Acids and Bases

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 Acids

Have a sour taste. Vinegar owes its taste to acetic acid. Citrus
fruits contain citric acid.
React with certain metals to produce hydrogen gas.
React with carbonates and bicarbonates to produce carbon
dioxide gas

Bases
Have a bitter taste.

Feel slippery. Many soaps contain bases.

4.3
Arrhenius acid is a substance that produces H+ (H3O+) in water

Arrhenius base is a substance that produces OH- in water

4.3
 A Brnsted acid is a proton donor
A Brnsted base is a proton acceptor

base acid acid base

conjugate conjugate
base acid
acid base

15.1
 Acid-Base Properties of Water

H2O (l) H+ (aq) + OH- (aq)

autoionization of water

+ + H -
H O + H O [ H O H ] O
H H H

conjugate
base
acid
H2O + H2O H3O+ + OH-
acid conjugate
base 15.2
 The Ion Product of Water

[H+][OH-]
H2O (l) H+ (aq) + OH- (aq) Kc = [H2O] = constant
[H2O]

Kc[H2O] = Kw = [H+][OH-]

The ion-product constant (Kw) is the product of the molar

concentrations of H+ and OH- ions at a particular temperature.

Solution Is
[H+] = [OH-] neutral
At 250C [H+] > [OH-] acidic
Kw = [H+][OH-] = 1.0 x 10-14
[H+] < [OH-] basic

15.2
What is the concentration of OH- ions in a HCl solution
whose hydrogen ion concentration is 1.3 M?

Kw = [H+][OH-] = 1.0 x 10-14

[H+] = 1.3 M

K w 1 x 10 -14
[OH-] = = = 7.7 x 10 -15
M
[H ]
+
1.3

15.2
 pH A Measure of Acidity

pH = -log [H+]

Solution Is At 250C
neutral [H+] = [OH-] [H+] = 1 x 10-7 pH = 7
acidic [H+] > [OH-] [H+] > 1 x 10-7 pH < 7
basic [H+] < [OH-] [H+] < 1 x 10-7 pH > 7

pH [H+]

15.3
 pOH = -log [OH-]

[H+][OH-] = Kw = 1.0 x 10-14

-log [H+] log [OH-] = 14.00

pH + pOH = 14.00

15.3
 Strong Electrolyte 100% dissociation
H2O
NaCl (s) Na+ (aq) + Cl- (aq)

Weak Electrolyte not completely dissociated

CH3COOH CH3COO- (aq) + H+ (aq)

Strong Acids are strong electrolytes

HCl (aq) + H2O (l) H3O+ (aq) + Cl- (aq)

HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)
HClO4 (aq) + H2O (l) H3O+ (aq) + ClO4- (aq)
H2SO4 (aq) + H2O (l) H3O+ (aq) + HSO4- (aq)
15.4
Weak Acids are weak electrolytes

HF (aq) + H2O (l) H3O+ (aq) + F- (aq)

HNO2 (aq) + H2O (l) H3O+ (aq) + NO2- (aq)
HSO4- (aq) + H2O (l) H3O+ (aq) + SO42- (aq)
H2O (l) + H2O (l) H3O+ (aq) + OH- (aq)

Strong Bases are strong electrolytes

H 2O
NaOH (s) Na+ (aq) + OH- (aq)
H2O
KOH (s) K+ (aq) + OH- (aq)
H2O
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)

15.4
Weak Bases are weak electrolytes

F- (aq) + H2O (l) OH- (aq) + HF (aq)

NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)

Conjugate acid-base pairs:

The conjugate base of a strong acid has no measurable
strength.
H3O+ is the strongest acid that can exist in aqueous
solution.
The OH- ion is the strongest base that can exist in aqeous
solution.

15.4
15.4
Strong Acid Weak Acid

15.4
 What is the pH of a 2 x 10-3 M HNO3 solution?
HNO3 is a strong acid 100% dissociation.
Start 0.002 M 0.0 M 0.0 M
HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)
End 0.0 M 0.002 M 0.002 M

pH = -log [H+] = -log [H3O+] = -log(0.002) = 2.7

What is the pH of a 1.8 x 10-2 M Ba(OH)2 solution?

Ba(OH)2 is a strong base 100% dissociation.
Start 0.018 M 0.0 M 0.0 M
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)
End 0.0 M 0.018 M 0.036 M
pH = 14.00 pOH = 14.00 + log(0.036) = 12.6
15.4
Weak Acids (HA) and Acid Ionization Constants

HA (aq) + H2O (l) H3O+ (aq) + A- (aq)

HA (aq) H+ (aq) + A- (aq)

[H+][A-]
Ka =
[HA]

Ka is the acid ionization constant

weak acid
Ka
strength

15.5
15.5
 Ionized acid concentration at equilibrium
percent ionization = x 100%
Initial concentration of acid

For a monoprotic acid HA

[H+]
Percent ionization = x 100% [HA]0 = initial concentration
[HA]0

15.5
Weak Bases and Base Ionization Constants

NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

[NH4+][OH-]
Kb =
[NH3]

Kb is the base ionization constant

weak base
Kb
strength

Solve weak base problems like weak acids

except solve for [OH-] instead of [H+].

15.6
15.6
15.8
 Molecular Structure and Acid Strength
H X H+ + X-

The The
stronger weaker
the bond the acid

HF << HCl < HBr < HI

15.9
 Molecular Structure and Acid Strength
- +
Z O H Z O- + H+

The O-H bond will be more polar and easier to break if:
Z is very electronegative or
Z is in a high oxidation state

15.9
 Molecular Structure and Acid Strength

1. Oxoacids having different central atoms (Z) that are from

the same group and that have the same oxidation number.

Acid strength increases with increasing electronegativity of Z

O O

H O Cl O H O Br O

Cl is more electronegative than Br

HClO3 > HBrO3

15.9
 Molecular Structure and Acid Strength

2. Oxoacids having the same central atom (Z) but different

numbers of attached groups.

Acid strength increases as the oxidation number of Z increases.

HClO4 > HClO3 > HClO2 > HClO

15.9
 Acid-Base Properties of Salts
Neutral Solutions:
Salts containing an alkali metal or alkaline earth metal
ion (except Be2+) and the conjugate base of a strong
acid (e.g. Cl-, Br-, and NO3-).
H2O
NaCl (s) Na+ (aq) + Cl- (aq)

Basic Solutions:
Salts derived from a strong base and a weak acid.
H2O
NaCH3COO (s) Na+ (aq) + CH3COO- (aq)

CH3COO- (aq) + H2O (l) CH3COOH (aq) + OH- (aq)

15.10
 Acid-Base Properties of Salts
Acid Solutions:
Salts derived from a strong acid and a weak base.

H2O
NH4Cl (s) NH4+ (aq) + Cl- (aq)

NH4+ (aq) NH3 (aq) + H+ (aq)

Salts with small, highly charged metal cations (e.g. Al3+,

Cr3+, and Be2+) and the conjugate base of a strong acid.

Al(H2O)63+(aq) Al(OH)(H2O)52+(aq) + H+ (aq)

15.10
 Acid-Base Properties of Salts
Solutions in which both the cation and the anion hydrolyze:

Kb for the anion > Ka for the cation, solution will be basic

Kb for the anion < Ka for the cation, solution will be acidic

Kb for the anion Ka for the cation, solution will be neutral

15.10
Oxides of the Representative Elements
In Their Highest Oxidation States

CO2 (g) + H2O (l) H2CO3 (aq)

N2O5 (g) + H2O (l) 2HNO3 (aq)

15.11
As defined at the time of discovery, acid-base
reactions are characterized by Arrhenius acids,
which dissociate in aqueous solution form
hydrogen or the later-termed oxonium (H3O+)
ions, and Arrhenius bases which form hydroxide
(OH-) ions.

More recent IUPAC recommendations now suggest the

newer term "hydronium be used in favor of the older
accepted term "oxonium.
 4- Brnsted-Lowry definition

1923

professor of inorganic and

physical chemistry at Copenhagen English physical chemist
The Brnsted-Lowry definition, formulated independently by its
two proponents Johannes Nicolaus Brnsted and Martin Lowry
in 1923 is based upon the idea of protonation of bases through
the de-protonation of acids -- more commonly referred to as the
ability of acids to "donate" hydrogen ions (H+) or protons to
bases, which "accept" them.

CH3COOH + H2O CH3COO- + H3O+

NH3 + H2O NH4+ + OH-

CH3COO- + H2O CH3COOH + OH-

NH4+ + H2O NH3 + H3O+

In contrast to the Arrhenius definition, the Brnsted-Lowry definition refers
to the products of an acid-base reaction as conjugate acids and bases to
refer to the relation of one proton, and to indicate that there has been a
reaction between the two quantities, rather than a "formation" of salt and
water, as explained in the Arrhenius definition

AH + B BH+ + A-
General formula for representing Brnsted-Lowry reactions.

HCl (aq) + H2O H3O+(aq) + Cl- (aq)

Hydrochloric acid completely reacts with water to form the
hydronium and chloride ions

CH3COOH + NH3 NH4+ + CH3COO-

Acetic acid reacts incompletely with ammonia, no hydronium
ions being produced
 In differentiation from the Arrhenius definition, the Brnsted-Lowry
definition postulates that for each acid, there is a conjugate acid and base
or "conjugate acid-base pair" that is formed through a complete reaction,
which also includes water, which is amphoteric

For example, zinc oxide (ZnO) reacts differently depending on the pH of the solution:
In acids: ZnO + 2H+ Zn2+ + H2O
In bases: ZnO + H2O + 2OH- [Zn(OH)4]2-

Base (Proton Acceptor): H2O + HCl H3O+ + Cl

Acid (Proton Donor): H2O + NH3 NH4+ + OH
(Indeed, it can do both at once: 2H2O H3O+ + OH )
 O (e.g. H2SO4) was originally thought to cause
acidic properties. Later, H was implicated, but
it was still not clear why CH4 was neutral.
Arrhenius made the revolutionary suggestion
that some solutions contain ions & that acids
produce H3O+ (hydronium) ions in solution.
Ionization +
H H
Cl H + O HO + Cl
H H
The more recent Bronsted-Lowry concept is
that acids are H+ (proton) donors and bases
are proton acceptors
 The Bronsted-Lowry concept
In this idea, the ionization of an acid by water
is just one example of an acid-base reaction.
H H
+
Cl H + O HO + Cl
H H
acid base conjugate acid conjugate base

conjugate acid-base pairs

Acids and bases are identified based on whether
they donate or accept H+.
Conjugate acids and bases are found on the
products side of the equation. A conjugate base
is the same as the starting acid minus H +.
 Practice problems
Identify the acid, base, conjugate acid,
conjugate base, and conjugate acid-base pairs:

HC2H3O2(aq) + H2O(l) C2H3O2(aq) + H3O+(aq)

acid base conjugate base conjugate acid

conjugate acid-base pairs

OH (aq) + HCO3(aq) CO32(aq) + H2O(l)
base acid conjugate base conjugate acid

conjugate acid-base pairs

Acid Base Strength
Strong Acid - Transfers all protons to water;
completely ionizes;
strong electrolyte;
conjugate base is weaker and has
negligible tendency to be protonated.
Weak Acid - Fraction of protons transferred to water;
partly ionized;
weak electrolyte;
conjugate base is stronger readily
accepting protons from water
As acid strength decreases, base strength increases.
The stronger the acid, the weaker its conjugate base
The weaker the acid, the stronger its conjugate base
Leveling effect
The term leveling effect refers to a solvent's ability to level
the effect of a strong acid or base dissolved in it.
When a strong acid is dissolved in water, it reacts with it to form
H3O+ in the following reaction (where "HA" is a generic strong
acid such as "HCl"):
HA + H2O A- + H3O+
Any acid that is stronger than H3O+ reacts with H2O to form
H3O+; therefore, no acid can be stronger than H3O+ in H2O.
This is true with any solvent, although usually to a lesser extent
than with water. Bases may be also leveled in solvents
The acidity and basicity in the aqueous solutions are limited by
H+ and OH . The acidity of any substance is stronger than H+
or the basicity is stronger than OH will be leveled off. This is
called leveling effect.
 2 EtOH = EtOH2 + + EtO- ; KAB = 10-20
2 NH3 = NH4+ + NH2- ; KAB = 10-29
2 H2SO4 = H3SO4+ + HSO4-
2 OPCl3 = OPCl4- + OPCl2+ (Cl transfer)
(phosphoryl halides)
 Which one is stronger?
A) HCl B) HClO4

Because of this leveling effect, HClO4 and HCl behave as if

they had the same acid strength; both are leveled to H3O+:
HClO4 + H2O H3O+ + ClO-
HCl + H2O H3O+ + Cl-

In acetic acid solvent, which is less basic than H2O, HClO4 and HCl
are not leveled to the same strength:
HClO4 + CH3COOH CH3COOH2+ + ClO4_ K= 1.3 10-5
HCl + CH3COOH CH3COOH2+ + Cl- K= 2.8 10-9
Lewis definition
a famous American physical chemist
known for his 1902
Lewis dot structures, his paper "The
Atom and the Molecule", which is
the foundation of modern
valence bond theory, developed in
coordination with Irving Langmuir .

his 1923 textbook

Thermodynamics and the
Free Energy of Chemical
Substances, written in
coordination with Merle Randall, Gilbert Newton Lewis
one of the founding books in (October 23, 1875 - March 23, 1946)
chemical thermodynamics

In 1926, Lewis coined the term "photon" for the smallest unit of radiant energy.
 Definition of An Acid
Arrhenius acid is a substance that produces H+ (H3O+) in water

A Brnsted acid is a proton donor

A Lewis acid is a substance that can accept a pair of electrons

A Lewis base is a substance that can donate a pair of electrons

H+ + OH- H O H


acid base
H H
+
H+ + N H H N H

H H
acid base
15.12
 Lewis Acids and Bases

F H F H
F B + N H F B N H

F H F H
acid base

No protons donated or accepted!

15.12
The Lewis definition of acid base reactions, devised by Gilbert N. Lewis
in 1923 is an encompassing theory to the Brnsted-Lowry and solvent-
system definitions with regards to the premise of a donation mechanism,
which conversely attributes the donation of electron pairs from bases
and the acceptance by acids, rather than protons or other bonded
substances and spans both aqueous and non-aqueous reactions

Ag+ + 2 :NH3 [H3N:Ag:NH3]+

A silver cation reacts as an acid with ammonia which acts as

an electron-pair donor, forming an ammonia-silver adduct

Acid - An electron
pair acceptor
Base - An electron
pair donor
Solvent-system definition
This definition is based on a generalization of the earlier
Arrhenius definition to all autodissociating solvents. In all such
solvents there is a certain concentration of a positive species,
solvonium cations and negative species, solvate anions, in
equilibrium with the neutral solvent molecules. For example:

2H2O H3O+ (hydronium) + OH- (hydroxide)

2NH3 NH4+ (ammonium) + NH2 (amide)

or even some aprotic systems:

N2O4 NO+ (nitrosonium) + NO3 (nitrate)
2SbCl3 SbCl2+ (dichloroantimonium) + SbCl4- (tetrachloroantimonate)
A solute causing an increase in the concentration of the
solvonium ions and a decrease in the solvate ions is an
acid and one causing the reverse is a base.

Thus, in liquid ammonia, KNH2 (supplying NH2-) is a strong base,

and NH4NO3 (supplying NH4+) is a strong acid.

Lux-Flood concept
acid - oxide ion (O2-) acceptor
base - oxide ion (O2-) donor

ex. CaO + SiO2 CaSiO3 (= Ca2+[SiO3]2-)

base acid
This definition, proposed by German chemist Hermann Lux in
1939, further improved by Hkon Flood circa 1947 and now
commonly used in modern geochemistry and electrochemistry
of molten salts, describes an acid as an oxide ion acceptor and
a base as an oxide ion donor. For example:

MgO (base) + CO2 (acid) MgCO3

CaO (base) + SiO2 (acid) CaSiO3
NO3- (base) + S2O72- (acid) NO2+ + 2SO42-
 Usanovich definition
The most general definition is that of the Russian chemist
Mikhail Usanovich, and can basically be summarized as
defining an acid as "anything that accepts negative species
or donates positive ones," and a base as the reverse. This
tends to overlap the concept of redox (oxidation-
reduction), and so is not highly favored by chemists. This
is because redox reactions focus more on physical electron
transfer processes, rather than bond making/bond breaking
processes, although the distinction between these two
processes is somewhat ambiguous.
 Chemistry In Action: Antacids and the Stomach pH Balance

NaHCO3 (aq) + HCl (aq)

NaCl (aq) + H2O (l) + CO2 (g)

Mg(OH)2 (s) + 2HCl (aq)

MgCl2 (aq) + 2H2O (l)
<Hard-Soft Acids & Bases>

- HSAB concept
- by Pearson

" Hard likes Hard & Soft likes Soft "

Trends in Kf
 Acid Base

ex. Ti4+, Si4+, Cr3+, Mo3+

ex. H3N, RO-, O2-
<Hard> high oxidation state
localized(= tight)
small size
lone pair
not very polarizable

ex. Hg2+, Pt2+, Au+

ex. R2S, RS-, R3P
<Soft> low oxidation state
diffuse(= soft)
large size
lone pair
very polarizable
H+
Hard acids
Li+ Be2+

Na+ Mg2+ Al3+

K+ Ca2+ Cr3+ Mn2+ Fe3+ Co3+ Ga3+

Sr2+

Tl3+

All ions with ox # =4 or higher

 Soft acids

Cu+

Ag+ Cd2+

Pt4+ Au+ Hg2+ Tl+ Pb2+

Pt2+ Hg22+

Metals with ox # = 0
Borderline acids

Fe2+ Co2+ Ni2+ Cu2+ Zn2+

Ru3+ Rh3+

Os2+ Ir3+
 Hard and soft bases
Hard bases Borderline bases Soft bases
H-
F- Br-, Cl- I-
H2O, OH-, O2- H2S, HS-, S2-
ROH, RO-, R2O, RSH, RS-, R2S
CH3COO-
NO , ClO
3
-
4
- NO2-, N3-, NSC- SCN-, CN-, RNC, CO
CO32-, SO42-, PO43- SO32- S2O3-
NH3, RNH2, N2H4 C6H5NH2, C5H5N, R3P, (RO) 3P, R3As,
N2 C2H4, C6H6
 Hard & Soft Bases
Hard ligands
Oxygen ligands in H2O, CO32-, NO3-, PO43-, ROPO32-, (RO)2PO3-,
CH3COO-, OH-, RO-, R2O, and crown ethers
Nitrogen ligands in NH3, N2H4, RNH2
Intermediate ligands
Br-, SO32-
nitrogen ligands in NO2-, N3-, N2, aniline, imidazole
Soft ligands
Sulfur ligands in RSH, RS-, R2S
R3P, RNC, CN-, CO, R-, H-, I-, S2O32-, (RS)2PO2-, (RO)2P(O)S-

Adapted from: Roat-Malone, R.M. Bioinorganic Chemistry: A Short Course, Wiley: New Jersey, 2002, p.6.
 SCN- - ambidentate ligand
soft hard
[Ag(SCN)2]-
[Cr(NCS)6]3-
Symbiosis

- termed by Jrgensen

BF3 + F- BF4-
hardhard

BH3 + H- BH4-
soft soft

BH3F- + BF3H- BH4- + BF4-

CH3F + CF3H CH4 + CF4

<Acid & Base Strength>

1. acidity of oxyacids:

a) electronegativity of central atom

H2CO3, H3PO4, H2SO4, HNO3, HClO4

stronger acid

b) inductive effect of substituent

CH3COOH, CH2FCOOH, CHF2COOH, CF3COOH

stronger acid

c) number of oxygen atoms

HClO, HClO2, HClO3, HClO4

stronger acid
2. acidity of binary hydrogen compounds:

P. T.

acidity

3. basicity of metal oxides:

BeO, MgO, CaO, SrO, BaO

more basic

() Be2+ size Mg2+ size

Be-O bond energy Mg-O bond energy
What is a strong Acid?
An Acid that is 100% ionized in water.

Strong Acids:
100% ionized (completely dissociated) in water.

HCl + H2O H3O+ + Cl-

often written as:

HCl H+ + Cl-
Strong Acids:
100% ionized (completely dissociated) in water.

HCl + H2O H3O+ + Cl-

Strong Acids:
Perchloric HClO4
Chloric, HClO3
Hydrobromic, HBr
Hydrochloric, HCl
Hydroiodic, HI
Nitric, HNO3
Sulfuric, H2SO4
 What is a strong Base?

A base that is completely dissociated in water (highly soluble).

NaOH(s) Na+ + OH-

Strong Bases:

Group 1A metal hydroxides

(LiOH, NaOH, KOH,
RbOH, CsOH)
Heavy Group 2A metal hydroxides
[Ca(OH)2, Sr(OH)2, and
Ba(OH)2]
Strong Acids:
100% ionized (completely dissociated) in water.

HCl + H2O H3O+ + Cl-

Note the one way arrow.

Weak Acids:
Only a small % (dissociated) in water.

HC2H3O2 + H2O H3O+ + C2H3O2-

Note the 2-way arrow.

Why are they different?

Strong Acids:

HCl HCl (H2O)

HCl
HCl
HCl

ADD WATER to MOLECULAR ACID

Strong Acids:
Cl-
H3O+
(H2O) Cl-
H3O+
H3O+ Cl - Cl-
H3O+
H3O+
Cl-

Note: No HCl molecules remain in

solution, all have been ionized in water.
 Weak Acid Ionization:

HC2H3O2
HC2H3O2
(H2O)
HC 2H 3O 2
HC2H3O2
HC2H3O2

Add water to MOLECULES of WEAK Acid

 Weak Acid Ionization:

HC2H3O2
HC
HC2HH3OO
2 H30+ C2H3O2-
2 3 2 (H2O)
HC2H3O2

H30+ C2H3O2-
HC2H3O2 HC 2H 3O 2

Note: At any given time only a small portion of the acid

molecules are ionized and since reactions are running in
BOTH directions the mixture composition stays the same.

This gives rise to an Equilbrium expression, K a

Super acid
Thus, in Solvent system concept
acid - a species that increases the concentration of the solvent cation
base - a species that increases the concentration of the solvent anion

ex. i) NH3 solvent

2NH3 NH4+ + NH2-

NH3 + CH3COOH NH4+ + CH3COO-

strong acid

NH3 + H2NC(O)NH2 NH4+ + H2NC(O)NH-

acid

ii) BrF3 solvent

2BrF3 BrF2+ + BrF4-

BrF3 + SbF5 BrF2+ + SbF6-

acid

BrF3 + KF K+ + BrF4-
base