Theme 8.

ACID-BASE
- 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 it´s pH determination
- Acido-Base Titrations. Equilibrium Curves. Acid-Base Indicators
- Lewis Theory of Acids and Bases
 ACID-BASE
Arrhenius BrØnsted and Lowry

( ) → + ( ) + ⇄ +

( ) → + ( ) + ⇄ +

An Acid is a compound that gives H+ ions
(Hidronio) when dissolved in water.
A Base is a compound that gives OH- ions
(Hidroxilo) when dissolved in water.
An Acid is any substance (molecule or ion) that
can transfer a proton (H+ ion) to another
substance.
A Base is any substance (molecule or
ion) that can accept a proton.
Conjugate Acid–Base Pairs
Strength of Acids
 Relative Strengths of Conjugate Acid-Base Pairs
Strength of Acids

( ) + ⇄ +
Weak acid Strong base

( ) → +
Strong base Weak acid
 Lewis Acids and Bases

A Lewis acid is a species that can form a covalent bond by accepting an electron pair from another
species; a Lewis base is a species that can form a covalent bond by donating an electron pair to
another species.

A Lewis acid is an electron pair acceptor.

A Lewis base is an electron pair donor.
Lewis Acids and Bases
If compared to the Bronsted-Lowry theory, the Lewis concept of acids and bases is of a more
general scope, as acidity is not restricted only to proton (H+) transfer reactions.
For instance, HCl is a Bronsted-Lowry acid, and also a Lewis acid:

H
H Cl + O Cl +
H H O
H H
Lewis Acids and Bases

Brønsted Acid and Lewis acid

Lewis and Brønsted Base

H
H Cl + O Cl +
H H O
H H

H
H
H N + O
H N H + O H
H H
H H
Lewis and Brønsted Base
Lewis and Brønsted acid
Lewis Acids and Bases

Other Species, as Metal Ions and BF3, are Lewis Acids, as they accept electron pairs, but
they are not Brønsted 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).

A Lewis acid is an electron

pair acceptor.
A Lewis base is an electron
pair donor.

Lewis Base
Lewis Acid
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.
Lewis Acids and Bases

A Brønsted 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.
Lewis Acids and Bases

Many nonmetal oxides are Lewis acids that react with water to give Bronsted acids.

The product, an H2CO3

molecule, is a Brønsted acid.

Lewis Lewis
acid Base

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.
 Acidic, basic and amphoteric oxides

An acidic oxide is an oxide that reacts with water to form a solution of a Brøsted acid:

Acidic oxides are

molecular compounds
like CO2
Lewis
Lewis acid Brønsted acid
base

Brønsted base

Lewis base and

Lewis acid
Brønsted acid
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 OH-
ions are related by the Water Self Ionization Constant, Kw.

At 25°C, Kw = 10-14 , for which reason is [H+] = [OH-] = 10-7 M (for pure water)
 Acid – Base. Acidity. pH
The Acidity (or Basicity) of a solution (after having dissolved an acid, base or salt 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 + H2 O H3O+ + A-
initial 10-3 M 0 0
change - 10-3 M 10-3 M 10-3 M
final 0 10-3 M 10-3 M
pH = - log ([H+]) = log ([H+]-1) = log(103) = 3

= =− [ ] (dimensionless)
[ ]

= =− [ ] + =
[ ]
Acid – Base. Acidity. pH
=− [ ] [ ]=

=− [ ] [ ]=

It is also possible to determine [ H+]

 Acid – Base. Acidity. pH

Ejercicio:
Calcular [H+], [OH-], pH, pOH, de la solución 0.01M de ácido nítrico (HNO3).

R/ [H+] = 10-2 M, pH = 2.0

[OH-] = 10-12 M, pOH = 12.0
Polyprotic Acids

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

very strong
H2SO4 + H2O H3O+ + HSO4- complete dissociation

[H3O+] x [SO42-]
HSO4- + H2O Ka H3O+ + SO42- Ka = = 1.3 x 10-2 M
[HSO4-]

First dissociation is essentially complete (strong acid), and second dissociation is rather weak.
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-
pH = -log ([H3O+])
initial 10-3 M 0 0
change - 10-3 M + 10-3 M + 10-3 M
final 0 10-3 M 10-3 M pH = 3.00

Example:
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.
 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.

HA + H 2O H3O+ + A-

initial c 0 0 (no dissociation)

change -x +x +x
final c-x x x (dissociation ended)

[H3O+] x [A-]
Ka =
[HA]
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 25°C. Ka = 1.8 x 10-5 M (25 °C)

CH3COOH + H 2O H3O+ + CH3COO-

initial 10-2 0 0
change -x +x +x
final 10-2 - x x x

[H3O+] x [A-] x2
therefore Ka = 1.8 x 10-5 = = and x = [H3O+] = 4,24 X 10-4 M
[HA] 10-2 -x

thus pH = - log [H+] = - log (4,24 X 10-4 ) = 3.37

 Degree of Dissociation (α)
Ka indicates the strength of an acid. Another measure of the strength of an acid is its percent
ionization, which is defi ned as

HA

HA A- + H+
initial c 0 0
α = x/Co  x = α Co
change - αc αc αc
eq c- αc αc αc
c(1 – α) Where α = degree of dissociation (fraction)
 Degree of Dissociation (α)

Determine el grado de disociación de una disolución de ácido nitroso (HNO2) 0,036 M a 25°C.
Ka = 4,5 * 10–4

x = 3,8 * 10–3 M

11% , α = 0,11
 Polyprotic Acids

Some Compounds (e.g. Brønsted Acids) can transfer more than one proton to a base. Those Acids
are called Polyprotic Acids.
Example: (a) Phosphoric Acid (H3PO4) can transfer three protons when dissolved in water
(b) For Phosphoric Acid (H3PO4) three dissociation constants (Ka1, Ka2 and Ka3) can be written

Ka1 [H3O+] x [H2PO4-]

1st dissociation H3PO4 + H2O H3O+ + H2PO4- Ka1 = = 7.5 x 10-3 M
(strongest) [H3PO4]
Ka2 [H3O+] x [HPO42-]
2nd dissociation H2PO4- + H2O H3O+ + HPO42- Ka2 = = 6.2 x 10-8 M
(weaker) [H2PO4-]
3rd dissociation Ka3 [H3O+] x [HPO42-]
(weakest)
HPO42- + H2O H3O+ + PO43- Ka3 = = 4.8 x 10-13 M
[HPO42-]

First dissociation is stronger than second, and second stronger than third.
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 + H 2O B-H+ + OH- (<70% protonation – weak base)

strong bases: NaOH, KOH, Ba(OH)2, … 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 + H 2O B-H+ + OH- [B-H+] x [OH-]

Kb =
[B]
Conjugated Acids and Bases

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

HA + H 2O H3O+ + A-
acid conjugated base
(weak) (strong)

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

HA + H 2O H3O+ + A-
acid conjugated base
(strong) (weak)
Ionization Constants of Some Weak Acids and Their Conjugate Bases at 25°C
Ionization Constants of Some Weak Acids and Their Conjugate Bases at 25°C
Acid-Base Properties of Salts
Salts are strong electrolytes that completely dissociate into ions in water.

Salts That Produce Neutral Solutions

Salts That Produce Basic Solutions

Salts That Produce Acid Solutions

The term salt hydrolysis describes the reaction of an anion or a cation of a salt, or both, with
water.
Salt hydrolysis usually affects the pH of a solution.
Acid-Base Properties of Salts. Salts That Produce Neutral Solutions

It means that dissolving a salt formed from a strong acid and a strong base (e.g. NaCl made from
HCl And NaOH) will result in a neutral solution.

conjugated base
(weak)
NaCl + H2O Na+ + Cl- and then H2O + Cl- X
H2O + Na+ X
conjugated acid
(weak)
Acid-Base Properties of Salts. Salts That Produce Basic Solutions
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 Na+ + Ac-

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- reaction

conjugated base
(strong)

NaAc + H2O Na+ + Ac- and then H2O + Na+ X no reaction

conjugated acid (weak)

Acid-Base Properties of Salts. Salts That Produce Acid Solutions
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+ reaction

conjugated acid
(strong)

NH4Cl + H2O NH4+ + Cl- and then H2O + Cl- X no reaction

conjugated base (weak)
Acid-Base Properties of Salts

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+ reaction

conjugated acid
(strong)

H2O + Ac- reaction

conjugated base (strong)

The final acidity (or basicity) of the solution will depend on the comparative strength of both ions.
Acid-Base Properties of Salts
Salts are strong electrolytes that completely dissociate into ions in water.

Salts That Produce Neutral Solutions

Salts That Produce Basic Solutions

Salts That Produce Acid Solutions

The term salt hydrolysis describes the reaction of an anion or a cation of a salt, or both, with
water.
Salt hydrolysis usually affects the pH of a solution.
Acid-Base Properties of Salts. Salts That Produce Neutral Solutions

It means that dissolving a salt formed from a strong acid and a strong base (e.g. NaCl made from
HCl And NaOH) will result in a neutral solution.

conjugated base
(weak)
NaCl + H2O Na+ + Cl- and then H2O + Cl- X no reaction
H2O + Na+ X no reaction
conjugated acid
(weak)

≈
Acid-Base Properties of Salts. Salts That Produce Basic Solutions
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 Na+ + Ac-

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 basic medium
(strong)
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+ X no reaction

conjugated acid (weak)

Acid-Base Properties of Salts. Salts That Produce Acid Solutions
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 acidic medium
(strong)

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- X no reaction

conjugated base (weak)
Acid-Base Properties of Salts

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.
Prediga si las siguientes disoluciones serán ácidas, básicas o esencialmente neutras:
(i) Ba(C2H3O2)2 ; (ii) NH4Cl; (iii) NH3CH3Br; (iv) NH4F; (v) K2HPO4; (vi) (NH4) 3PO4; (vi) (NH4)HSO4
 Acid-Base Titrations (Neutralization)
Solution
The Amount of an Acid in a solution can be determined by reacting of NaOH OH-
Na+ Na+
it with a Base (Neutralization): OH- OH
-

Na+ Na+
OH-
In aqueous solutions, with protic acids, the reaction will proceed
proton (H+) to proton. It means Solution
that any proton given up by a (protic) acid is consumed of HCl
H+ Cl-
(neutralized) by a base. Cl-
H+
H+
25 mL H+ Cl-
Cl-

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 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

n(H3O+) = n(OH–)
MA,B: Molarity
VA,B: volume
MA x VA x nA = MB x VB x nB nA,B: # of H+ ions in the acid
or OH- ions in the base
 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 HCl is neutralized (titrated) with 25,0 mL of 0,1 M NaOH solution. What is
the molar concentration of acid?

HCl (aq) + NaOH (aq) NaCl (aq) + H2O (l)

=
25 ∗ á ∗ 1 = 25 ∗ 0,1 ∗1
25 ∗ 0,1 ∗ 1
á = = 0,1
25 ∗1
Example: A 25, 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 concentration of acetic acid?
 Acid-Base Titrations (Neutralization)

Ejemplo: En un experimento de valoración, 12.5 mL de H2SO4 0.500 M neutralizan a 50.0 mL de NaOH.

Cual es la concentracion de la disolucion de NaOH?

Ejemplo: 100 ml de una disolución de H2SO4 se neutralizan con 25 mL de una disolución 2 M de Al(OH)3
¿Cuál será la [H2SO4 ] en M y N?

3 + 2 → 3 + 3 + 6 ()

= á =2∗ á
100 ∗ á ∗ 2 = 25 ∗2 ∗3
á = 2 ∗ 0,75 = 1,5 N
25 ∗2 ∗3
á = = 0,75
100 ∗2
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:
Acid solution (unknown
The Volume of the Analyte is concentration) plus indicator
known (added with a pipette) and
that of the Titrant is measured
with a Burette.
Acid-Base Titrations (Neutralization), Indicators.

Acid-Base Indicators change color with pH, allowing to visualise the Equivalence Point

For intance, phenolphthalein goes Fromm colorless in acidic médium to pink at basic pH

The volumen of added titrant at wich the indicator change color, thus corresponding to the equivalence
point, is then used in the calculations (titration equation)
Acid-Base Titrations (Neutralization), Indicators.

In order to accurately visualise the equivalence point, the Indicator must be properly chosen,
as each indicator changes color at determined pH range.
Indicators should ideally change color at the pH range at which there is the greates pH
variation (as seen in a tritation curve)
Acid-Base Titrations (Neutralization), Indicators.
Indicators should ideally change color at the pH range at which there is the greatest pH variation
(as seen in a titration curve)
To titrate a strong acid with a strong base (or viceversa), both indicators (phenolphtalein and
methyl red) are valid.
Acid-Base Titrations (Neutralization), Indicators.

Color changes for several acid-base indicators