6.1.

1 History of Acid-Base Models

▪ Acid-Base definitions for general use
1) Arrhenius: hydrogen and hydroxide ion formation
2) Brønsted-Lowry: hydrogen ion donors and acceptors
3) Lewis: electron-pair acceptors and donors

▪ Others in narrow range of situation

- Lux-Flood: oxide ion (O2-) as the unit transformer b/w acids and bases
- Usanovich: any reactions leading to a salt (oxidation-reduction rxn)
electrophilic reagent – acids
- Ingold & Robinson:
nucleophilic reagent – bases

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 6.1.1 History

TABLE 6.1 Acid-Base Definition History

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▪ Arrhenius acid: form hydrogen ions in aqueous solution (hydronium or oxonium, H3O +)
▪ Arrhenius base: form hydroxide ions in aqueous solution

acid + base → salt + water

▪ example: H+ + Cl- + Na+ + OH- → Na+ + Cl- + H2O

ions accompanying the hydrogen and hydroxide ions form a salt

▪ works well in aqueous solutions, but inadequate for nonaqueous solutions (gas-phase,
solid-state rxns)

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 ▪ acid: a species w/ a tendency to lose a hydrogen ion base: a
species w/ a tendency to gain a hydrogen ion

include the gases HCl and NH3 & others

▪ conjugate acids & bases: differing in the preserve or absence of H+

H 3O + + NO- 2 → H2O +
HNO
acid1 2 base2 base1
acid2

conjugated acid-base pairs Acid Base

H 3O + H 2O
HNO 2 NO2 -

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 ▪ H++ Cl- + Na+ + OH- → Na+
+ Cl- + H2O
acid conjugated base of H3 O +
base
(H 3 O +) conjugated acid of OH-

▪ in nonaqueous solvent, NH3 (aq)

NH 4+ + Cl- + Na+ + NH2- → Na+ + Cl-

+ 2NH 3
conjugated
acid base
base
conjugated acid
▪ The direction of rxn: favors the formation of weaker acids or bases than reagents

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 Comparing Acidity
▪ Using Hess’s law (to get the enthalpy change of some rxn that do not go to completion)
ex) enthalpy & entrophy of ionization of a weak acid, HA
1) enthalpy of rxn of HA w/ NaOH
2) enthalpy of a strong acid (HCl) w/ NaOH
3) equilibrium const. for dissociation of the acid

enthalpy change
- -
1. HA + OH → A ∆H1 º
+ H 2 O 2. ∆H2 º
+ -
H
3.3 O +HA + OH
H2 O →H O+3 2H
+ A2-O ∆H3º
Ka

▪ from the usual thermodynamic relationship…

4. ∆H3 º = ∆H1 º - ∆H2 º

[because rxn 3 = rxn 1 -
rxn 2] 5. ∆S 3 º = ∆S 1 º -
∆S 2 º
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6. ∆G 3 º = -RT lnKa =
Inc.

∆H3 º - T∆S 3 º
TABLE 6.4 Thermodynamics of Acetic Acid Ionization

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▪ gas-phase proton affinity indicates… how difficult to remove H+ ion ?

BH+ (g) → B(g) + H + (g), ∆G = Gas-phase Basicity

∆H = proton affinity B: strong base in

gas phase

BH+ : weak acid

▪ indirect measurement: there will be the voltage change of the ionizing electron beam
in mixture of B & H 2 when BH + appears

: large uncertainties - 1) due to excited states of molecules

2) no BH + fragment produced
3) solvent or environmental conditions

: but, useful in sorting out other factors influencing acid-base behavior

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▪ in aqueous solution, basicity: Me 2NH > MeNH 2 > Me 3N > NH 3
(smaller pK b stronger base)

: Et2NH > EtNH2 = Et3N > NH 3

weaker base than expected based on the inductive effect!!

(∵ reduced solvation of their protonated cations)

▪ solvation E order of,,,

Rn H4-nN+(g) + H 2O → Rn H4-nN+ (aq)

RNH3+ > R2NH 2+ > R 3NH +

solvation is depend on the # H-atom available for H-bonding to water… fewer H for

H-bonding → less basic

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▪ binary hydrogen compounds: H + one other element
ex) HCl, HBr, HI, NH3 , CH 4
(strong) (weak) (none)

Difficult to remove H+
Easier to remove H+

Fig. 6.4

Acidity of binary H compds.

enthalpy of dissociation in gas phase
AH(g) → A- (g) + H + (g)

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▪ Fig. 6.5

- within a column: going down the series → acidity ↑

H 2 Se > H2S > H2O
(strongest acid)
largest, heaviest member w/ an low electronegativity
∵ conjugated base (SeH- , SH - , OH- )
lower charge density
→ smaller attraction to H+
→ weaker conjugate base
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▪ Fig. 6.5
N
O
F

- within a period: to the right → electronegativity ↑ → acidity ↑

explanation: dividing -1 charge of conjugate bases among the lone pairs
conjugate base: 1) NH2 :- -1 over 2 lone pair (1/2 each)

2) OH- : -1 over 3 lone pair (1/3 each)

3) F- : -1 over 4 lone pair (1/4 each)
∴ strongest attraction for H +
weakest acid

∴ NH3 <
H2O < HF © 2014 Pearson Education,
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▪ the acid strength of the oxyacids of chlorine in aqueous solution,,,
Nonhydrated O draw e- from a central atom
HClO4 > HClO3 > HClO2 > HOCl
positive charge on the central ↑
(strongest)(weakest)
the central draw e- toward itself

weaker O-H bond

∴ easier to lose the H+ (= stronger acid)

# O ↑ → the acid strength of the molecule ↑

▪ semiquantitative prediction of the strength of acids
pKa ≈ 9-7n (n = # nonhydrated oxygen atoms/ molecules)
pKa ≈ 8-5n

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Not very accurate, but provides approximate value!!

▪ if more than one ionized H,,, → pKa increases by 5 units w/ H
removal

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▪ from the view point of the conjugated base

negative charge is spread over all the nonhydrated O

the largest # O to share the negative charge,,, the more

stable

the weaker the conjugated base

the stronger the hydrated acid

∴ the larger # nonhydrated O,,

the stronger the acid!!

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the largest # O to
share the negative
charge
the more stable
the anion

The weaker the

conjugate base

The stronger the

hydrated acid
 6.3.9 Brønsted-Lowry Acidity of Aqueous
Cations
▪ positive metal ions exhibit acidic behavior in solution

ex) [Fe(H 2 O)6 ] 3+ + [Fe(H 2 O)5 (OH)]2++ H 3 O+

H 2 O [Fe(H2 O)5 (OH)]2+ [Fe(H 2 O)4 (OH) 2 ] + +
+ H2O H 3 O+

▪ in more basic solutions, 1) hydroxide or oxide bridge form

2) high + charge promotes more H + dissociation

3) hydrated metal hydroxide precipitates

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▪ in general, metal ions w/ larger charge & smaller radii

stronger acids
4+ or higher: monoatomic ion
exist as oxygenated ion

▪ - alkali metal: no acidity

- alkaline-earth metal: slight acidity
- 2+ TM ions: weakly acidic
- 3+ TM ions: moderately acidic TABLE 6.8 Hydrated Metal Ion Brønsted-Lowry Acidity (298 K)

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▪ at extremely high charge, oxygenated ions exist rather than free metals ions

Mn7+ → MnO 4- (permanganate)

Cr6+ → CrO 42- (chromate)
U5+ → UO 2+ (uranyl)
V 5+ → VO2+ (dioxovanadium)
V 4+ → VO2+ (vanadyl)

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▪ base: electron-pair donor acid: electro-pair acceptor

encompasses the Brønsted-Lowry and solvent-system definitions

- also include reactions such as,,,

1) Ag+ + 2:NH3 → [H3N:Ag:NH3]+

cation anion product →

adduct

2) BF3 + :NH3 →
BF3·NH3

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 6.4 Lewis Acid-Base Concept and Frontier Orbitals

▪ Fig. 6.6 Donor-Acceptor Bonding in BF 3·NH3

▪ empty lone pair in the HOMO

LUMO of interact w/ of NH3 molecule
the BF3

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▪ Fig. 6.7 Simplified Energy Level Diagram for the
Donor-Acceptor Bonding in BF 3 ·NH 3

▪ Fig. 6.8 Boron Trifluoride-Ether Adduct Formation from a Lewis

Perspective

m.p. – 99.9 ºC m.p. 34.5 ºC m.p. 125 ºC, 126 ºC

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▪ Frontier molecular orbitals: occupied/unoccupied frontier

▪ Example) Fig. 5.30: NH3 + H+ → NH4+

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 6.4.1 Frontier Orbitals and Acid-Base Reactions

Fig. 6.9 NH + H+ →
▪ NH34+

molecular energy level

-4 bonding orbitals (a 1 , t 2 )
-4 antibonding orbitals (a 1 , t 2 )
-change in symmetry: C 3v → Td
(NH 3 )(NH 4 ) +

-net result: lowering E

(∵nonbonding a1 →
bonding t2 )
-In acid-base reactions, a HOMO-LUMO
lone-pair
empty combination forms new HOMO & LUMO
orbitals of the product.

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▪ A single species can act as an oxidizing agent, an acid, a base, or a reducing agent (depending on
the other reactant)

▪ Example 6.1) HOMO-LUMO interaction

- water: reactant A
1) Water as Oxidizing Agent: reaction w/ B Energy of orbitals: EA << EB

no adduct can form transfer of electron B → A

2H2 O + Ca → Ca2+ + 2OH - + H2

(as oxidant)

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▪ Example 6.1)
2) Solvation of an Anion: reaction w/ C Energy of orbitals:
EA ≈ Ec

bonding orbital will have lower E than the reactant HOMO’s

net decrease in E
- an adduct is formed

nH 2 O + Cl- → [Cl(H 2O) n]-

solvated chloride ion

(as acid)
(acceptor using LUMO)

▪ Reformulated Lewis acids and bases in terms of frontier orbitals

A base has an electron pair in a HOMO of suitable symmetry to interact w/ the LUMO of the acid.
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Solvation of
cation
6 H2O(l) + Mg2+ → [Mg(H2O)6]2+(aq) (water as Lewis base)

Water as reducing
agent
2 H2O(l) + 2 F 2(g) → 4 F-(aq) + 4 H+(aq) + O 2(g) (water as reductant)

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▪ effect of adduct formation: I2 + solvent → change in spectra &
visible light
due to the E level change
Fig. 6.10
1) nondonor solvent (hexane): same color
2) π-e- solvent (benzene): more reddish
3) good donor (ether, alcohol, amine): brown

solubility of I 2 ↑
in gas phase
-absorb Y, G, B (500 transition from π*g → σ*u
nm)
-leave red, violet
higher E, blue shift
(more yellow, green pass
thru)
lone-pair

net single bond

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 6.4.2 Spectroscopic Support for Frontier Orbital Interactions

purple/violet
water – not very good → slightly soluble, yellow
▪ donor:
brown I - - very good donor → very soluble, brown

purple/violet

if interaction ↑ → LUMO (adduct) w/ a higher E

donor – acceptor transition (π* g → σ* u)

red violet
↑

yellow brown

brown
Fig. 6.11

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6.4.2 Spectroscopic Support for Frontier Orbital Interactions

▪ charge transfer (CT): new band @ ~230 to 400 nm

: due to the transition σ → σ* b/w two new orbitals
: E is less predictable
hv
: I 2·Donor [I
CT
] - ·[Donor]
2
+

transfer e - permanently → oxidation-reduction reaction

donor: oxidized acceptor:

reduced

[Fe(H 2 O)6 ] 3+ + X- → [Fe(H 2 O)5 X]2+

+ H2O
(acid) (base)

Lewis basicity must be confirmed via correlating spectroscopic

data (for example, how much did the chemical shift or visible
absorption change?) to KBA or ∆Ho values for the complexation
reactions.
Fig. 6.11 © 2014 Pearson Education,
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 6.4.6 Inductive Effects on Lewis Acidity and Basicity

▪ Substitution of more electronegative atom for H on ammonia or phosphine

becomes weaker base

(∵ F, Cl draw e- density toward them)

less negative charge on N or P

▪ Example 1)

(weaker base)
▪ Example 2) amine: alkyl group (e- contributing group) substitution for H

NMe3 > NHMe2 > NH 2 Me > NH3

(stronger base)
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▪ exception) boron halides

since significant π-bonding on BF3 and BCl3

increase e- density on B

∴ BF3 << BCl 3 < BBr3 < BI3

would expect to be the strongest acid, but, in fact, this is the weakest acid !!
due to the e - density caused by π-bonding !!

as the halogen size increases → B-X bond lengthens → π-interaction decreases!!

Intra-molecular acid-base
interaction to become saturated
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▪ when bulky group are forced together by adduct formation,, mutual repulsion →
less favorable reaction

1) front (F) strain: bulky acid or base group interfere directly w/ each other

2) back (B) strain: bulky acid or base group interfere when VSEPR effects force them
to bend away the other molecule
3) internal (I) strain: electronic difference within similar molecules

▪ Example 6.2) 1) base strength of substituted pyridines

2,6-dimethylpyridine > 2-methylpyridine > 2-t-
butylpyridine > pyridine

t- butyl group: counter balancing

-
∵ e donation from alkyl group inductive & steric effect
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▪ Example 6.2)
2) reaction w/ larger acid, BF 3 or BMe3

pyridine > 2-methylpyridine > 2,6-dimethylpyridine > 2-t-

butyl pyridine

∵ interference b/w F - or CH3 - on boron and ortho- groups on pyridine

substituted pyridine is less favorable (F strain)

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 6.4.7 Steric Effects on Lewis Acidity and Basicity

TABLE 6.12 Ranking of the Enthalpies of Formation for Adduct Formation for Amines and Lewis Acids

▪ basic strength (according to proton affinity): Me3N > Me 2NH > MeNH 2 > NH 3
∵ electron donation by methyl group → e- density ↑

▪ when react w/ larger acids: 1) w/ BF 3 : Me2NH > MeNH 2 > Me 3N > NH 3

2) w/ B(t-Bu)3 : MeNH2 > NH 3 > Me 2NH > Me 3N
(opposite to the proton affinity order)

∵ Me-group crowding at the back of N (B strain) © 2014 Pearson Education,

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 TABLE 6.12 Ranking of the Enthalpies of Formation for Adduct Formation for Amines and Lewis Acids

▪ quinuclidine vs. triethylamine: proton affinities are similar

967 vs. 958 KJ/mol

: mixed w/ Me3 B
quinuclidine reaction is twice favorable!! (-84 vs. -42 KJ/mol)

∵ less interference on quinuclidine w/ pinned back chains !!

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▪ MO for the symmetric FHF -
HF + F- → FHF -

1) lowest orbital: bonding, no node b/w atoms

2) Middle orbital (HOMO): (essentially nonbonding),

Fig.6.12 nodes through each nuclei

3) Highest orbital (LUMO): antibonding, nodes b/w

each pair of atoms

2p z

2p x , 2py

(∵ no matching
orbitals on the H
atom)

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▪ unsymmetrical hydrogen bonding: B + HA
BHA

Fig.6.12 - similar pattern

- two electron pairs in the lower orbitals have a
lower total E than the total for the e- s in the
two reactants
total E of product is lower than the sum of
the E of the reactants

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▪ For the general case of B + HA → three possibilities
a) poor match of E: E (occupied reactants) < E (hydrogen-bonded
products)
b) good match of E: E (occupied reactants) > E (hydrogen-bonded
products)

no H-bonding
no new product

H-bonded product form

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▪ For the general case of B + HA → three
possibilities

c) very poor match of E : E +

BH + A
-
<E B + HA
→ ∴ H+ ion
transfer!!

* No useful adduct
orbital

can be formed !!

B + HA

H + ion transfer

BH + + A-

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▪ when A is a highly electronegative elements : F, O, N
highest occupied orbital of A has the lower E
than the H 1s orbital

H-A bond → weak

most e - density near A

lowering overall E of HA bonding orbital & improving overlap

w/ B orbital

as reactant HA → H+ ···A - → hydrogen bonding is more likely

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▪ extended pi system can hold molecules or portions of molecules together
1) large scale: protein folding, biochemical process
2) small scale: molecular electronic devices

▪ “ball and socket” str.: π – π interactions b/w1) concave receptors &

2) fullerene (C60)
1) concave receptors (molecular tweezers or clips) porphyrin
rings, corannulene, other pi systems
ex) Fig. 6.13 – “double-concave hydrocarbon buckycatcher”
1:1 of C60H24 + C 60 in toluene

- w/ two concave corannulene “hands”

wrapping around C60

- d(C-C) = 350 pm, π-π interaction

- e - transfer from receptor to C 60 on absorption

of light → photovoltaic device Fig. 6.13
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▪ Three experimental observations related to the hard and soft acids & bases

1. Relative solubilities of halides

1) silver halides in water: as going down the column of halogens → ↓
AgF(s) + H2O → Ag+(aq) + F- (aq) Ksp = 205 (most)
AgCl(s) + H2O
→ Ag+(aq) + Cl- (aq) Ksp = 1.8 X 10-10
AgBr(s) + H2O
→ Ag+(aq) + Br - (aq) Ksp = 5.2 X 10-13
AgI(s) + H2O → Ag+(aq) + I - (aq) Ksp = 8.3 X 10-17 (least)

- Hg- halide → similar to Ag-halide

* On the other hand, for the light metals, such as Li, Mg, Al,,,
- Li-halide
Mg-halide → LiF, MgF2, AlF3 : fluorine compounds are less soluble!!
Al-halide

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▪ Three experimental observations related to the hard and soft acids & bases

2. Coordination of thiocyanate to metals (SCN- )

ligand: forms bonds to metal ions

to large, polarizable metal ion (Hg2+): thru sulfur ([Hg(SCN)4]2-) to

smaller, less polarizable metal ion (Zn2+): thru N ([Zn(NCS)4]2-)

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 6.6 Hard and Soft Acids and
Bases

▪ Three experimental observations related to the hard and soft acids & bases

3. Equilibrium constants of exchange reactions

example) [CH3Hg(H 2O)]+ + HCl → CH3HgCl + H 3O+ K = 1.8 X 1012

[CH3Hg(H 2O)]+ + HF → CH3HgF + H 3O+ K = 4.5 X 10-2

Small charge
▪ Hard and soft acids and bases (HSABs): soft ?? : polarizable acids & bases to radius ratio
hard ?? : nonpolarizable acids & bases
Large charge
to radius ratio
hard - hard and soft – soft combinations are stronger!!!

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▪ Case 1. Relative solubilities:
metal cation ?? : Lewis acid → Ag+: soft
halide anion ?? : Lewis base → Iodine ion: soft (more polarizable)
: stronger interaction w/ Ag +
: more covalent bond in AgI

AgI → AgBr → AgCl, AgF

yellow slightly yellow white
(strongest interaction) (weakest interaction)

- Li-halide: solubility

LiBr > LiCl > LiI > LiF

hard-soft interaction hard-hard interaction

SOFTER!!! (solubility: F - > Cl- > Br- > I - )

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▪ Fig. 6.14 Location of class (b) metals in the periodic table

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▪ Case 2. Coordination of thiocyanate to metals: SCN -
Hg2+: larger, more polarizable (soft)
Zn 2+: smaller, harder

Other examples

[Hg(SCN)4]2- = Pd 2+, Pt2+

[Zn(NCS)4]2- = Ni2+, Cu2+

intermediate TM-ion: Co3+ → either end

[Co(NH 3)5SCN]2+ &
[Co(NH 3)5NCS]2+

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▪ Case 3. Equilibrium Constants of Exchange Reactions ex) [CH3Hg(H 2O)]+ + BH+ [CH3HgB]+ + H 3O+

exchange of water and base B = competition b/w H2O & B to attachment on Hg

TABLE 6.13 Equilibrium Constants for Reactions of Mercury Complexes

* 1 - 4: as the halide larger, softer (F - → I - ) → K ↑

* 6, 7 : relatively soft S → K ↑
* 1, 5 : harder F, O → K ↓
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 class (a) metal ions – hard
▪ by Pearson:
acids class (b) metal ions – soft
acids
base → hard or soft in terms of polarizability

▪ polarizability?
- the degree to which a molecule or ion is easily distorted
by interaction w/ other molecules or ions

▪ hard acids and bases : small, compact, nonpolarizable

: acids - large positive charge (3+ or larger)
- d e - are unavailable for π-bonding
(alkaline earth ions, Al 3+)

- exceptions: Cr3+, Mn2+, Fe 3+, Co 3+

▪ soft acids : d e - or orbitals are available for π-bonding (neutral, 1+, 2+)
: larger, more e- , more polarizable
: 2nd , 3rd row TM w/ 45 < e -
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TABLE 6.14 Hard and Soft
Bases

2- 2- (in the same Group) * S2- vs. Cl - (w/ the same # e - )

* S vs. O
Softer
Softer ∵ smaller
∵ more e-
larger volume more nuclear charge larger

polarizability size

more polarizability © 2014 Pearson Education,

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 6.6.1 Theory of Hard and Soft Acids and
Bases
TABLE 6.15 Hard and Soft Acids

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▪ By Drago & Wayland (about reactivity)

- using electrostatic (E) & covalent (C) factors

- ∆H = EA EB + CA CB
tendency to form covalent
bonds enthalpy of rxn A + B → AB in gas phase

capacity for electrostatic (ionic) interactions

- reference values: acid → Iodine (I2 ), CA = 1.00, EA = 1.00

base → N,N-dimethylacetamide, EB = 1.32

→ diethyl sulfide, CB = 7.40

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▪ By Drago & Wayland
TABLE 6.17 CA , E A , CB , and E B Values (kcal/mol) - Combination of these values for acid-base pairs
enthalpy of reaction

- Most other acids have lower CA values than

I2
higher EA value than

∵ I 2: no permanent dipole → little electrostatic

attraction for base

low EA

: strong tendency to bond w/ other bases

higher C A

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 6.6.2 HSAB Quantitative Measures

▪ By Drago & Wayland

- example)
I2 + C6 H 6 → I 2·C 6H6

(acid) (base)

∆H = -(EA EB + CA CB )
= -([1.00 X 0.68] + [1.00 X 0.525])
= -1.206 kcal/mol → weaker
adduct

*experimental value, ∆H = -1.3

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- both E and C increases at the same time

unlike other descriptions as electrostatic (ionic) bonding ↑

covalent bonding ↓

explains acid-base adduct formation better than the HSAB

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 6.6.2 HSAB Quantitative Measures

▪ Example 6.5) Calculate the enthalpy of adduct formation predicted by Drago’s E, C equation
for the reactions of I2 w/ diethyl ether and diethyl sulfide.

Rxn w/ Diethyl sulfide is dominant!!

∵ Soft S reacts more strongly w/ soft I2 !!

▪ Both Drago’s E and C parameters and Pearson’s HSAB are useful, but neither covers every case.

if E and C numbers are available → quantitative comparison !! if not → qualitative

HSAB approach for a rough guide !!

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