Acid - Base Equilibria

Acids and Bases

 Arrhenius acids have properties that

are due to the presence of the
hydronium ion (H+ (aq)) They turn
litmus red.
 Arrhenius bases have properties that
are due to the presence of the
hydroxide ion (OH- (aq)). They turn
litmus blue.
 Brønsted-Lowery
Acids and Bases
 Bronsted-Lowery definitions state that
acid-base reactions involve the
transfer of hydronium ions (H+) from
one substance to another.
 A hydronium ion is simply a proton
with no surrounding valence
electrons.
 Remember – acids donate and bases
accept!
Hydronium
ion
Proton transfer reactions

 The polar water molecule promotes

the ionization of acids in water
solution by accepting a proton to form
H3O+.
 Brønsted-Lowery definitions

ACID
BASE
Acids
donate Bases
protons accept
protons
The Hydronium ion

 The hydronium ion (H3O+) is a

hydrated proton. When water accepts
a proton from an acid, the product is a
hydronium ion.

 Hydronium ions are represented by

either the H3O+(aq) or H+(aq)
Conjugate Acid-Base Pairs

 Conjugate acid-base pairs are two

substances in an aqueous solution
whose formulas differ by an H+.
 The acid is the more positive species
having an extra H.
Amphoteric

 An amphoteric substance is a
substance that can act as either an
acid or a base.
 Relative Strengths
of Acids and Bases
 A strong acid completely transfers its
protons to water, leaving no
undissociated molecules in water. It
totally dissociates in water.
Relative Strengths, continued

 A weak acid only partially dissociates

in water, and exists as a mixture of
acid molecules and their constituent
ions.
 The conjugate base of a weak acid is
a weak base.
Relative Strengths, continued

 A substance with negligible acidity,

such as CH4, contains hydrogen, but
does not demonstrate any acidic
behavior in water.
 It’s conjugate base is a strong base,
reacting completely with water.
Acid-Base Equilibrium

 In every acid-base reaction the

position of equilibrium favors transfer
of the proton from the stronger acid to
the stronger base to form the weaker
acid and the weaker base.
Autoionization of Water

 Water has the ability to act as either

an acid or a base.
The ion product of water

 Because the autoionization of water is

an equilibrium process, there is an
equilibrium-constant expression:

 Kc = [H3O+][OH-]
 Ion-Product Constant for H2O

Kw = [H3O+][OH-] = 1.0 x 10 -14

can also be written

= [H ][OH ] = 1.0 x 10
+ - -14
Acid and Base Ionization
Constants
 The acid ionization constant (Ka) is
the equilibrium constant for the
ionization of a weak acid in water.
 The base ionization constant (Kb) is
the equilibrium constant for a weak
base.
 For any conjugate acid-base pair,

Kw = Ka x Kb.
pH Scale

 pH = -log[H+]
 Neutral solution:

pH = -log(1.0 x 10-7) = -(-7.00) =

7.00

The pH decreases as the [H+] increases.

The pH
Scale
The pH Scale
 Calculating the pH of a
Basic Solution
Calculate the pH of a basic solution, where the
[OH-] > 1.0 x 10-7 M. Suppose [OH-] = 2.0 x10-3 M.
Calculate the H+ value for this solution.

Kw 1.0 x 10-14
[H+] = = = 5.0 x 10-12 M
[OH-] 2.0 x 10-3

pH = -log(5.0 x 10-12) = 11.30

pH and pOH

 pH and pOH = 14.00

Measuring pH

 pH meter
 Acid-base indicators (less precise)
 Methyl orange
 Litmus
 phenolphthalein
 Etc.
 Strong Acids and Bases
 The seven most common strong acids include
6 monoprotic acids (HCl, HBr, HI, HNO3,
HClO3, and HClO4) and one diprotic acid,
H2SO4.

 HNO3(aq) + HOH(l) → H3O+(aq) + NO3-(aq)

 HNO3(aq) → H+(aq) + NO3-(aq)

Calculating the pH of a
strong acid
 What is the pH of a 0.040 M solution
of HClO4?

 pH = -log(0.040) = 1.40
Strong Bases

 Common strong bases are the ionic

hydroxides of alkali metals and the
heavy alkaline earth metals.
 The cations of these metals have
negligible acidity.
Weak Acids
 Weak acids are only partially ionized (or
dissociated.)
 They are weak electrolytes.
 HA(aq) + HOH(l) ↔ H3O+(aq) + A-(aq)
[H3O+][A-]
 Ka =
[HA]
 The larger the value of Ka, the stronger the
acid.
Polyprotic Acids
 Polyprotic acids have more than one
ionizable proton, such as H2SO3.
 These acids have acid-dissociation
constants that decrease in magnitude
in the order Ka1>Ka2>Ka3.
 Because nearly all the H+(aq) in a
polyprotic solution comes from the first
dissociation, the pH can usually be
estimated using only Ka1.
Weak Bases

 Weak bases include NH3, amines and

the anions of weak acids.
 Kb = the dissociation constant for the

base.
 The relationship between the strength
of an acid and the strength of its
conjugate base is expressed by the
equation Ka x Kb = Kw
 Using Kb to Calculate OH -

NH3(aq) + HOH(l) ↔ NH4+(aq) + OH-(aq)

[NH4+][OH-]
Kb = = 1.8 x 10-5
[NH3]

Reference the problem example on page 691.

 Hydrolysis
 Acid-base properties of salts can be
attributed to the behavior of their respective
cations and anions.
 The reaction with water, with a resulting
change in pH, is called hydrolysis.
 Cations of alkali metals and alkaline earth
metals and anions of strong acids don’t
hydrolyze.
 Salt + water = acid + base
Acid-Base Behavior and
Chemical Structure
 A molecule containing H will transfer a
proton only of the H-X bond is
polarized:
Bond Strength

 Strong bonds do not dissociate as

easily as weaker bonds, so they are
less likely to form acidic ions in
solution.
 Since HF has such a strong bond due
to the electronegativities, it does not
dissociate readily and is therefore a
weak acid.
Oxyacids

 Oxyacids are acids in which OH

groups and possible additional oxygen
atoms are present.
 What determines whether it is an acid
or a base?
 Generally, as the electronegativity of
the attached element increases, so
will the acidity of the substance.
 Oxyacids

 The strength of an acid will increase

as additional electronegative atoms
bond to the central atom.

Electronegativity
Acid strength increases as the
number of oxygen atoms attached
to the central atom increases.
Carboxylic Acids
 Acids that contain carboxyl groups are
called carboxylic acids.

These form
the largest
category of
organic
acids.
Lewis Acids and Bases
 The Lewis concept of acids emphasizes
the shared electron pair rather than the
proton.
 A Lewis acid is an electron-pair
acceptor.
 A Lewis base is an electron-pair donor.
 This concept is more general than the
Brønsted-Lowery definition – it explains
why many hydrated metal cations can
form acidic aqueous solutions.
 Acidity of Metal Cations
 The acidity of a hydrated metal cation
depends on the cation charge and size.