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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, Base proton
acceptor
Whats the physical meaning of
Brnsted-Lowry 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


(self-ionization)

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 EtOH2+ + EtO- KAB = 10-20

2 NH3 NH4+ + NH2- KAB = 10-29

2 H2SO4 H3SO4+ + HSO4-

2 OPCl3 OPCl4- + OPCl2+ (Cl


transfer)

(phosphoryl halides)
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.
OPCl3
Me4N+Cl- Me4N+ + Cl-
FeCl3 + OPCl3 FeCl4- + OPCl2+
OPCl2+ + Cl- 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 (double bond


resonance?)

Steric effect
N N N

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 R
R
R R
N > N > N

R R R

I (internal)-strain: oxygen basicity drops with


the decreasing ring size.

O O
Me Me O
N Me N N
> >

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, Stille


reaction (AX/RnSnX4-n), Suzuki reaction
(ArX/RB(OH)2), etc.

R R' RX
0
Pd

R R
Pd Pd
R' X

EX 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 ionic
bonding

III Measurements of Acidity and Basicity

Aqueous basicity & acidity


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.
Bond enthalpy
-HA(BH)
B(g) + H(g) BH(g)

-HIE(H) +e- -e- HIE(BH)

-PA
B(g) + H+(g) 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

H
O O O 2-

S S S
H O H O O
O O O
O O O

hydrogen sulfate ion sulfate ion

sulfuric acid water


b.p. 300 C 100 C

m.p. 10.371 C 0 C

d 1.83 g cm-3 (25 C) 1.00 g cm-3 (4 C)

dielectric constant 110 e0 (20 C) 81.7 e0 (18 C)

specific conductance 1.04x10-2 W-1cm-1 (25 4x10-8 W-1cm-1


C)
viscosity 1.01 g cm-1s-1 (20 C)
24.54 g cm-1s-1 (20 C)
ion product constant 1.008x10-14 (25 C)
2.7x10-4 (25 C)
3 ammonia

ammonia water
b.p. -33.38 C 100 C

m.p. -77.7 C 0 C

d 0.725 g cm-3 (-70 1.00 g cm-3 (4 C)


C)
dielectric 81.7 e0 (18 C)
constant 26.7 e0 (-60 C)
4x10-8 W-1cm-1
specific 1x10-11 W-1cm-1
1.01 g cm-1s-1 (20
conductance
0.254 g cm-1s-1 (-33 C)
viscosity C)
1.008x10-14 (25 C)
ion product 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