Chapter 7

Acids and Bases

History
Svante Arrhenius in 1884
acids contain hydrogen ions and bases contain
hydroxide ions
the solvent problem
difference in properties of a compound in two different
solvents

The salt problem

salts should be neutral

Ionization and Dissociation

Dissociation
the separation of ions
Na+OH-(s)

dissolve in water

Na+(aq)

OH-(aq)

Ionization
the breaking of covalent bonds resulting in ion
formation
HCl(g)

H2O(l)

dissolve in water

H3O+(aq)

OH-(aq)

Brnsted-Lowry Theory
Acids
proton donor

Bases
proton acceptor

Water
undergoes
d
autoionization
i i i

Autoionization
H2O(l) + H2O(l) H3O+(aq)
( ) + OH-(aq)
( )
Kw = [H3O+][OH-] = 1.0 x 10-14 at 25C
15 at 0C and 4.8
13 at 100C
1.2
1 2 x 10-15
4 8 x 10-13

Conjugate acid-base pairs

one molecule donates a proton (acid), another accepts
one (base)
when the reaction is reversed, the hydronium ion
donates a proton (acid) and the hydroxide ion accepts a
proton (base)

Amphiproticity
acting as either an acid or a base

Hydronium Ion
H3O+
tetrahedral molecular geometry
naturally exists as a trihydrate in solution
H9 O4 +

Acid-Base Behavior
Water functioning as a base
( q) + H2O(l)
( ) H3O+((aq)
q) + F-((aq)
q)
HF(aq)
HF is the acid, H2O is the base
H3O+ ((conjugate
j g acid),
), F- ((conjugate
j g base))

Water functioning as an acid

NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
H2O is the acid, NH3 is the base
NH4+ ((conjugate
j g acid),
), OH
O - ((conjugate
j g base))

Strong Acids and Bases

H3O+Cl-(aq) + Na+OH-(aq) 2H2O(l) + Na+Cl-(aq)
H3O+(aq) + OH-(aq) 2H2O(l)
Strong bases and strong acids dissociate
completely in water
O2-(aq) + H2O(l) 2OH-(aq)
HClO4(aq) + H2O(l) H3O+(aq) + ClO4-(aq)

Acid-Base
Acid
Base Chemistry in Other
Solvents
Ammonia (NH3) also undergoes
autoionization
NH3(l) + NH3(l) NH4+(NH3) + NH2-(NH3)
Acid-base
Acid base reactions in ammonia
NH4+Cl-(NH3) + Na+NH2-(NH3)
Na+Cl-(s) + 2NH3(l)

Acid-Base Equilibrium Constants

Acid ionization constant, Ka
measure of how easily a proton can be removed
HA(aq) + H2O(l) H3O+(aq) + A-(aq)
Ka expression written as:
Ka

pKa:

[H3O+][A-]
[HA]

pKa = -(log10Ka)
the more negative pKa, the stronger the acid

Acid-Base Equilibrium Constants

Base ionization constant, Kb
measure of how easily a proton is accepted
A-(aq) + H2O(l) HA(aq) + OH-(aq)
Kb expression written as:
Kb

[HA][OH-]
[A-]

pKb:
pKb = -(log10Kb)
the more positive pKb, the weaker the base

Acid-Base Equilibrium Constants

Ion product constant for water, Kw
Kw = [Ka][Kb] = [H3O+][OH-] = 1 x 10-14
pKw = pKa + pKb = 14
th
the stronger
t
the
th base,
b
the
th weaker
k the
th conjugate
j t
acid and vice versa

Brnsted-Lowry Acids
If Ka > 1 (negative pKa values),
regarded as a strong acid
undergo 100% ionization

If Ka < 1 (positive pKa values),

values)
regarded as a weak acid
establish
t bli h an equilibrium
ilib i
(less
(l than
th 100%
ionization)

Binary Acids
Most common are the hydrohalic acids
HF is the only weak acid of the four
HI is
i the
h strongest acid
id
HX(aq) + H2O(l) H3O+(aq) + X-(aq)
Acid

pKa

Bond Energy (kJ/mol)

HF(aq)

+3

565

HCl(aq)

-7
7

428

HBr(aq)

-9

362

HI(aq)

-10

295

H2O (l)

+7

459

Oxyacids
Ternary acids containing oxygen
the ionizable hydrogen is bond to oxygen
HNO3 (HONO2)

the more oxygen atoms, the stronger the acid

HNO3 (pKa = -1.4) vs. HNO2 (pKa = +3.3)
O
H

(OH)nXOm
(m=0, pKa=8);(m=1, pKa=2);(m=2, pKa=-1);(m=3, pKa=-8)

Polyprotic Acids
Acids containing more than one ionizable
hydrogen
y g
H2SO4(aq) + H2O(l) H3O+(aq) + HSO4(aq)
(pKa = -2)
2 (aq)
HSO4-(aq)
( ) + H2O(l) H3O+(aq)
( ) + SO42( )
(pKa = +1.9)

Brnsted-Lowry Bases
OH- is the most important base
NH3 is the next most important
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)

Other equilibria
q
PO43-(aq) + H2O(l) HPO42-(aq) + OH-(aq)
(pKb = 1.35))
(p
S2-(aq) + H2O(l) HS-(aq) + OH-(aq) (2.04)
F-(aq) + H2O(l) HF(aq) + OH-(aq) (10.55)

Multiple Ionizations in Bases

S2-(aq) + H2O(l) HS-(aq) + OH-(aq) (2.04)
HS-((aq)
q) + H2O(l)
( ) H2S(aq)
( q) + OH-((aq)
q) ((6.96))
and
PO43-(aq) + H2O(l) HPO42-(aq) + OH-(aq) (1.35)
(1 35)
HPO42-(aq) + H2O(l) H2PO4-(aq) + OH-(aq)
(6 79)
(6.79)
H2PO4-(aq) + H2O(l) H3PO4(aq) + OH-(aq)
(11 88)
(11.88)

The Acidity of Metal Ions

Dissolving metal ions in water give
hydrated ions
weakly held water molecules (low charge
density) are neutral
strongly
l held
h ld water molecules
l l (high
(hi h charge
h
density) tend to be acidic
[Fe(OH2)6]3+(aq) + H2O(l) H3O+(aq) +
[[Fe(OH
( 2)5((OH)]
)]2+((aq)
q)

The Acidity of Metal Ions

Ions with +3 or higher are always acidic
reaction with water is called hydrolysis
Acidity of Some Metal Ions
Li+

Be2+

slightly acidic weakly acidic

Na+

Mg2+

Al3+

neutral

weakly acidic

acidic

K+

Ca2+

Sc3+

Ti4+

neutral

slightly acidic

acidic

very acidic

pKa Values for Metal Ions

As many as there are positive charges
[Fe(OH2)6]3+(aq) + H2O(l) H3O+(aq) +
[Fe(OH2)5(OH)]2+(aq) (pKa1)
2 (aq) + H O(l) H O+(aq) +
[Fe(OH2)5(OH)]2+
2
3
[Fe(OH2)4(OH)2]+(aq) (pKa2)

[Fe(OH2)4(OH)2]+(aq) + H2O(l) H3O+(aq) +

Fe(OH)3(aq) + 3H2O(l) (pKa3)

Basicity of Nonmetal Anions

Dissolving anions
in water g
give
neutral to basic
species
p
the lower the
charge
g density,
y the
more basic the
solution

Basicity of Some Nonmetal Ions

N3-

O2-

F-

very basic very basic

weakly basic

P3-

Cl-

S2-

very basic
b i basic
b i

neutrall

As3-

Br-

Se2-

very
y basic basic
Te2-

neutral
I-

weakly basic neutral

Basicity of Nonmetal Anions

Weakly basic
F-(aq) + H2O(l) HF(aq) + OH-(aq)
Basic
2 (aq)
S2( ) + H2O(l) HS-(aq)
( ) + OH-(aq)
( )
Very Basic
O2-(aq) + H2O(l) 2OH-(aq)

Basicity of Oxyanions
Depends upon the number of oxygen atoms
and ion charge
g
XOn as n decreases,, the basicity
y increases
the greater oxygen content weakens the O-H bond,
making hydrolysis more difficult

XO4n as the charge increases, the basicity increases

Basicity of Oxyanions
Basicity of Some XOn- Oxyanions

Basicity of Some XO4n- Oxyanions

Classification Type

Examples

Classification Type

XO4-

ClO4-, MnO4-

Neutral

XO3-

NO3-,ClO3-

Weakly basic XO42- SO42-,CrO42-

Weakly basic XO2-

NO2-,ClO2-

Moderately
b i
basic

XO43- PO43-,VO43-

Strongly
basic

XO44- SiO42-

Neutral

Moderately
basic

XO-

ClO-

XO4-

Examples
ClO4-,MnO4-

Oxides
Show many different properties
most metal oxides
basic

most nonmetal oxides

acidic

weak metal oxides

amphoteric

a few nonmetal and metal oxides

neutral

Acid-Base Reactions of Oxides

Reaction of nonmetal acidic oxides with
basic metal oxides
CaO(s) + SO2(g) CaSO3(s)
2CaSO3(s) + O2(g) 2CaSO4(s)
CaCO3(s) + heat CaO(s) + CO2(g)

Acid-Base Reactions of Oxides

Reaction of acidic, nonmetal oxides with
bases
CO2(g) + 2NaOH(aq) Na2CO3(aq) + H2O(l)
Reaction of basic
basic, metal oxides with acids
MgO(s) + 2HNO3(aq) Mg(NO3)2(aq) +
H2O(l)

Comparing Acidities
Measure the free energy change of the
reaction of different acids with the same base
CaO(s) + CO2(g) CaCO3(s)
G = -134
134 kJ/mol
CaO(s) + SO3(g) CaSO4(s)
G = -347 kJ/mol
the larger
g the G,, the stronger
g the acid

Comparing Basicities
Measure the free energy change of the
reaction of different bases with the same acid
Na2O(s) + H2O(l) 2NaOH(s)
G = -142
142 kJ/mol
CaO(s) + H2O(l) Ca(OH)2(s)
G = -59 kJ/mol
the larger
g the G,, the stronger
g the base

Acid/Base Chemistry in Geology

Silicate rocks can be classified according to
their oxide content
combination of basic metal oxides and acidic
silicon dioxide

>66% SiO2, acidic

52-66% SiO2, intermediate
45-52% SiO2, basic
<45% SiO2, ultrabasic

Pearson Hard-Soft
Hard Soft Acid/Base
(HSAB) Concept
Lewis acids/bases can be classified as either
hard or soft
a reaction will proceed in which the softer acids
would ppair with the softer bases
NaI + AgNO3 AgI + NaNO3 ???
g + NaNO3 NaI + AgNO
g 3 ???
AgI

Hard Acids
class a metal ions
consist of most of the metal ions
low electronegativities
high charge densities

H+

B3+ C4+ Fe3+

Soft Acids
class b metal ions
lower right portion of the metallic elements
lower charge densities
higher electronegativities

Au+ Ag
g+ Cu+

Borderline Acids
intermediate metal ions
intermediate charge densities
intermediate electronegativities

Cu+, charge
g densityy 51 C/mm3, soft
Cu2+, charge density 116 C/mm3, borderline
Fe3+, charge density >200 C/mm3, hard
Fe2+, charge density ~100 C/mm3, borderline

HSAB Acid Classification

Hard Bases
class a ligands
high charge densities
high electronegativities
fluorine and oxygen-bonded species

oxide
hydroxide
nitrate
phosphate
fluoride

Soft Bases
class b ligands
low charge densities
low electronegativities

carbon
sulfur
phosphorus
iodine

Borderline Bases
bromide
azide
ambidentate ligands
thiocyanate
thi
t
-NCS, borderline
-SCN,
SCN soft base

Applications of the HSAB

Concept
Prediction of chemical reactions
HgF2(g) + BeI2(g) BeF2(g) +
soft-hard
hard-soft
hard-hard
AgBr(s) +
softborderline

I-(aq)
soft

AgI(s)
soft-soft

HgI2(g)
soft-soft
Br-(aq)
borderline

Applications of the HSAB

Concept
Qualitative
Q li i analysis
l i
Group I metals
cat
cations
o s which
w c form
o insoluble
so ub e chlorides
c o des

Group II metals
cations which form soluble chlorides and very insoluble
sulfides

Group III metals

cations which form soluble chlorides and insoluble sulfides

Group
G
IV metals
t l
cations which form soluble chlorides and soluble sulfides

Groupp V metals
cations which form few, insoluble salts

Applications of the HSAB

Concept
Qualitative analysis
Group I

Group II

Group III

Group IV

Group V

AgCl

HgS

MnS

CaCO3

Na+

PbCl2

CdS

FeS

SrCO3

K+

Hg2Cl2

CuS

CoS

BaCO3

NH4+

SnS2

NiS

A 2S3
As

Z S
ZnS

Sb2S3

Al(OH)3

Bi2S3

Cr(OH)3

Mg2+

Applications of the HSAB

Concept
Qualitative analysis
Group I
[Ag(OH2)n]+(aq) + [Cl(H2O)m]-(aq) AgCl(s) + (n+m)H2O(l)
soft-hard

borderline-hard

Group II

softbord.

hard-hard

[[Cd(OH
( 2)n]2+((aq)
q) + [[S(H
( 2O))m]2-((aq)
q) CdS(s)
( ) + ((n+m)H
) 2O(l)
()
soft-hard

soft-hard

softsoft

hard-hard

HSAB in Geochemistry
Classification of the chemical elements
siderophiles
metals found in elemental form on the surface of the Earth

chalcophiles
sulfides

lithophiles
metals and nonmetals which occur as oxides, silicates, sulfates,
or carbonates

atmophiles
natural elements in the atmosphere

HSAB in Geochemistry
Lithophiles
hard acids
prefer oxygen-bound hard bases
Al2O3 (bauxite)
CaCO3 (limestone, chalk, marble)

HSAB in Geochemistry
Chalcophiles
borderline/soft acids
prefer soft bases such as sulfide
ZnS (sphalerite, wurtzite)
HgS (cinnabar)

Interpretation of the HSAB

Concept
Hard acid hard base combination
pairing of a low electronegativity cation with a
high electronegativity anion
ionic behavior

Soft acid soft base combination

pairing of a higher electronegative cation with a
lower electronegative anion
covalent behavior

Biological Aspects
Toxic elements
elements which are toxic at very low concentrations

beryllium
b
lli
arsenic
selenium
cadmium
indium
tellurium
mercury
thallium
lead

Biological Aspects
Cysteine, an amino acid
NH2
HS

H2
C

C
H

CO2H

zinc (borderline acid) normally binds to the thiol site

(soft base)
all the toxic metals (except beryllium) are softer acids
than zinc
the toxic nonmetals are soft bases which preferentially
bind to iron(II)
( ) and zinc