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
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

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 2

 Gas Phase Acid-Base
 Not covered by Arrhenius definition
Ex. NH3(g) + HCl(g)  NH4Cl(s)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 3

 Brønsted-Lowry Definition
 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+
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 4
 Conjugate Acid-Base Pair
 Species that differ by H+
Ex. HCl + H2O  H3O+ + Cl–
 HCl = acid
 Water = base
 H3O+
 Conjugate acid of H2O
 Cl–
 Conjugate base of HCl

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 5

 Formic Acid is Bronsted Acid
 Formic acid (HCHO2) is a weak acid
 Must consider equilibrium
 HCHO2(aq) + H2O CHO2–(aq) + H3O+(aq)
 Focus on forward reaction

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 6

 Formate Ion is Bronsted Base
 Now consider reverse reaction
 Hydronium ion transfers H+ to CHO2

conjugate pair

HCHO2 + H2O H3O+ + CHO2

acid base acid base

conjugate pair
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 7
 Learning Check
 Identify the Conjugate Partner for Each
conjugate base conjugate acid
Cl– HCl
NH3 NH4+
C2H3O2– HC2H3O2
CN– HCN
F– HF

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 8

 Learning Check
 Write a reaction that shows that HCO3– is a
Brønsted acid when reacted with OH–

 HCO3–(aq) + OH–(aq) H2O(ℓ) + CO32–(aq)

 Write a reaction that shows that HCO3– is a

Brønsted base when reacted with H3O+(aq)

 HCO3–(aq) + H3O+(aq) H2CO3(aq) + H2O(ℓ)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 9

 Your Turn!
In the following reaction, identify the acid/base
conjugate pair.
(CH3)2NH + H2SO4 → (CH3)2NH+ + HSO4-

A. (CH3)2NH / H2SO4 ; (CH3)2NH+ / HSO4-

B. (CH3)2NH / (CH3)2NH+ ; H2SO4 / HSO4-
C. H2SO4 / HSO4- ; (CH3)2NH+ / (CH3)2NH
D. H2SO4 / (CH3)2NH ; (CH3)2NH+ / HSO4-

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 10

 Amphoteric Substances
 Can act as either acid or base
 Also called amphiprotic
 Can be either molecules or ions
Ex. hydrogen carbonate ion:
 Acid:
HCO3–(aq) + OH–(aq)  CO32–(aq) + H2O(ℓ)
 Base:
HCO3–(aq) + H3O+(aq)  H2CO3(aq) + H2O(ℓ)
 2H2O(ℓ) + CO2(g)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 11

 Your Turn!
Which of the following can act as an
amphoteric substance?

A. CH3COOH
B. HCl
C. NO2-
D. HPO42-

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 12

 Strengths of Acids and Bases
Strength of Acid
 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)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 13

Reactions of Strong Acids and Bases
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

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 14

 Position of Acid-Base Equilibrium
 Acetic acid (HC2H3O2) is weak acid
 Ionizes only slightly in water
HC2H3O2(aq) + H2O(ℓ) H3O+(aq) + C2H3O2–(aq)
weaker acid weaker base 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

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 15

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

A. HCl
B. H2O
C. H3O+
D. Cl-

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 16

 In General
 Stronger acids and bases tend to react with
each other to produce their weaker
conjugates
 Stronger Brønsted acid has weaker
conjugate base
 Weaker Brønsted acid has stronger
conjugate base
 Can be applied to binary acids (acids made
from hydrogen and one other element)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 17

 Learning Check
Identify the preferred direction of the following
reactions:

H3O+(aq) + CO32–(aq) HCO3–(aq) + H2O(ℓ)

Cl–(aq) + HCN(aq) HCl(aq) + CN–(aq)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 18

 Trends in Binary Acid Strength
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

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 19

 Trends in Binary Acid Strength
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

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 20

 Learning Check
 Which is stronger?
 H2S or H2O  H2S

 CH4 or NH3  NH3

 HF or HI  HI

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 21

 Trends in Oxoacid Strength
Oxoacids (HnYOm)
 Acids of H, O, and one other element
 HClO, HIO4, H2SO3, H2SO4, etc.
1. Acids with same number of O’s 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 
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 22
 Trends in Oxoacid Strength
Oxoacids (HnYOm)
2. For same Y
 Acid strength  as number of O’s 
 H2SO3 < H2SO4
 More oxygens, remove more electron density
from central atom, weakening O—H bond
and make H more acidic

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 23

 Learning Check
Which is the stronger acid in each pair?
 H2SO4 or H3PO4 H SO
2 4

 HNO3 or H3PO3
HNO3
 H2SO4 or H2SO3
H2SO4
 HNO3 or HNO2

HNO3
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 24
 Your Turn!
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

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 25

Alternate Definition of Acid Strength
 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 O Cl O H O Cl O

O
HClO3 HClO4
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 26
 Comparing Basicity
 
 O   O 
 ||   || 
HO  S  O  HO  P  O 
|| |
   
 O   OH 
HSO4 (3 lone O) H2PO4 (2 lone O)
 Lone O’s carry most of () charge
 ClO4 has 4 O atoms, so each has ¼ 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
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 27
 Learning Check
 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

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 28

 Strength of Organic Acids
 Organic acid —COOH
 Presence of electronegative atoms (halide,
nitrogen or other oxygen) near —COOH group
 Withdraws electron density from O—H bond
 Makes organic acid, stronger acids
Ex.
CH3CO2H < CH2ClCO2H < CHCl2CO2H < CCl3CO2H

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 29

 Your Turn!
Which of the following is the strongest
organic acid?
A H O B H O C H O

I C C OH Br C C OH H C C OH

H H H

D H O E H O

F C C OH Cl C C OH

H H

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 30

Lewis Definition of Acid and Base
 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 e’s
 Formation of coordinate covalent bond
 Lewis base
 Any ionic or molecular species that can
donate pair of e’s
 Formation of coordinate covalent bond
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 31
 Lewis Neutralization
 Formation of coordinate covalent bond between
electron pair donor and electron pair acceptor

Addition Compound

 NH3BF3 = addition compound

 Made by joining two smaller molecules
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 32
 Lewis Acid-Base Reaction

 Electrons in coordinate covalent bond

come from O in hydroxide ion
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 33
 Lewis Acids:
1. Molecules or ions with incomplete valence
shells
Ex. BF3 or H+
2. Molecules or ions with complete valence
shells, but with multiple bonds that can be
shifted to make room for more electrons
Ex. CO2
3. 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
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 34
 SO2 as Lewis Acid

O2–

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 35

 Lewis Bases:
 Molecules or ions that have unshared
electron pairs and that have complete
shells
 Ex. O2– or NH3
Lewis Definition is Most General
 All Brønsted acids and bases are Lewis acids and
bases
 All Arrhenius acids and bases are Brønsted acids
and bases

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 36

H+ Transfer from Lewis Perspective
Ex. H2O—H+ + NH3  H2O + H+—NH3

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 37

 Learning Check
Identify the Lewis acid and base in the following:
 NH3 + H+ NH4+
Base Acid

 F– + BF3 BF4 –
Base Acid

 SeO3 + O2– SeO42–

Acid Base

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 38

 Your Turn!
Which of the following species can act as a
Lewis base ?

A. Cl-
B. Fe2+
C. NO2-
D. O2-

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 39

Acid-Base Properties of Elements and
Their Oxides
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(ℓ)  H2SO4(aq)
 N2O5(g) + H2O(ℓ)  2HNO3(aq)
 CO2(g) + H2O(ℓ)  H2CO3(aq)
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 40
 Acid-Base Properties of Elements
and Their Oxides
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(ℓ)  2NaOH(aq)
 CaO(s) + H2O(ℓ)  Ca(OH)2(aq)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 41

 Metal Oxides MxOy
 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(ℓ)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 42

 Your Turn!
What is the acid formed by P2O3 when it
reacts with water ?

A. H2PO4
B. H2PO2
C. H3PO4
D. H3PO3

 P2O3 + 3H2O → 2H3PO3

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 43

 Metal Ions in Solution (once anion
removed)
 Exist with sphere of polar H2O's with  of O's
in toward Mn+
 Mn+(aq) + mH2O(ℓ) M(H2O)mn+(aq)
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)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 44

 Hydrated Metal Ions = Weak
Brønsted Acids

M(H2O)n+(aq) + H2O(ℓ) M(OH)n+(aq) + H3O+(aq)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 45
 Your Turn!
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 OH-

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 46

 Hydrated Metal Ions Can Act as
Weak Acids
 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
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 47
Acidity of Hydrated Metal Ions
 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 O—H bond
  acidity of H+

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 48

 Acidity of Hydrated Metal Ions
2. As  Size of Cation,  Acidity
 Smaller, more concentrated charge
 Means  pull of e density from O—H bond
  acidity of H+
 Net result
 Very small, highly charged cations are very
acidic
[Al(H2O)6]3+(aq) + H2O(ℓ) [Al(H2O)5(OH)]2+(aq) +
H3O+(aq)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 49

 Your Turn!
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+

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 50

 Trends in Acidity of Mn+
 Acidity  up group (column) as cation size 
 Acidity  across period (row) as cation size 
Alkali Metal Ions All weak
(Li+, Na+, K+, Rb+, Cs+) (+1, large size)

Be2+ Moderately weak

Other Alkaline earth Very Weak
metals (Ba2+, Ca2+ Sr2+,
Mg 2+
)
Transition metal ions, Al3+ Quite acidic
(often +3, +4 charges)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 51

 Learning Check
 Identify each of the following as acidic or
basic and give their reaction with water:
 P2O5 acidic
P2O5(s) + 3H2O(ℓ) 2H3PO4(aq)
2H+(aq) + 2H2PO4(aq)
 MnO2 basic
MnO2(s) + 2H2O(ℓ) Mn2+(aq) + 4OH(aq)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 52

 Ceramic Materials
 Date back to prehistoric times
 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
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 53
 Traditional Ceramic Synthesis
1. Pulverize components of ceramic into fine
powders
2. Mix with
 Water and pour into mold or
 Binder and press into desired shape
3. 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
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 54
 Sol-Gel Process
 Synthesis of ceramics that avoid problems of particle
size and uniformity
 Based on acid–base reactions
 Starting materials are
 Metal salts or
 Compounds where metal or metalloid (e.g., Si) is bonded to
some number of alkoxide groups

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 55

 Sol-Gel Process
 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–
 C2H5O– + H2O  100%C H OH + OH–
2 5

 Basis of Sol-Gel Process

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 56

 Your Turn!
Which of the following is an example of an
alkoxide ion ?

A. CH3OCH2+
B. CH3CH2CHO-
C. CHCOO-
D. OH-

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 57

 Sol-Gel Process
 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

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 58

 Sol-Gel Process
 As more H2O is added:
 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

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 59

 Sol-Gel Process
 Sol-gel used in various ways
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
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 60
Sol-gel Technologies and Products

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 61