Acid and Bases

Acid and Bases

Acid and Bases
 Acid--Base Concepts
Acid
I. Unifying Concepts
A. The Acid-Base Concept
1) There
Th are many
m n acid-base
id b s ddefinitions,
finiti ns eachh att times
tim s
useful
2) Acid-Base concepts are not facts or even theories,
but are useful generalizations for classification, and
organization
3) Acid
Acid-Base
Base concepts are powerful ways to explain
data and predict trends
B. Arrhenius Concept
1) An
A acidid f
forms H+ in
i water;
t abbase fforms OH- ini
water
2) Applicable to aqueous solutions only
3) HCl + NaOH  H+ + OH- + Na+ + Cl-
C. Bronsted-Lowery Concept
1) Acid is a proton donor; Base is a proton
acceptor
2) Conjugate acid/base pairs differ only by a
proton
3) Reactions proceed to produce the weakest acid
and base
4) H3O+ + NO2-  H2O + HNO2
5) Includes non-aqueous systems
NH4+ + NH2-  2 NH3
Brønsted-
Brønsted -Lowry Acids and Bases
+
The H Ion in Water
Proton Transfer Reactions
• Focus on the H+(aq).
• Brønsted-Lowry: acid donates H+ and base accepts H+.
• Brønsted-Lowry base does not need to contain OH-.
• C id HCl(aq) + H2O(l) → H3O+(aq) + Cl-(aq):
Consider )
– HCl donates a proton to water. Therefore, HCl is
an acid.
acid
– H2O accepts a proton from HCl. Therefore, H2O is
a base.
• Water can behave as either an acid or a base.
• Amphoteric substances can behave as acids and
bases.
bases
Proton Transfer Reactions
 Brønsted-
Brønsted -Lowry Acids and Bases
Conjugate Acid-
Acid-Base Pairs
• Whatever is left of the acid after the proton is
donated is called its conjugate base.
• Similarly, whatever remains of the base after it
accepts a proton is called a conjugate acid.
acid
• Consider
– After HA ((acid)) loses its p
proton it is converted into
A- (base). Therefore HA and A- are conjugate acid-
base pairs.
– After
Aft H2O (base)
(b s ) gains
i s a proton
t it is converted
t d iinto
t
H3O+ (acid). Therefore, H2O and H3O+ are
j g
conjugate acid-base ppairs.
• Conjugate acid-base pairs differ by only one proton.
 Conjugate Acids and Bases:

Reactions between acids and bases always

yield their conjugate bases and acids.
acids
D. Solvent System Concept

1) Useful for aprotic, non-aqueous systems

2)) Applies
pp to anyy solvent that can dissociate to
cation (acid) and anion (base)
3) For water: 2 H2O  H3O+ + OH-
a)) Any
A solute
l iincreasing
i [H3O+] iis an acid
id
HCl + H2O  H3O+ + Cl-
b) Any solute increasing [OH-] is a base
NH3 + H2O  NH4+ + OH-
4) Aprotic, non
non-aqueous
aqueous example
example: 2 BrF3 
BrF2+ + BrF4-
a) Acid: SbF5 + BrF3  BrF2+ + SbF6-
b) Base: F- + BrF3  BrF4-
5) The acid-base reaction:
a) Arrhenius: acid + base = salt + water
b) Bronsted: acid1 + base2 = base1 + acid2

6) pKion = -log[acid][base]
a) pKW = -log([H3O+][OH-]) = -log[10-7][10-7] = 14
b) pKKH2SO4 = -log([H
l ([H3SO O4+][HSO
][H O4-]) = 3.4
34
c) The smaller the number, the more dissociation has
occurred
E. Lewis Conceptp
1) Acid = e- pair acceptor; Base = e- pair donor
2) Includes metal ions and non-aqueous systems;
encompasses other
th concepts t
3) Metal ion Example: Ag+ + 2 :NH3  [Ag(NH3)2]+
a) Acid-Base
Acid Base product is called an adduct
b) If the acid is a metal ion, it is also called a
coordination compound
p or a coordination complex
p
or a complex ion
4) A non-metal example: BF3 + NH3  H3N:BF3
( BF3 • NH3)
(or
II. Acid-Base Strength

A. Thermodynamic Measurement
1) We can easily measure pH, but that doesn’t really
t ll us about
tell b t acid
id strength
t th
Ka [H 3O + ][A − ]
2) HA + H2O H3O+ + A- Ka =
[HA]

3) DGo = -RTlnKa = DH - TDS

a) G = free energy
b) H = enthalpy
c) S = entropy
− ΔH ΔS
4) Solving for Ka: lnK a = +
RT R
Acid and Base Strength

• Strong acids are

completely dissociated
in water.
A. Their conjugate bases
are quite weak.
• Weak acids only
dissociate partially in
water.
A. Their conjugate bases
are weak bases.
• Substances with
negligible acidity do
not dissociate in
water.
water
- Their conjugate bases
are exceedingly strong.
Factors Affecting Acid Strength

Consider H-X. For this substance to be an acid we

need:
• HH-XX bond to be polar w
with
th H δ+ and X δ- ((if
f X iss a
metal then the bond polarity is H δ- , X δ+ and
the substance is a base)
• The H-X bond must be weak enough to be
broken
• The conjugate base, X-, must be stable
The Lewis Concept

Acid Strength is a measure for the tendency of

an acid to accept an electron pair to form
chemical bond : An acid is called to be stronger as
the tendency increases.

Base Strength is a measure for the tendency of

a base to donate an electron pair to form
chemical bond : A base is called to be stronger as
the tendency increases.
The Strength of Bases

Donor of Electron Pair

The ability of a base to furnish a pair of
electrons to an acceptor depends on :

The more negatively

charged
h d th
the donor
d n atom,
t m
δ- δ+ the more effective the
chemical bond formed

THE NEGATIVE
PARTIAL CHARGE OF
THE DONOR ATOM
 Involvement of the Donor
in Bond Multiplicity

δ- δ+ Capacity of the Groups

Attached to the Donor

Polarizability of the Donor

THE NEGATIVE Concentration of the Donor

PARTIAL CHARGE OF Electron Pair
THE DONOR ATOM
 The Strength of Acids

Empty
O bit l
Orbital Acceptor of Electron Pair
The ability of an acid to gain a pair of
electrons from a donor depends on :

The more ppositively

y charged
g
the acceptor atom, the more
effective the chemical bond
f
formedd
THE POSITIF PARTIAL
CHARGE OF THE ACCEPTOR
ATOM
 The more empty orbitals
available in the acceptor
atom the more effective
atom,
the chemical bond formed

THE EMPTY ORBITALS

AVAILABLE IN THE
ACCEPTOR ATOM
B. Binary Hydrogen Compounds
1) Acidity increases down a column of the periodic table
a) H2Se > H2S > H2O
b) HI > HBr > HCl > HF
c) Conjugate bases of larger ions have lower charge
density, thus a smaller attraction for H+

2) Acidity increases from left to right of the periodic table

a) NH3 < H2O < HF
b) The more electronegative the conjugate base is, the
easier
si is it for
f H+ tot diss
dissociate
i t
• HF is a weak acid because the bond energy is high.
• The electronegativity difference between C and H is
so small that the C-H bond is non-polar and CH4 is
neither an acid nor a base.
C. Inductive Effects (electron pulling/pushing through
sigma bonds)
1) Electronegative substituents increase acidity and
decrease basicity
B
Basicity: :PF
PF3 < :PH
PH3

2) Electron Donating substituents decrease acidity and

i
increase
s bbasicity
si it
Basicity: NMe3 > NHMe2 > NH2Me > NH3

3) O
Oxyacids:
id ththe more unprotonated
t t d Oxygens,
O th
the
stronger the acid
a) Acidity: HOClO3 > HOClO2 > HOClO > HOCl
b) The electronegative O’s pull e- away from the
H—O bond
c) The electronegative O’s
O s stabilize the conjugate
base
Oxyacids
• Oxyacids contain O-H bonds.
• All oxyacids have the general structure Y-O-H.
Y O H
• The strength of the acid depends on Y and the
atoms attached to Y. Y
– If Y is a metal (low electronegativity), then
the substances are bases.
bases
– If Y has intermediate electronegativity (e.g.
I, EN = 2.5),
.5), the electrons are between Y
and O and the substance is a weak oxyacid.
– If Y has a large electronegativity (e.g. Cl,
EN = 3.0), the electrons are located closer
to Y than O and the O-H bond is polarized
to lose H+.
– The number of O atoms attached to Y
increase the O-H bond polarity and the
stren th of the acid increases (e
strength (e.g. HOCl is
a weaker acid than HClO2 which is weaker
than HClO3 which is weaker than HClO4
which is a strong acid).
For a series of oxyacids,
oxyacids acidity increases
with the number of oxygens.
Organic Acids
Carboxylic Acids
• These are organic acids which contain a COOH group
(R is some carbon containing
O unit):
C
R OH

• When the proton is removed, the negative charge is

delocalized over the carboxylate anion:
O O
C C
R O R O

• The acid strength increases as the number of

electronegative
l i groups on R iincreases.
Resonance iin the
R h conjugate
j b
bases of
f
carboxylic acids stabilizes the base and
makes the conjugate acid more acidic.
acidic
D. Cations in Aqueous Solution
1) Cationic metal ions are generally Lewis acids in
water solutions
2) Example:
[Fe(H2O)6]3+ + H2O  [Fe(H2O)5(OH)]2+ + H3O+
3)) Large
g chargeg and small radii increase acidity y
a) Alkali metals are not acidic (Na+); Alkaline
Earths are weakly acidic (Ca2+)
b) 2+ Transition Metals are weak acids; 3+
Transition Metals are strong acids
c) All 4+ or higher metals are very strong acids
Æ MxOy
• Cations with acidic protons
(like NH4+) will lower the pH
of a solution.
• Most metal cations that are
hydrated in solution also
lower the pH of the solution.
• Attraction between nonbonding
electrons on oxygen and the
metal causes a shift of the
electron density in water.
• This makes the O-H bond more
polar and the water more acidic.
• Greater charge and smaller size
make
k a cation
ti more acidic.
idi
4) The stronger acid the cation is, the less soluble the
hydroxide complex is. OH- can’t dissociate to dissolve
b
because of
f strong
t charge
h attraction.
tt ti
We can use this property to estimate the acid
strength of the cation
E. Steric Effects

1) Steric bulk can repel an acid-base partner,

modifyin the acid
modifying acid-base
base strength
stren th
2) The order of basicity can scramble depending
on bulk of
f the acid
F Solvation
F.

1) Solvation is interaction with solvent molecules

2) Basicity
B i i in i water: NHM
NHMe2 > NH2Me M > NMe
NM 3 >
NH3
a) By induction
induction, the more substituted amine
should be the most basic
b) This amine has less H’s to interact with
water
G. Non-aqueous Solvents
1) The
Th L Leveling
li Effect:
Eff the
h strongest acidid possible
ibl in
i
a solvent is the solvent cation; the strongest base
possible in a solvent is the solvent anion.
a) H2SO4 + H2O H3O+ + HSO4- (100%
dissociation)
b) Na2O + H2O  2 Na+ + 2 OH- (100%
dissociation)
c) H2SO4 + HOAc  H2OAc+ + HSO4- (< 100%)
d) NH3 + HOAC
HO C  NH4+ + OAc O - (100%)

2) HNO3, H2SO4, HClO4, HCl are all equally acidic in

water
t (H3O+)

3) HClO4 > HCl > H2SO4 > HNO3 in HOAc

4) Hydrocarbon Solvents don’t level acids or bases