Brdy 6ed Ch16 AcidBases

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Chapter 16:
Acids and Bases,
A Molecular Look
Chemistry: The Molecular Nature

of Matter, 6E
Jespersen/Brady/Hyslop
Arrhenius Acids and Bases

Acid produces H3O+ in water
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Base gives OH
Acid-base neutralization
Acid and base combine to produce water and a

salt.
Ex. HCl(aq) + NaOH(aq) H2O + NaCl(aq)
H3O+(aq) + Cl(aq) + Na+(aq) + OH(aq)
2H2O + Cl(aq) + Na+(aq)
Many reactions resemble this without

forming H3O+ or OH in solution
Chemistry: The Molecular Nature of Matter, 6E
Gas Phase Acid-Base
Not covered by Arrhenius definition
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Ex. NH3(g) + HCl(g) NH4Cl(s)
Brnsted-Lowry Definition
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Acid = proton donor

Base = proton acceptor
Allows for gas phase acid-base reactions
Ex. HCl + H2O
H3O+ + Cl
HCl = acid
Donates H+
Water = base
Accepts H+
Conjugate Acid-Base Pair
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Species that differ by H+

Ex. HCl + H2O H3O+ + Cl
HCl = acid
Water = base
H3O+
Conjugate acid of H2O
Cl
Conjugate base of HCl
Formic Acid is Bronsted Acid
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Formic acid (HCHO2) is a weak acid

Must consider equilibrium
HCHO2(aq) + H2O
CHO2(aq) + H3O+(aq)
Focus on forward reaction
Formate Ion is Bronsted Base
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Now consider reverse reaction

Hydronium ion transfers H+ to CHO2
conjugate pair
HCHO2 + H2O
acid
base
H3O+ + CHO2
acid
base
conjugate pair
Learning Check
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Identify the Conjugate Partner for Each

conjugate base
Cl
NH3
conjugate acid
HCl
NH4+
C2H3O2
HC2H3O2
CN
HCN
HF
Learning Check
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Write a reaction that shows that HCO3 is a

Brnsted acid when reacted with OH
HCO3(aq) + OH(aq)
H2O() + CO32(aq)
Write a reaction that shows that HCO3 is a

Brnsted base when reacted with H3O+(aq)
HCO3(aq) + H3O+(aq)
H2CO3(aq) + H2O()
Your Turn!
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In the following reaction, identify the acid/base

conjugate pair.
(CH3)2NH + H2SO4 (CH3)2NH+ + HSO4A. (CH3)2NH / H2SO4 ; (CH3)2NH+ / HSO4B. (CH3)2NH / (CH3)2NH+ ; H2SO4 / HSO4C. H2SO4 / HSO4- ; (CH3)2NH+ / (CH3)2NH
D. H2SO4 / (CH3)2NH ; (CH3)2NH+ / HSO4-
10
Amphoteric Substances
Can act as either acid or base
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Also called amphiprotic

Can be either molecules or ions
Ex. hydrogen carbonate ion:

Acid:
HCO3(aq) + OH(aq) CO32(aq) + H2O()
Base:
HCO3(aq) + H3O+(aq) H2CO3(aq) + H2O()
2H2O() + CO2(g)
11
Your Turn!
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Which of the following can act as an

amphoteric substance?
A. CH3COOH
B. HCl
C. NO2D. HPO42-
12
Strengths of Acids and Bases

Strength of Acid
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Measure of its ability to transfer H+

Strong acids
React completely with water Ex. HCl and HNO3
Weak acids
Less than completely ionized Ex. CH3COOH and CHOOH
Strength of Base classified in similar fashion:

Strong bases
React completely with water Ex. Oxide ion (O2) and OH
Weak bases
Undergo incomplete reactions

Ex. NH3 and NRH2 (NH2CH3, methylamine)
13
Reactions of Strong Acids and Bases
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In water
Strongest acid = hydronium ion, H3O+

If more powerful H+ donor added to H2O
Reacts with H2O to produce H3O+
Similarly,
Strongest base is hydroxide ion (OH)
More powerful H+ acceptors
React with H2O to produce OH
14
Position of Acid-Base Equilibrium

Acetic acid (HC2H3O2) is weak acid
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Ionizes only slightly in water
HC2H3O2(aq) + H2O()
weaker acid
weaker base
H3O+(aq) + C2H3O2(aq)
stronger acid
stronger base
Hydronium ion
Better H+ donor than acetic acid

Stronger acid
Acetate ion
Better H+ acceptor than water

Stronger base
Position of equilibrium favors weaker acid and base

15
Your Turn!
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In the reaction:
HCl + H2O H3O+ + Cl-
which species is the weakest base ?

A. HCl
B. H2O
C. H3O+
D. Cl-
16
In General
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Stronger acids and bases tend to react with

each other to produce their weaker
conjugates
Stronger Brnsted acid has weaker
conjugate base
Weaker Brnsted acid has stronger
conjugate base
Can be applied to binary acids (acids made
from hydrogen and one other element)
17
Learning Check
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Identify the preferred direction of the following

reactions:
H3O+(aq) + CO32(aq)
Cl(aq) + HCN(aq)
HCO3(aq) + H2O()
HCl(aq) + CN(aq)
18
Trends in Binary Acid Strength
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Binary Acids = HnX
X = Cl, Br, P, As, S, Se, etc.

1. Acid strength from left to right within
same period (across row)
Acid strength as electronegativity of X
Ex. HCl is stronger acid than H2S which is
stronger acid than PH3
or
PH3 < H2S < HCl
19
Trends in Binary Acid Strength
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Binary Acids = HnX
X = Cl, Br, P, As, S, Se, etc.

2. Acid strength from top to bottom
within group
Acid strength as size of X
Ex. HCl is weaker acid than HBr which is
weaker acid than HI
or
HCl < HBr < HI
20
Learning Check
H2S
CH4 or NH3
NH3
HF or HI
HI
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Which is stronger?
H2S or H2O
21
Trends in Oxoacid Strength

Oxoacids (HnYOm)
Acids of H, O, and one other element
HClO, HIO4, H2SO3, H2SO4, etc.
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1. Acids with same number of Os and

differing Y
a. Acid strength from bottom to top within group
HIO4 < HBrO4 < HClO4
b. Acid strength from left to

right within period
H3PO4 < H2SO4 < HClO4
as electronegativity of central atom

22
Trends in Oxoacid Strength

Oxoacids (HnYOm)
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2. For same Y
Acid strength as number of Os
H2SO3 < H2SO4
More oxygens, remove more electron density
from central atom, weakening OH bond
and make H more acidic
23
Learning Check
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Which is the stronger acid in each pair?

H2SO4 or H3PO4 H2SO4
HNO3 or H3PO3
HNO3
H2SO4 or H2SO3
H2SO4
HNO3 or HNO2
HNO3
24
Your Turn!
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Which corresponds to the correct order of

acidity from weakest to strongest acid ?
A. HBrO3, HBrO, HBrO2
B. HBrO, HBrO2, HBrO3
C. HBrO, HBrO3, HBrO2
D. HBrO3, HBrO2, HBrO
25
Alternate Definition of Acid Strength
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Acid strength can be analyzed in terms of

basicity of anion formed during ionization
Basicity
Willingness of anion to accept H+ from H3O+
Consider HClO3 and HClO4:

O
O
H
Cl
Cl
HClO3
HClO4
26
Comparing Basicity
[ ] [ ]
HSO 4
HOP O
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HOS O
OH
(3 lone O)
H 2 PO 4
(2 lone O)
Lone Os carry most of () charge
ClO4 has 4 O atoms, so each has charge

ClO3 has 3 O atoms, so each has 1/3 charge
ClO4 weaker base than ClO3
Thus conjugate acid, HClO4, is stronger acid
HClO4 stronger acid as more fully ionized

27
Learning Check
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Arrange the following in order of increasing

acid strength:
HBr, AsH3, H2Se
AsH3 < H2Se < HBr
H2SeO4, H2SO4, H2TeO4
H2TeO4 < H2SeO4 < H2SO4
HBrO3, HBrO, HBrO4, HBrO2
HBrO < HBrO2 < HBrO3 < HBrO4
28
Strength of Organic Acids
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Organic acid COOH

Presence of electronegative atoms (halide,
nitrogen or other oxygen) near COOH group
Withdraws electron density from OH bond
Makes organic acid, stronger acids
Ex.
CH3CO2H < CH2ClCO2H < CHCl2CO2H < CCl3CO2H
29
Your Turn!
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Which of the following is the strongest

organic acid?
OH
Br
OH
OH
Cl
OH
OH
H
30
Lewis Definition of Acid and Base
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Broadest definition of species that can be

classified as either acid or base
Definitions based on electron pairs
Lewis acid
Any ionic or molecular species that can accept
pair of es
Formation of coordinate covalent bond
Lewis base
Any ionic or molecular species that can

donate pair of es
Formation of coordinate covalent bond
31
Lewis Neutralization
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Formation of coordinate covalent bond between

electron pair donor and electron pair acceptor
Addition Compound
NH3BF3 = addition compound

Made by joining two smaller molecules
32
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Lewis Acid-Base Reaction
Electrons in coordinate covalent bond

come from O in hydroxide ion
33
Lewis Acids:
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1. Molecules or ions with incomplete valence

shells
Ex. BF3 or H+
1. Molecules or ions with complete valence

shells, but with multiple bonds that can be
shifted to make room for more electrons
Ex. CO2
1. Molecules or ions that have central atoms that

can expand their octets
Capable of holding additional electrons
Usually, atoms of elements in Period 3 and below
Ex. SO2
34
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SO2 as Lewis Acid
O2
35
Lewis Bases:
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Molecules or ions that have unshared

electron pairs and that have complete
shells
Ex. O2 or NH3
Lewis Definition is Most General

All Brnsted acids and bases are Lewis acids and
bases
All Arrhenius acids and bases are Brnsted acids
and bases
36
H+ Transfer from Lewis Perspective
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Ex. H2OH+ + NH3 H2O + H+NH3
37
Learning Check
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Identify the Lewis acid and base in the following:

NH4+
NH3 + H+
Base Acid
F + BF3
BF4
Base Acid
SeO3 + O2
Acid
SeO42
Base
38
Your Turn!
A. ClB. Fe2+
C. NO2D. O2-
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Which of the following species can act as a

Lewis base ?
39
Acid-Base Properties of Elements and

Their Oxides
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Nonmetal oxides
React with H2O to form acids
Upper right hand corner of periodic table
Acidic Anhydrides
Neutralize bases
Aqueous solutions red to litmus
SO3(g) + H2O() H2SO4(aq)
N2O5(g) + H2O() 2HNO3(aq)
CO2(g) + H2O() H2CO3(aq)
40
Acid-Base Properties of Elements

and Their Oxides
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Metal oxides
React with H2O to form hydroxide (Base)

Group 1A and 2A metals (left hand side of
periodic table)
Basic Anydrides
Neutralize acids
Aqueous solutions blue to litmus
Na2O(s) + H2O() 2NaOH(aq)
CaO(s) + H2O() Ca(OH)2(aq)
41
Metal Oxides MxOy
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Solids at RT
Many insoluble in H2O
Why?
Too tightly bound in crystal

Can't remove H+ from H2O
Do dissolve in solution of strong acid

Now H+ free, can bind to O2 and remove from
crystal
Fe2O3(s) + 6H+(aq) 2Fe3+(aq) + 3H2O()
42
Your Turn!
A. H2PO4
B. H2PO2
C. H3PO4
D. H3PO3
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What is the acid formed by P2O3 when it

reacts with water ?
P2O3 + 3H2O
2H3PO3
43
Metal Ions in Solution (once anion

removed)
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Exist with sphere of polar H2O's with of O's

in toward Mn+
M(H2O)mn+(aq)
Mn+(aq) + mH2O()
Lewis Acid
Lewis Base
hydrated metal ion

= addition compound
n = charge on metal ion

= 1, 2, or 3 depending on metal atom
For now assume m = 1 (monohydrate)
44
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Hydrated Metal Ions = Weak

Brnsted Acids
M(H2O)n+(aq) + H2O()
M(OH)n+(aq) + H3O+(aq)
45
Your Turn!
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The following reactions:

Al(OH)3 + 3H+ Al3+ + H2O
Al(OH)3 + OH-
Al(OH)4-
illustrate the concept of
A. Neutralization
B. Amphoteric property of Al(OH)3
C. Oxidation of Al
D. Reduction of OHJespersen/Brady/Hyslop
46
Hydrated Metal Ions Can Act as

Weak Acids
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Electron deficiency of metal cations causes

them to induce electron density towards
metal from water of hydration
Higher charge density = more acidic metal
ionic charge
charge density=
ionic volume
Acidity left to right across period
Acidity top to bottom down group
47
Acidity of Hydrated Metal Ions
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Degree to which M(H2O)mn+ produces

acidic solutions depends on
1. Charge on cation
2. Cation's size
1. As Charge on Mn+, Acidity

M's ability to draw electron density to
itself and away from OH bond
acidity of H+
48
Acidity of Hydrated Metal Ions

2. As Size of Cation, Acidity
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Smaller, more concentrated charge

Means pull of e density from OH bond
acidity of H+
Net result
Very small, highly charged cations are very

acidic
[Al(H2O)6]3+(aq) + H2O()
[Al(H2O)5(OH)]2+(aq) +
H3O+(aq)
49
Your Turn!
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In the following list of pairs of ions, which is

the more acidic ?
Fe2+ or Fe3+; Cu2+ or Cu+; Co2+ or Co3+
A. Fe3+, Cu+, Co2+
B. Fe2+, Cu2+, Co3+
C. Fe3+, Cu2+, Co3+
D. Fe2+, Cu2+, Co2+
50
Trends in Acidity of Mn+
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Acidity up group (column) as cation size

Acidity across period (row) as cation size
Alkali Metal Ions
(Li+, Na+, K+, Rb+, Cs+)
Be2+
All weak
(+1, large size)
Moderately weak
Other Alkaline earth

Very Weak
metals (Ba2+, Ca2+ Sr2+,
2+
Mg
)
Transition
metal ions, Al3+ Quite acidic
(often +3, +4 charges)
51
Learning Check
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Identify each of the following as acidic or

basic and give their reaction with water:
P2O5
acidic
P2O5(s) + 3H2O()
MnO2
basic
2H3PO4(aq)
2H+(aq) + 2H2PO4(aq)
MnO2(s) + 2H2O()
Mn2+(aq) + 4OH(aq)
52
Ceramic Materials
Date back to prehistoric times
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Pottery as far back as 13,000 years old
Today found in brick, cement, and glass

Porcelain dinnerware, tiles, sinks, toilets, artistic
pottery and figurines
Composed of Silicates compounds containing
anions composed of silicon and oxygen
Advanced Ceramic Materials
Made in chemistry laboratories

High-tech applications
Found in cell phones and diesel engines
53
Traditional Ceramic Synthesis
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1. Pulverize components of ceramic into fine

powders
2. Mix with
Water and pour into mold or
Binder and press into desired shape
1. Heat in kiln, T > 1000 C
Sintering particles fuse together to form ceramic
Problems:
Hard to form uniform, very small particles

Ceramics formed often have small cracks
which decreases their strength
Composition not easily reproducible
54
Sol-Gel Process
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Synthesis of ceramics that avoid problems of particle

size and uniformity
Based on acidbase reactions
Starting materials are
Metal salts
or
Compounds where metal or metalloid (e.g., Si) is bonded to
some number of alkoxide groups
55
Sol-Gel Process
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Metal alkoxide salts generally soluble in

alcohols
Alcohols are very weak acids
Essentially no tendency to lose H+
Alkoxide ions very strong bases
React with water to form alcohol and OH

100%
C2H5O + H2O C2H5OH + OH
Basis of Sol-Gel Process
56
Your Turn!
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Which of the following is an example of an

alkoxide ion ?
A. CH3OCH2+
B. CH3CH2CHOC. CHCOOD. OH-
57
Sol-Gel Process
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Gradually add water to alcohol solution of

alkoxide salts
Alkoxide ions gradually replaced by OH ions
Hydrolysis reaction
Zr(C2H5O)4 + H2O Zr(C2H5O)3OH + C2H5OH
When 2 Zr(C2H5O)3OH encounter each other,

undergo acid-base reaction with loss of H2O
58
Sol-Gel Process
As more H2O is added:
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More alkoxide ions converted to alcohols

Form more oxide linkages bridging Zr ions
Result is very fine particles of metal oxides with
residual OH ions suspended in alcohol (gel-like)
Sol-gel used in various ways
1. Dip coated on surface yields thin film ceramics

2. Cast into mold produces semisolid gelatin-like material
= wet gel
Dry wet gel by evaporation gives porous gel = xerogel
Heating xerogel yields dense ceramic or glass with
uniform structure
59
Sol-Gel Process
Sol-gel used in various ways
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3. Remove solvent from wet gel

at temperature above critical TiN
coating
temperature of solvent yields
very porous and extremely low
density solid = aerogel
4. Adjust viscosity of gel
Ceramic heat tiles
suspension and spinning yields
ceramic fibers
5. Precipitation of sol-gels yields
ultrafine and uniform ceramic
powders
60
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Sol-gel Technologies and Products
61

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Chemistry: The Molecular Nature

Arrhenius Acids and Bases

Acid and base combine to produce water and a

Many reactions resemble this without

Chemistry: The Molecular Nature of Matter, 6E

Gas Phase Acid-Base

Not covered by Arrhenius definition

Ex. NH3(g) + HCl(g) NH4Cl(s)

Chemistry: The Molecular Nature of Matter, 6E

Acid = proton donor

Ex. HCl + H2O

Chemistry: The Molecular Nature of Matter, 6E

Conjugate Acid-Base Pair

Species that differ by H+

Conjugate base of HCl

Chemistry: The Molecular Nature of Matter, 6E

Formic Acid is Bronsted Acid

Formic acid (HCHO2) is a weak acid

Focus on forward reaction

Chemistry: The Molecular Nature of Matter, 6E

Formate Ion is Bronsted Base

Now consider reverse reaction

Chemistry: The Molecular Nature of Matter, 6E

Identify the Conjugate Partner for Each

Chemistry: The Molecular Nature of Matter, 6E

Write a reaction that shows that HCO3 is a

Write a reaction that shows that HCO3 is a

Chemistry: The Molecular Nature of Matter, 6E

In the following reaction, identify the acid/base

Chemistry: The Molecular Nature of Matter, 6E

Also called amphiprotic

Ex. hydrogen carbonate ion:

Chemistry: The Molecular Nature of Matter, 6E

Which of the following can act as an

Chemistry: The Molecular Nature of Matter, 6E

Strengths of Acids and Bases

Measure of its ability to transfer H+

React completely with water Ex. HCl and HNO3

Less than completely ionized Ex. CH3COOH and CHOOH

Strength of Base classified in similar fashion:

React completely with water Ex. Oxide ion (O2) and OH

Undergo incomplete reactions

Chemistry: The Molecular Nature of Matter, 6E

Reactions of Strong Acids and Bases

Strongest acid = hydronium ion, H3O+

Chemistry: The Molecular Nature of Matter, 6E

Position of Acid-Base Equilibrium

Ionizes only slightly in water

Better H+ donor than acetic acid

Better H+ acceptor than water

Position of equilibrium favors weaker acid and base

Chemistry: The Molecular Nature of Matter, 6E

which species is the weakest base ?

Chemistry: The Molecular Nature of Matter, 6E

Stronger acids and bases tend to react with

Chemistry: The Molecular Nature of Matter, 6E

Identify the preferred direction of the following

Chemistry: The Molecular Nature of Matter, 6E

Trends in Binary Acid Strength

Binary Acids = HnX

X = Cl, Br, P, As, S, Se, etc.

PH3 < H2S < HCl