Acid-Base Theory

Contents
I Background
1 Arrehnius Theory
2 Brnsted-Lowry Theory
II Acid-Base Theories
1 Lewis Acid-Base Theory
2 Lux-Flood Theory
3 Hard-Soft Acid-Base Theory
III Measurements of Acidity & Basicity
IV Descriptive Chemistry of Acids & Bases

I Background
What is Arrhenius (Ostwald) Theory?
What is Arrhenius acid and Arrhenius
base?
Acid - proton donor, Base hydroxide
donor
What is the core concept of Arrhenius
Theory?
What is ionization theory?
Why is water special to Arrhenius Theory?
What is self-ionization?
Are there other substances that can have
self ionization?

 What is the Brnsted-Lowry Theory?

What is the difference between the
Arrhenius Theory and the Brnsted-Lowry
Theory?
Acid proton donor,
acceptor

Base proton

Whats the physical meaning of BrnstedLowry Theory?

1 competition for protons rather than
proton & hydroxide donors
2 A-B conjugate
3 insight of the atom transfer processes
4 useful in non-aqueous systems

Substances that have auto-dissociation (selfionization)

Aqueous system:

2 H2O

H3O+ + OH- Kw = 1.0x10-14 at 24.8 C, 1

atm

Neutral point: (1/2)pKw = 7.0

leveling effect 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

2 NH3
2 H2SO4

EtOH2+ + EtO- KAB = 10-20

NH4+ + NH2- KAB = 10-29

H3SO4+ + HSO4-

2 OPCl3
transfer)
(phosphoryl halides)

OPCl4- + OPCl2+ (Cl

Solvolysis

A process in which the solute can

combine
with
the
ionic
component of the solvent or have
the solvent ionized.

1 Hydrolysis combination of H+ in water

NaOAc + H2O

HOAc + NaOH

OPCl3 + 3 H2O

OP(OH)3 + 3 HCl

2 Non-aqueous solvolysis
OPCl3 + PCl5

OPCl2+ + PCl6-

Alcoholysis
OPCl3 + 3 ROH

OP(OR)3 + 3 HCl

Gutman elaborates the reaction of Me4N+Cl

and ferric chloride in phosphoryl chloride as
solvolysis via chloride-transfer pathway.

Me4N+Cl-

OPCl3

FeCl3 + OPCl3
OPCl2+ + Cl-

Me4N+ + ClFeCl4- + OPCl2+

OPCl3

As for the amphoteric substance, such as

Al(OH)3 is insoluble in water, but dissolves in
strong acid and strong base. Similarly, Al2(SO3)3
is insoluble in liquid sulfur dioxide, but dissolves
by adding SOCl2 or CsSO3.

Question: Does the reaction of thionyl chloride

with sulfite undergo solvolysis in SO2?
n A clever experiment of isotope labeling shows
no exchange between 32SOCl2 and 35SO2.
n No oxygen exchange observed for the reverse
reaction either.
n However, the halide exchange between SOCl2
and SOBr2 was observed.

Lewis Acid-Base Theory

In water:
B(OH)3+H2OH++B(OH)4, so B(OH)3 is an
Arrehnius acid.
NH3+H2ONH4++OH, so NH3 is an Arrehnius
base.
Boric acid being an acid is not only because it is
ionized to give proton, but for it decreases
[OH]
B(OH)3 + OH B(OH)4
Ammonia being a base is not only because it is
ionized to give proton, but for it decreases
[H+]
NH3 + H+ NH4+
Lewis Base electron pair donor,

Lewis Acid electron pair acceptor

For the reactions in which adducts are formed.
Me3N(g) + BF3(g) R3N-BF3(s) (m.p. > 200 C)

Inductive effect
Base strength: Me3N>NH3>NF3
Acid

strength:

Me3B<BH3<BF3

(how

to

determine it)
BF3<BCl3<BBr3
resonance?)

Steric effect

(double

bond

BMe3

BMe3

BMe3

DHrxn = 71

74

42 kJ/mol

B(mesityl)3 does not react even with MeO.

f-strain: front steric hindrance

b-strain: back steric hindrance

R

R
N
R

>

N
R

>

N
R

I (internal)-strain: oxygen basicity drops with

the decreasing ring size.

O
Me

O
Me

>

Me

>

Lewis A-B theory is important to coordination

chemistry (Chp 11, 12).
2 NH3 + Ag+ Ag(NH3)2+
Acid electron density deficiency (poorness)
Base electron density abundance (richness)

1 The chemistry correlates the reactivity due to

the

change

of

electron-density

with

thermodynamics.
2 Energetically, HOMO are often low-lying and
LUMO are often high lying.
3 The donor atom that has less s-character or
more p-charcater has stronger basicity.

Lux-Flood Theory Reactions of Atom

Transfer
Base oxide donor
Acid oxide acceptor
Oxides are important to the molten chemistry.
But oxides do not exist in the aqueous solutions.
O2 + H2O 2OH

CaO + SiO2 CaSiO3 (major content of slag)

(base) (acid)

SiO2 + H2O H2SiO3 (important to sol gel

process)
Sol:A colloid of tiny solid particles dispersed
throughout a liquid.
Solid Emulsion: A colloid of tiny droplets of
liquid or solid particles dispersed through
out a solid.
Gel: A soft solid emulsion but holds its shape.

Hard-Soft Acid-Base Theory

Irving-William series
For a given ligand, the stability of complexes
with M2+ follow the following order: Ba2+ < Sr2+ <
Ca2+ < Mg2+ < Mn2+ < Fe2+ < Co2+ < Ni2+ < Cu2+ >
Zn2+

Different Coordination Correlations

Class (a):
1 alkali metal ions
2 alkaline earth metal ions
3 light transition metal ions in high oxidation
states:
Ti4+, Cr3+, Fe3+, Co3+
4 Al3+, H+
Class (b): metal ions in low oxidation states
Cu+, Ag+, Hg+, Hg2+, Pd2+, Pt2+
Borderline:
Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Rh3+, Ir3+, Ru3+,Os2+,
Sn2+, Pb2+, carbonium ions, NO+

Donors having tendency to bind with Class (a)

metal ions

N >> P > As > Sb

O >> S > Se > Te

F > Cl > Br > I
Donors having tendency to bind with Class (b)
metal ions

N << P > As > Sb

O << S > Se ~ Te
F < Cl < Br < I
Ralph G. Pearson suggested the term hard for
the metal ions of Class (a) and their
corresponding bases; soft for the metal ions of
Class (b) and their corresponding bases.

Hard acids prefer to bind to hard bases; and

soft acids prefer to bind to soft bases.

MeHgF + HSO3 MeHgSO3 + HF Keq ~ 103

MeHgOH + HSO3 MeHgSO3 + H2O Keq >

107
Transmetallation used in the Synthesis of
Organometals
metathesis

MXn + n RLi MRn + n LiX

MXn + n RMgX MRn + n MgX2
Carbon or hydride nucleophiles: LiR, NaH,
Na(C5H5), NaBH4, KHB(SitBu)3, LiAlH4 (LAH),
AlR3, AlRn(OR)3-n, GaMe3, R2Mg, R2Zn, RZnX,
LiCuR(CN), NaNH2,
radical donor: RHgX, R4Sn
Electrophiles: proton sauce, RX, R3SiX, CO2,
ROTs, ROTf, Ph3C+BF4-,
Anions: X, BF4, BArf4, PF6, ClO4, NO3

Coupling

Reactions:

Heck

reaction

(AX/RnSnX4-n),

reaction,
Suzuki

Stille

reaction

(ArX/RB(OH)2), etc.

Pd

R'

Pd

RX

Pd

R'
EX

R
X

R'E

Physical meanings behind HSAB

1 ionization energy & electronegativity
2 polarizability
3 HOMO-LUMO gap: large for hard species,
small for soft species

4 soft-soft interactions imply covalency; and

hard-hard

interactions

are

for

bonding

III Measurements of Acidity and Basicity

Aqueous basicity & acidity

ionic

pH = log[H+]; pH + pOH = 14.0 at 24.8 C, 1

atm
Ka, DG = -RTlnK; DS = kln
Either the logarithm of an equilibrium constant
or of a measurement for the arrangement of the
states means a thermodynamic function.

Gase-Phase basicity & acidity

Proton affinity of a base B is defined as the
negative value of the enthalpy for the reaction:
B(g) + H+(g) BH+(g)
Using Born-Haber cycle, PA may be determined
by measuring ionization energies of H and BH
as well as bond enthalpy of BH.

Bondenthalpy
-HA(BH)
B(g) + H(g)
BH(g)
-e- HIE(BH)

-HIE(H) +eB(g) +

H+(g)

-PA

BH+(g)

proton affinity
Some determined PA (kJ/mol):
For N3, 3084; NH2, 2565; NH2, 1689 (charge
effect)
NH3, 872; NF3, 604; Me3N, 974 (inductive effect)
Difference between NH3 and NF3 is 268 kJ/mol;
between PH3 and PF3 is only 106, but DEN is
larger for PF. This is attributed to the
resonance effect, thus the charge in PF3H+ is
substantially delocalized.

Gase-phase acidity for a conjugate acid of B will

be the enthalpy of dissociation of BH+.
Gase-phase acidity for the Lewis acids of metal
cations parallels the electron affinities.
Acidity of Oxides
An

acidity

scale

for

the

oxides

is

the

measurement of the reaction enthalpy, and

make aBaA = (DHrxn)1/2.
For instance
CaO + SiO2 CaSiO3 DH = 86 kJ/mol aBaA =
9.5
The a parameter is calibrated with awater =
0.0. Therefore, the negative values for the a
parameter indicates high basicity, e.g. 15.2 for
Cs2O; and the positive values for the nonmetal
oxides, e.g. 11.5 for Cl2O7, an anhydride of
orthochloric acid.

Drago-Wayland Equation for the HSAB

DH = EAEB + CACB for the reaction: A + B
AB
wherein E stands for electroststic and C for
covalent.

IV Descriptive Chemistry of Acids & Bases

1 general guidelines
Basicity of metal oxides increases while
going down the periodic table. BeO is
amphoteric.

With increasing covalency,

oxides become more acidic or less basic.

The acidity of nonmetal oxides increases
when the values of (aB-aA) increases.
The acidity of the hydrated metal ions of
high positive charge density increases when

the value of z2/r increases. Hydration and

hydrolysis are more feasible with the same
trend. The metal ions of high charge to size
density are more acidic, e.g. Fe3+ pKa 2.19;
Fe2+ pKa 10.1.
The EN of the central atom is directly
influence the acidity of oxyacids. Acidity:
HClO4 ~ HNO3 > H2SO4 >> H3PO4 > H2CO3
>> H3BO3
The more oxygens around the central atom,
the larger acidity is.
Acidity: HClO4 > HClO3 > HClO2 > HClO

Change

the

inductive

effect

of

the

substituents of amines, change the basicity.

NH2OH < NH2NH2 < NH3 < MeNH2; NF3 is
not a base;

2 sulfuric acid

O
H

S
O

S
O

2-

O
O
O

S
O

O
O

hydrogen sulfate ion sulfate ion

sulfuric acid

water

b.p.

300 C

100 C

m.p.

10.371 C

0 C

1.83 g cm-3 (25 C)

1.00 g cm-3 (4 C)

110 e0 (20 C)

81.7 e0 (18 C)

d
dielectric constant

specific conductance 1.04x10-2 W-1cm-1 (25 C)

viscosity
ion product constant

4x10-8 W-1cm-1

24.54 g cm-1s-1 (20 C)

1.01 g cm-1s-1 (20 C)

2.7x10-4 (25 C)

1.008x10-14 (25 C)

3 ammonia
b.p.

ammonia

water

-33.38 C

100 C

m.p.

-77.7 C

0 C

0.725 g cm-3 (-70 C)

1.00 g cm-3 (4 C)

dielectric constant

26.7 e0 (-60 C)

81.7 e0 (18 C)

specific

1x10-11 W-1cm-1

4x10-8 W-1cm-1

conductance

0.254 g cm-1s-1 (-33 1.01 g cm-1s-1 (20 C)

viscosity
ion

C)
product

1.008x10-14 (25 C)

5.1x10-27

constant

Ammonia is a poor solvent for highly charged

ions, including carbonates, sulfates, phosphates,
etc.,

but

nonpolar

molecules,

or

large

polarizable ions such as iodide, thiocyanate are

soluble in ammonia.
Sovolysis takes place in the presence of chlorine
or phosphoryl chloride. The former reaction
may also be considered as disproportionation.
4 oxoacids

Oxoacids are customarily written as HmXO(m+n).

The functional formula is XOn(OH)m. Hydrated
oxometals such as uranyl UO22+, vanadyl VO2+.
Acidity:
HClO4 > HClO3 > HClO2 > HClO > HBrO >
HIO
HClO4 > H2SO4 > H3PO4 or OP(OH)3 > H2CO3 >
H3BO3
CrO3 > Cr2O3 > CrO (basic)
CrO3 + H2O H2CrO4 (chromic acid)
5 binary oxides
Oxides of the metals of Groups 1 and 2 are
generally

basic,

except

BeO.

Al2O3

is

amphoteric. Nonmetal oxides are generally

acidic.
Acidity: Cl2O7 > SO3 > P4O10 > SiO2
5 solid acids:

Clays and Zeolites are porous solids. The

clays have layer structures, and the zeolites
are aluminosilicates with channels. They have
replaceable cations and may be exchanged
with H+, thereby forming solid acids.
The open channels of zeolites vary in size, thus
may serve as catalysts for specific selectivity.
For instance, ZSM-5 (Na3(AlSi31O64)316H2O)
is used to produce gasoline from methanol.
6 superacids:
The protonated solvent molecules of the already
strong acids.
Examples: SbF5 produces extremely strong
proton donor in HF or HSO3F.
SbF5 + 2 HF H2F+ + SbF6
SbF5 + 2 HSO3F H2SO3F+ +
FSO3SbF5