(g) + 2 H2O(l) 4 HNO3(aq)
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
pH of Rain in Different Regions
Weather Patterns
The prevailing winds in the United States travel

west to east
Weather patterns may cause rain to be acidic
in regions other than where the nonmetal
oxide is produced
Much of the northeast United States has rain of
very low pH, even though it has very low sulfur
emissions, due in part to the general weather
patterns
Sources of SO2 from Utilities
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 affects aquatic life
Soil acidity causes more dissolving of minerals
and leaching more minerals from soil
making it difficult for trees
Damage from Acid Rain
Acid Rain Legislation
1990 Clean Air Act attacks acid rain

forces utilities to reduce SO2
Result is acid rain in the Northeast stabilized
and beginning to be reduced

Chapter 15

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Chapter 15

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Chemistry: A Molecular Approach, 2nd Ed.

Mild cases of heartburn can be cured by

Binary acids have acid hydrogens attached

Most ionic bases contain OH ions

HCl ionizes in water, NaOH dissociates in water,

The H+ from the acid combines with the OH

In a Brnsted-Lowry acidbase reaction, an H+

NH3 and NH4+ constitute

CO32 because CO32 does not have an H, it

H2SO4 + H2O HSO4 + H3O+

HCO3 + H2O H2CO3 + HO

HSO4(aq) + HCO3(aq) SO42(aq) + H2CO3(aq)

Acid Base Conjugate Conjugate

HBr HBr + H2O Br + H3O+

HSO4 HSO4 + H2O SO42 + H3O+

CO32 + H2O HCO3 + OH

Weak acids donate a small

Check: the units are correct; the fact that the

Check: the units are correct; the fact that the

Check: pH is unitless; the fact that the pH > 7 means

Check: pH is unitless; the fact that the pH < 7 means

Check: because the pH < 7, [OH] should be less

Check: pH is unitless; the fact that the pH > 7 means

Given: [H3O+] = 2.5 x 109 M

Check: pH is unitless; the fact that the pH < 7 means

because no products initially, Qc = 0, and the reaction is proceeding

the approximation is valid

though not exact,

write the reaction HC6H4NO2 + H2O C6H4NO2 + H3O+

the approximation is valid

substitute x into the [HA] [A] [H3O+]

substitute [H3O+] [HA] [A] [H3O+]

check by substituting [HA] [A] [H3O+]

the values match

the approximation is invalid

the answer matches

construct an ICE change

Because [ionized acid]equil = [H3O+]equil

(Ka = 1.4 x 105 @ 25 C)

substitute into the

the approximation is valid

though not exact,

Check: pH is unitless; the fact that the pH < 7 means

Check: pH is unitless; the fact that the pH > 7 means

write the reaction NH3 + H2O NH4+ + OH

the approximation is valid

substitute [H3O+] change x +x +x

though not exact,

write the reaction

represent the B + H2O BH+ + OH

determine the Kb for morphine = 1.6 x 106

the approximation is valid

Many reference books only give tables of Ka

Calculate the value

the approximation is valid

Kb for CHO2 = 5.6 x 1011

though not exact,

write the reaction [A] [HA] [OH]

the approximation is valid

substitute x into the [HA] [A] [H3O+]

substitute [H3O+] [HA] [A] [H3O+]

check by substituting Ka1 for H2CO3 = 4.3 x 107

the values match

enter the initial change