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Acidic

Theme 11. ACIDS and BASES

Neutral

Basic

Theme 11. Acids and Bases


- Acids and bases.
- Arrhenius Theory of Acids and Bases.
- Brnsted-Lowry Theory of Acids and Bases.
- Properties acid-base of water
Kw
pH
- Strength of Acids and Bases. Acidity and Basicity Constant (Ka and Kb). Conjugated Acid-Base Pairs.
- Polyprotic Acids
- Acid-Base Properties of Salts.
- Acid Strength and Molecular Structure
Hydrolysis. Buffer Solutions and its pH determination
Acido-Base Titrations. Equilibrium Curves. Acid-Base Indicators
- Lewis Theory of Acids and Bases

Arrhenius Theory of Acids and Bases.


An Acid is a compound that gives H+ ions when
dissolved in water.
A Base is a compound that gives OH- ions when
dissolved in water.

ACID-BASE CHEMISTRY

Arrhenius Theory. Strength of Acids

The Arrhenius Theory limits the concept of Acid and Base to, respectively, protic acids (HA) and
metal hydroxides (MOH) and in aqueous solution.
When dissociation of an Acid HA into H+ and A- is virtually complete (70-100%), it is said to be a
Strong Acid.
HA(aq)

H+(aq) + A-(aq)

But if dissociation is only partial (less than 70%), it is a Weak Acid (represented by a double arrow).
HA(aq)

ACID-BASE CHEMISTRY

H+(aq) + A-(aq)

Arrhenius Theory. Strength of Acids

ACID-BASE CHEMISTRY

Arrhenius Theory. Strength of Acids

ACID-BASE CHEMISTRY

Acidity. pH
The Acidity (or Basicity) of a solution (after having dissolved an acid or a base in water) can be
conveniently expressed by the pH, which is defined as the decimal logarithm of the inverse of the
molar concentration of H+ (or H3O+) ions.
HA +
initial concentration ([H3O]+)
final concentration

10-3 M
0

H 2O

H3O+
0
10-3 M

A0
10-3 M

Thus, in this case

pH = -log ([H3O+]) =- log(10-3) = 3 (dimensionless)

ACID-BASE CHEMISTRY

Self-Ionization of Water. Chemical Equilibrium

The molecule of Water also partially (very weakly) dissociates into H+ and OH- ions.

H2O(l)

H+(aq) +

OH-(aq)

Water would act as a weak electrolyte (very low dissociation). The double arrow indicates that
the reaction takes place simultaneously in both directions (forward and backwards).

It is a Dynamic Process.

ACID-BASE CHEMISTRY

Brnsted and Lowry Theory of Acids and Bases.

A base is any substance (molecule or


ion) that can accept a proton.

An acid is any substance (molecule or ion) that can


transfer a proton (H+ ion) to another substance.

In short, acids are proton donors, bases are proton acceptors and acid-base reactions are protontransfer reactions.
ACID-BASE CHEMISTRY

Brnsted and Lowry Theory


According to the Brnsted and Lowry Theory, acid-base neutralizations are reactions in which H+
ions (protons) are transferred (from the acid to the base).

Brnsted Acid (protic)

A Brnsted Acid (protic) will


give (transfer) a H+ ion if and
only if there is a Base capable
to accept that proton, and
viceversa.
Dissociation of a protic acid
HA in water (like dissolution of
an ionic electrolyte) can be
formally regarded as an acidbase reaction in which water
acts as the base.

ACID-BASE CHEMISTRY

Brnsted and Lowry Theory of Acids and Bases.

Likewise, dissolution of a
base in water can be
envisaged as an acid-base
reaction
where
water
becomes the acid (transfers
a proton to the base).

In either case, the lower or higher degree of dissociation will indicate the strength of the acid
or base.
ACID-BASE CHEMISTRY

Strength of Acids

The lower or higher degree of dissociation into H3O+ and A- ions will indicate the comparative
strength of the acid.

HA + H2O

H3O+ + A-

(70-100% dissociation strong acid)

HA + H2O

H3O+ + A-

(<70% dissociation weak acid)

Strong acids: HCl, HBr, HI, HNO3, H2SO4,

ACID-BASE CHEMISTRY

Weak acids: H3PO4, H2S, CH3COOH,

Strength of Acids

In the case of strong acids (full dissociation), the molar concentration of H3O+ (represented
as [H3O+]) can be calculated straight away.
HA +

H 2O

H3O+

A-

initial concentration ([H3O]+)

10-3 M

final concentration

10-3 M

10-3 M

Example:

ACID-BASE CHEMISTRY

pH = 3.00

Acidity constant

For weak acids (partial dissociation), the molar concentration of H3O+ ([H3O+]) has to be worked
out using the Equilibrium Acidity Constant, KA.
HA +

H 2O

H3O+

A-

The Acidity Constant Ka relates the molar concentration of undissociated HA (reactant) to those
of H3O+ and A- (products) at the moment that the reaction comes to its end (no net dissociation
anymore) and at a given temperature.

ACID-BASE CHEMISTRY

Acidity constant
The Acidity Constant KA relates the molar concentration of undissociated HA (reactant) to those
of H3O+ and A- (products) at the moment that the reaction comes to its end (no net dissociation
anymore) and at a given temperature.
KA =

[H3O+] x [A-]
[HA]

HA +

H 2O

H3O+

A-

initial concentration

(no dissociation)

final concentration

c-x

(dissociation ended)

ACID-BASE CHEMISTRY

Acidity constant

Example: Determine the molar concentration of H3O+ ([H3O+]) and the pH of a 10-2 M solution of
acetic acid (CH3COOH) in water at 25C
HA +

H3O+

H 2O

A-

initial concentration (M)

10-2

final concentration (M)

10-2 - x

therefore

Ka = 1.8 x 10-5 =

[H3O+] x [A-]

[HA]

x2

10-2 - x

Ka = 1.8 x 10-5 M (25 C)

ACID-BASE CHEMISTRY

and

x = [H3O+] = 4.24 X 10-4 M

Acidity constant

Example: Determine the molar concentration of H3O+ ([H3O+]) and the pH of a 10-2 M solution of
acetic acid (CH3COOH) in water at 25C
Ka = 1.8 x 10-5 M (25 C)

HA +

initial concentration (M)

10-2

final concentration (M)

10-2 - x

H 2O

H3O+

A-

x2

as

Ka = 1.8 x

10-5

ACID-BASE CHEMISTRY

10-2 - x

and

x = [H3O+] = 4.24 X 10-4 M,

thus pH = log (

4.24 x 10-4

) = 3.37

Strength of Bases

The same reasoning applies to strong and weak bases. Lower or higher degree of accepting H+
(protonation), this resulting in B-H+ and OH- ions, would correlate to the strength of the base.

B + H 2O

B-H+ + OH-

(70-100% protonation strong base)

B + H2O

B-H+ + OH-

(<70% protonation weak base)

strong bases: NaOH, KOH, Ba(OH)2,

ACID-BASE CHEMISTRY

weak bases: NH3, triethylamine,

Basicity constant

Likewise with weak acids, the molar concentration of unprotonated base, [B] (reactant) and
those of the B-H+ and OH- ions, ([B-H+] and [OH-], products) at the moment when there is no
more net protonation and at a given temperature, are numerically related by the Equilibrium
Basicity Constant, Kb.

B + H2O

ACID-BASE CHEMISTRY

B-H+ + OH-

Kb =

[B-H+] x [OH-]
[B]

Water Self Ionization Constant.

Water, on top of acting as an acid or as a base, can also (partially) self dissociate into the H+ and
OH- ions.
H2O (l)

H+ (aq) + OH- (aq)

Kw = [H+] x [OH-]

When this self dissociation is finished (equilibrium), the molar concentrations of the H+ and OHions are related by the Water Self Ionization Constant, Kw.
At 25C, Kw = 10-14 , for which reason is [H+] = [OH-] = 10-7 M (for pure water), and thus pH = 7.00

ACID-BASE CHEMISTRY

Conjugated Acids and Bases

When a protic acid HA dissolves in water, the A- anion is known as the Conjugated Base of the HA
acid.
HA +

H 2O

H3O+

acid

A-

conjugated base

For a base B, also dissolved in water, the B-H+ cation is known as the Conjugated Acid of the B
base.
B +
base

ACID-BASE CHEMISTRY

H2O

B-H+

conjugated acid

OH-

Conjugated Acids and Bases


The Conjugated Base (A-) of a weak acid (HA) is comparatively strong.
HA +

H 2O

H3O+

acid
(weak)

A-

conjugated base
(strong)

Whereas the conjugated base of a strong acid is itself weak.


HA +
acid
(strong)

ACID-BASE CHEMISTRY

H 2O

H3O+

A-

conjugated base
(weak)

Conjugated Acids and Bases

It means that dissolving a salt formed from a weak acid and a strong base (e.g. sodium acetate,
made from acetic acid and sodium hydroxide) will result in a basic solution.

NaAc + H2O

ACID-BASE CHEMISTRY

Na+ + Ac-

and then

Conjugated Acids and Bases


Dissolution of a salt formed from a weak acid and a strong base (e.g. sodium acetate) will result
in a basic solution, as the conjugated base (A-) is strong and can take a H+ ion from water.
NaAc + H2O

Na+ + Ac-

and then

H2O + Ac-

OH- + HAc

conjugated base
(strong)

basic medium

On the other hand, the Na+ ion (the conjugated acid of an strong base, NaOH) is of weak character,
and it is not capable (not strong enough) to take an OH- ion from water
NaAc + H2O

Na+ + Ac-

and then

H2O + Na+

conjugated acid (weak)

ACID-BASE CHEMISTRY

no reaction

Conjugated Acids and Bases


Likewise, dissolution of a salt formed from a weak base and a strong acid (e.g. ammonium chloride)
will result in an acidic solution, as the conjugated base (NH4+) can give a H+ ion to water.
NH4Cl + H2O

NH4+ + Cl-

and then

H2O + NH4+

H3O+ + NH3

conjugated acid
(strong)

acidic medium

Also, the Cl- ion (the conjugated base of an strong acid, HCl) is of weak character, thus will not be
able (not strong enough) to take an H+ ion from water
NH4Cl + H2O

NH4+ + Cl-

and then

H2O + Cl-

conjugated base (weak)

ACID-BASE CHEMISTRY

no reaction

Conjugated Acids and Bases


A more complex case is that of the dissolution of a salt formed from a weak acid and a weak base
(e.g. ammonium acetate), in which both the conjugated base (acetate anion, Ac-) and conjugated
acid (ammonium cation, NH4+) can react with water.
NH4Ac + H2O

NH4+ + Ac-

and then

H2O + NH4+

H3O+ + NH3

conjugated acid
(strong)

H2O + Ac-

OH- + HAc

conjugated base (strong)

The final acidity (or basicity) of the solution will depend on the comparative strength of both ions.
ACID-BASE CHEMISTRY

ACID-BASE CHEMISTRY

Los cidos fuertes y bases fuertes


ms frecuentes

Los cidos dbiles y bases dbiles ms frecuentes y sus constantes de disociacin

ACID-BASE CHEMISTRY

Polyprotic Acids
Some Compounds (e.g. Brnsted Acids) can transfer more than one proton to a base. Those Acids
are called Polyprotic Acids.
Example: Phosphoric Acid (H3PO4) can transfer three protons when dissolved in water

H3PO4 + H2O

H3O+ + H2PO4-

1st dissociation (strongest)

H2PO4- + H2O

H3O+ + HPO42-

2nd dissociation (weaker)

HPO42- + H2O

H3O+ + PO43-

3rd dissociation (weakest)

And three dissociation constants (Ka1, Ka2 and Ka3) can be written, one for each reaction.

ACID-BASE CHEMISTRY

Chemical Reactions in Aqueous Solutions. Acid Base Neutralization Reactions. Polyprotic Acids
Example: For Phosphoric Acid (H3PO4) three dissociation constants (Ka1, Ka2 and Ka3) can be written
H3PO4 + H2O
H2PO4- + H2O
HPO42- + H2O

Ka1
Ka2
Ka3

H3O+ + H2PO4-

Ka1 =

H3O+ + HPO42-

Ka2 =

H3O+ + PO43-

Ka3 =

First dissociation is stronger than second, and second stronger than third.

ACID-BASE CHEMISTRY

[H3O+] x [H2PO4-]
[H3PO4]

[H3O+] x [HPO42-]
[H2PO4-]
[H3O+] x [HPO42-]
[HPO42-]

= 7.5 x 10-3 M
= 6.2 x 10-8 M
= 4.8 x 10-13 M

Polyprotic Acids
Another Example of polyprotic acid is Sulphuric Acid (H2SO4), that can transfer two protons
H2SO4 + H2O

HSO4- + H2O

very strong
KA

H3O+ + HSO4-

complete dissociation

H3O+ + SO42-

KA =

[H3O+] x [SO42-]
[HSO4-]

= 1.3 x 10-2 M

First dissociation is essentially complete (strong acid), and second dissociation is rather weak.

ACID-BASE CHEMISTRY

Theme 11. cido-Base


- Acids and bases.
- Arrhenius Theory of Acids and Bases.
- Brnsted-Lowry Theory of Acids and Bases.
- Properties acid-base of water
Kw
pH
- Strength of Acids and Bases. Acidity and Basicity Constant (Ka and Kb). Conjugated Acid-Base Pairs.
- Polyprotic Acids
- Acid-Base Properties of Salts.
- Acid Strength and Molecular Structure
Hydrolysis. Buffer Solutions and its pH determination
Acido-Base Titrations. Equilibrium Curves. Acid-Base Indicators
- Lewis Theory of Acids and Bases

Acid Strength and Molecular Structure


The Strength of a Protic Acid H-A will depend on the following (combination thereof):
- The H-A bond must be polarized in such way that some positive charge density (d+) is located
on the hydrogen atom.

- The H-A bond must not be very strong (the lower the H-A bond energy, the stronger the acid).
- An H-A acid will be strong if the conjugated base A- (anion) is stable.

ACID-BASE CHEMISTRY

Acid Strength and Molecular Structure


The Strength of a Protic Acid H-A will depend on the following (combination thereof):
- The H-A bond must not be very strong (the lower the H-A bond energy, the stronger the acid).
Example:

ACID-BASE CHEMISTRY

Acid Strength and Molecular Structure


The Strength of a Protic Acid H-A will depend on the following (combination thereof):
- An H-A acid will be strong if the conjugated base A- (anion) is stable.
Example:

The presence of electronegative atoms stabilizes the


negative charge of the anion (conjugated base).

weak acid (Ka = 1.6 x 10-5 M)

ACID-BASE CHEMISTRY

H
H

H
H

stronger acid (Ka = 1.4 x 10-3 M)

even stronger (Ka = 0.16 M)

Common Ion Effect

ACID-BASE CHEMISTRY

Common Ion Effect

ACID-BASE CHEMISTRY

Buffered Solution
Buffer: a solution in which the pH resists change when small amounts of strong acids or bases are added.
A buffer consists of an aqueous solution of a weak acid and its conjugate base supplied as a salt, or a weak
base and its conjugate acid supplied as a salt.

A solution can act as a


buffer if it contains a
weak acid, HA, which
donates
protons
when a strong base is
added,
and
the
conjugate base, A-,
which
accepts
protons
when
a
strong acid is added.
ACID-BASE CHEMISTRY

A buffer solution contains a


weak base that acts as a
sink for the protons
supplied by a strong acid
and a weak acid that acts as
a source of protons to
supply to a strong base
being added. The joint
action of the source and
sink keeps the pH constant
when strong acid or base is
added.

Buffered Solution

A buffer solution will contain similar amounts of each species.

A buffer is a mixture of a weak conjugate acidbase pair that stabilizes the pH of a solution by
providing both a source and a sink for protons.

Buffered Solution, pH.


The pH of a Buffered Solution depends on the value of the Acidity Constant, Ka, (or basicity
constant, Kb) and on the relationship between the concentrations of acid and conjugated base
(or base and conjugated acid).

3 + [ ]
=
[]
+

[3 ] =

[]

[ ]

Henderson-Hasselbalch Equation

Buffered Solution, pH.


As long as the initial concentrations of HA and A- are similar and large enough (compared to the
added acid or base):

If:

= []

The pH of a buffer solution is close to the pKa of the weak acid component when the acid and
base have similar concentrations.

ACID-BASE CHEMISTRY

Selecting the composition for a buffer solution with a given pH


Calculate the ratio of the molarities of CO32- and HCO3- ions required to achieve buffering at
pH 9.50. The pKa2 of H2CO3 is 10.25.

ACID-BASE CHEMISTRY

Selecting the composition for a buffer solution with a given pH

Calculate the ratio of the molarities of CO32- and HCO3- ions required to achieve buffering at
pH 9.50. The pKa2 of H2CO3 is 10.25.
Solve

The solution acts as a buffer with a pH close to 9.50 if it is prepared by mixing the solutes in the
ratio 0.18 mol CO32- to 1.0 mol HCO3-.
ACID-BASE CHEMISTRY

Acid-Base Titrations (Neutralization)


The Amount of an Acid in a solution can be determined by reacting it with a Base (Neutralization):
In aqueous solutions, with protic acids, the reaction will proceed proton (H+) to proton. It means
that any proton given up by a (protic) acid is consumed (neutralized) by a base.
Example:
HCl (aq) + NaOH (aq)

NaCl (aq) + H2O (l)

In order that the reaction runs to completion (100% of protons neutralized) it is necessary that
the base is strong enough.

ACID-BASE CHEMISTRY

Chemical Reactions in Aqueous Solutions. Acid-Base Titrations (Neutralization)


The Amount of an Acid in a solution can be determined by reacting it with a Base (Neutralization):
As the reaction proceeds proton to proton, the amount (number of moles of H+ present in the
solution) can be calculated as follows:
HCl (aq) + NaOH (aq)

NaCl (aq) + H2O (l)

moles H+ from acid = moles OH- from base


[molar concentration of H+ aq] x (volume of acid) = [concentration of base] x (volume of base)
[HA] x VA = [Base] x VB

ACID-BASE CHEMISTRY

Chemical Reactions in Aqueous Solutions. Acid-Base Titrations (Neutralization)


The Amount of an Acid in a solution can be determined by reacting it with a Base (Neutralization):
Example: A 25.0 mL sample of vinegar (diluted acetic acid, CH3COOH) is neutralized (titrated) with
94.7 mL of 0.2 M NaOH solution. What is the molar concentartion of acetic acid?
CH3COOH (aq) + NaOH (aq)

CH3COONa (aq) + H2O (l)

moles H+ from acetic acid = moles H+ neutralized by NaOH


[molar concentration of H+ aq] x (volume of acid) = [concentration of base] x (volume of base)
[CH3COOH] x 25.0 mL = 0.20 M x 94.7 mL

ACID-BASE CHEMISTRY

[CH3COOH] = 0.7576 M

Acid-Base Titrations (Neutralization)

Base solution
(known
concentration)

In real case Titrations, the moment at which all acid has been consumed
(Equivalence Point) is visualized with an Indicator (a substance that changes
color depending upon pH).
This can be graphically seen
with a Titration Curve:
The Volume of the Analyte is
known (added with a pipette) and
that of the Titrant is measured with
a Burette.

ACID-BASE CHEMISTRY

Acid solution (unknown


concentration) plus indicator

Acid-Base Titrations (Neutralization), Indicators.

ACID-BASE CHEMISTRY

Acid-Base Titrations (Neutralization), Indicators.

ACID-BASE CHEMISTRY

Acid-Base Titrations (Neutralization), Indicators.

ACID-BASE CHEMISTRY

Lewis Acids and Bases

ACID-BASE CHEMISTRY

A Lewis acid is an electron pair acceptor.


A Lewis base is an electron pair donor.

Lewis Acids and Bases


Other Species, as Metal Ions and BF3, are Lewis Acids, as they accept electron pairs,
but they are not Brnsted and Lowry acids, as no protons are transferred.
In the reaction between NH3 and boron trifluoride (BF3), the lone pair on the nitrogen
atom of NH3 is donated to the Boron atom, as it has a vacant orbital in its Valence
Shell (this electron pair becomes a N-B bonding pair, so it is a Lewis acid-base
reaction).

Lewis Base
ACID-BASE CHEMISTRY

Lewis Acid

A Lewis acid is an electron pair acceptor.


A Lewis base is an electron pair donor.

Lewis Acids and Bases


Lewis Acids have an incomplete electron Octet.

Simple Metal Ions (e.g. Fe3+) also act as Lewis Acids when reacting with species that are
electron pair donors.

Fe3+ + 6 CN-

[Fe(CN)6]3-

Fe3+ has vacant orbitals and can accommodate up to six cyanide anions (CN-), resulting a
chelate or complex (hexacyanoferrate(III) ion) in a Lewis acid-base reaction.

ACID-BASE CHEMISTRY

Lewis Acids and Bases


A Lewis acid is an electron pair acceptor.
A Lewis base is an electron pair donor.
A Brnsted base is a special kind of Lewis base. For instance, an oxide ion is a Lewis base. It forms
a coordinate covalent bond to a proton, a Lewis acid, by supplying both the electrons for the
bond:

When the ammonia dissolves in water,


some of the molecules accept protons from
water molecules.
Selected the Lewis acid and base in this
case.
ACID-BASE CHEMISTRY

Lewis Acids and Bases


A Lewis acid is an electron pair acceptor.
A Lewis base is an electron pair donor.
Many nonmetal oxides are Lewis acids that react with water to give Bronsted acids.

Lewis Base

The product, an H2CO3


molecule, is a Bronsted
acid.

Lewis acid
In this reaction, the C atom of CO2, the Lewis acid, accepts an electron pair from the O atom of a
water molecule, the Lewis base, and a proton migrates from an H2O oxygen atom to a CO2 oxygen
atom.
ACID-BASE CHEMISTRY

Acidic, basic and amphoteric oxides

Acidic oxides are molecular


compounds like CO2.
Lewis acid

Bronsted acid
Bronsted base

Lewis acid
ACID-BASE CHEMISTRY

Lewis base and


Bronsted acid

The three theories.

ACID-BASE CHEMISTRY