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 d
definitions,
finiti ns each
h 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 acid
id f
forms H+ in
i water;
t
ab
base f
forms OH- in
i
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

BrnstedBrnsted
-Lowry Acids and Bases

+
The H Ion in Water

Proton Transfer Reactions

Focus on the H+(aq).

Brnsted-Lowry: acid donates H+ and base accepts H+.
Brnsted-Lowry base does not need to contain OH-.
C
Consider
id HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq):
)
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

BrnstedBrnsted
-Lowry Acids and Bases
Conjugate AcidAcid-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 acidbase 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
acid-base p
pairs.
conjugate
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 any
y solvent that can dissociate to
cation (acid) and anion (base)
3) For water: 2 H2O  H3O+ + OHa)) Any
A solute
l
iincreasing
i [H3O+] iis an acid
id
HCl + H2O  H3O+ + Clb) Any solute increasing [OH-] is a base
NH3 + H2O  NH4+ + OH4) Aprotic, non
non-aqueous
aqueous example
example: 2 BrF3 
BrF2+ + BrF4a) Acid: SbF5 + BrF3  BrF2+ + SbF6b) 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) pK
KH2SO4 = -log([H
l ([H3SO
O4+][HSO
][H O4-]) = 3.4
34
c) The smaller the number, the more dissociation has
occurred

E. Lewis Concept
p
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 doesnt really
t ll us about
tell
b t acid
id strength
t
th
2) HA + H2O

Ka

H3O+ + A-

3) DGo = -RTlnKa = DH - TDS

a) G = free energy
b) H = enthalpy
c) S = entropy
4) Solving for Ka:

H S
+
lnK a =
RT
R

[H 3O + ][A ]
Ka =
[HA]

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:
H-X
X bond to be polar w
with
th H + and X - ((if
f X iss a
H
metal then the bond polarity is H - , X + 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
the more effective the
chemical bond formed

THE NEGATIVE
PARTIAL CHARGE OF
THE DONOR ATOM

Involvement of the Donor

in Bond Multiplicity
-

Capacity of the Groups

Attached to the Donor
Polarizability of the Donor

THE NEGATIVE
PARTIAL CHARGE OF
THE DONOR ATOM

Concentration of the Donor

Electron Pair

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 p
positively
y charged
g
the acceptor atom, the more
effective the chemical bond
f
formed
d
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+ to
t 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 b
basicity
si it
Basicity: NMe3 > NHMe2 > NH2Me > NH3
3) O
Oxyacids:
id th
the more unprotonated
t
t d Oxygens,
O
th
the
stronger the acid
a) Acidity: HOClO3 > HOClO2 > HOClO > HOCl
b) The electronegative Os pull e- away from the
HO bond
c) The electronegative Os
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):
R

OH

When the proton is removed, the negative charge is

delocalized over the carboxylate anion:
R

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 charge
g 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
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- cant 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 Hs to interact with
water

G. Non-aqueous Solvents
1) The
Th L
Leveling
li Effect:
Eff
the
h strongest acid
id 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 dont level acids or bases