Common acid-base theories

City of Mandaluyong Science High School

Acid and Bases
Acid and Bases
Acid and Bases
1- Lavoisier definition
August 26, 1743
May 8, 1794
Lavoisier's knowledge of
strong acids was mainly
restricted to oxyacids, which
tend to contain central atoms
in high oxidation states
surrounded by oxygen, such
as HNO3 and H2SO4
An oxoacid is an acid which
contains oxygen. More
specifically, it is an acid which:
contains oxygen;
contains at least one other
element;
has at least one hydrogen
atom bound to oxygen; and
forms an ion by the loss of one
or more protons
The name oxyacid is sometimes used, although this is not
recommended
Generally, oxoacids are simply polyatomic ions with a
hydrogen cation
Although carboxylic acids fulfill the criteria above, they
are not generally considered as oxoacids
2- Liebig definition
(May 12, 1803 April 18, 1873)
This definition was proposed by
Justus von Liebig circa 1838, based
on his extensive works on the
chemical composition of organic
acids.
This finished the doctrinal shift from oxygen-
based acids to hydrogen-based acids, started
by Davy
According to Liebig, an acid is a hydrogen-containing substance in which the
hydrogen could be replaced by a metal. Liebig's definition, while completely
empirical, remained in use for almost 50 years until the adoption of the Arrhenius
definition.
3- Arrhenius definition
Nobel prize in chemistry in 1903
The Arrhenius definition of acid-base
reactions is a more simplified acid-
base concept devised by Svante
Arrhenius, which was used to
provide a modern definition of bases
that followed from his work with
Friedrich Wilhelm Ostwald in
establishing the presence of ions in
aqueous solution in 1884
As defined at the time of discovery, acid-base
reactions are characterized by Arrhenius acids,
which dissociate in aqueous solution form
hydrogen or the later-termed oxonium (H3O+)
ions, and Arrhenius bases which form hydroxide
(OH-) ions.
More recent IUPAC recommendations now suggest the
newer term "hydronium be used in favor of the older
accepted term "oxonium.
Arrhenius acids form hydrogen ions in aqueous
solution with Arrhenius bases forming hydroxide ions.
acid+ + base- salt + water
2NaOH + H2SO4 2 H2O + Na2SO4
4- Brnsted-Lowry definition
1923
professor of inorganic and physical
chemistry at Copenhagen English physical chemist
The Brnsted-Lowry definition, formulated independently by its
two proponents Johannes Nicolaus Brnsted and Martin Lowry in
1923 is based upon the idea of protonation of bases through the
de-protonation of acids -- more commonly referred to as the ability
of acids to "donate" hydrogen ions (H
+
) or protons to bases, which
"accept" them.
CH
3
COOH + H
2
O === CH
3
COO
-
+ H
3
O
+

NH
3
+ H
2
O === NH
4
+
+ OH
-

CH
3
COO
-
+ H
2
O === CH
3
COOH + OH
-

NH
4
+
+ H
2
O === NH
3
+ H
3
O
+
In contrast to the Arrhenius definition, the Brnsted-Lowry definition refers
to the products of an acid-base reaction as conjugate acids and bases to
refer to the relation of one proton, and to indicate that there has been a
reaction between the two quantities, rather than a "formation" of salt and
water, as explained in the Arrhenius definition
AH + B BH
+
+ A
-

General formula for representing Brnsted-Lowry reactions.
HCl (aq) + H2O H3O
+
(aq) + Cl
-
(aq)
Hydrochloric acid completely reacts with water to form the hydronium
and chloride ions
CH3COOH + NH3 NH4+ + CH3COO-
Acetic acid reacts incompletely with ammonia, no hydronium
ions being produced
In differentiation from the Arrhenius definition, the Brnsted-Lowry definition
postulates that for each acid, there is a conjugate acid and base or
"conjugate acid-base pair" that is formed through a complete reaction,
which also includes water, which is amphoteric
For example, zinc oxide (ZnO) reacts differently depending on the pH of the solution:
In acids: ZnO + 2H
+
Zn
2+
+ H
2
O
In bases: ZnO + H
2
O + 2OH
-
[Zn(OH)
4
]
2-
Base (Proton Acceptor): H
2
O + HCl H
3
O
+
+ Cl

Acid (Proton Donor): H
2
O + NH
3
NH
4
+
+ OH

(Indeed, it can do both at once: 2H
2
O H
3
O
+
+ OH

)
The more recent Bronsted-Lowry concept is
that acids are H
+
(proton) donors and bases
are proton acceptors
Ionization
+ Cl H
H
H
O
+
H
H
H O
Cl
+
O (e.g. H
2
SO
4
) was originally thought to
cause acidic properties. Later, H was
implicated, but it was still not clear why CH
4

was neutral.
Arrhenius made the revolutionary
suggestion that some solutions contain ions
& that acids produce H
3
O
+
(hydronium) ions
in solution.
The Bronsted-Lowry concept
In this idea, the ionization of an acid by
water is just one example of an acid-base
reaction.
Acids and bases are identified based on
whether they donate or accept H
+
.
Conjugate acids and bases are found on
the products side of the equation. A
conjugate base is the same as the starting
acid minus H
+
.
+ Cl H
H
H
O
+
H
H
H O
Cl
+
acid base conjugate acid conjugate base
conjugate acid-base pairs
Practice problems
Identify the acid, base, conjugate acid,
conjugate base, and conjugate acid-base pairs:
acid base conjugate acid conjugate base
HC
2
H
3
O
2
(aq) + H
2
O(l) C
2
H
3
O
2

(aq) + H
3
O
+
(aq)
conjugate acid-base pairs
acid base conjugate acid conjugate base
OH

(aq) + HCO
3

(aq) CO
3
2
(aq) + H
2
O(l)
conjugate acid-base pairs
Acid Base Strength
Strong Acid - Transfers all protons to water;
completely ionizes;
strong electrolyte;

conjugate base is weaker and has
negligible tendency to be protonated.
Weak Acid - Fraction of protons transferred to water;
partly ionized;
weak electrolyte;
conjugate base is stronger readily
accepting protons from water
As acid strength decreases, base strength increases.
The stronger the acid, the weaker its conjugate base
The weaker the acid, the stronger its conjugate base
Leveling effect
The term leveling effect refers to a solvent's ability to level the effect of a
strong acid or base dissolved in it.
When a strong acid is dissolved in water, it reacts with it to form
H
3
O
+
in the following reaction (where "HA" is a generic strong
acid such as "HCl"):
HA + H
2
O -> A
-
+ H
3
O
+
Any acid that is stronger than H
3
O
+
reacts with H
2
O to form H
3
O
+
;
therefore, no acid can be stronger than H
3
O
+
in H
2
O.
This is true with any solvent, although usually to a lesser extent
than with water. Bases may be also leveled in solvents
Which one is stronger?
A) HCl B) HClO
4
Becouse of this leveing effect, HClO
4
and HCl behave as if they
had the same acid strength; both are leveled to H
3
O
+
:
HClO
4
+ H
2
O ---- H
3
O
+
+ ClO
-
HCl + H
2
O ---- H
3
O
+
+ Cl
-
In acetic acid solvent, which is less basic than H
2
O, HClO
4
and HCl are
not leveled to the same strength:
HClO
4
+ CH
3
COOH === CH
3
COOH
2
+
+ ClO
4
_
K= 1.3 10
-5
HCl + CH
3
COOH === CH
3
COOH
2
+
+ Cl
-
K= 2.8 10
-9
5-Lewis definition
Gilbert Newton Lewis
(October 23, 1875 - March 23, 1946)
a famous American physical chemist
known for his 1902 Lewis dot
structures, his paper "The Atom and
the Molecule", which is the foundation
of modern valence bond theory,
developed in coordination with Irving
Langmuir .
his 1923 textbook
Thermodynamics and the Free
Energy of Chemical
Substances, written in
coordination with Merle Randall,
one of the founding books in
chemical thermodynamics
In 1926, Lewis coined the term "photon" for the smallest unit of radiant energy.
The Lewis definition of acid base reactions, devised by Gilbert N. Lewis in
1923 is an encompassing theory to the Brnsted-Lowry and solvent-
system definitions with regards to the premise of a donation mechanism,
which conversely attributes the donation of electron pairs from bases
and the acceptance by acids, rather than protons or other bonded
substances and spans both aqueous and non-aqueous reactions
Ag
+
+ 2 :NH
3
[H
3
N:Ag:NH
3
]
+

A silver cation reacts as an acid with ammonia which acts as an
electron-pair donor, forming an ammonia-silver adduct
Acid - An electron pair
acceptor
Base - An electron pair
donor

6-Solvent-system definition
This definition is based on a generalization of the earlier Arrhenius definition to
all autodissociating solvents. In all such solvents there is a certain concentration
of a positive species, solvonium cations and negative species, solvate anions,
in equilibrium with the neutral solvent molecules. For example:

2H
2
O H
3
O
+
(hydronium) + OH
-
(hydroxide)
2NH
3
NH
4
+
(ammonium) + NH
2

(amide)

or even some aprotic systems:
N
2
O
4
NO
+
(nitrosonium) + NO
3

(nitrate)
2SbCl
3
SbCl
2
+
(dichloroantimonium) + SbCl
4
-
(tetrachloroantimonate)
A solute causing an increase in the concentration of the solvonium ions and a
decrease in the solvate ions is an acid and one causing the reverse is a base.
Thus, in liquid ammonia, KNH
2
(supplying NH
2
-
) is a strong base, and
NH
4
NO
3
(supplying NH
4
+
) is a strong acid.
Other acid-base theories
Usanovich definition
Lux-Flood definition
Pearson definition
What is a strong Acid?
An Acid that is 100% ionized in water.
Strong Acids:
100% ionized (completely dissociated) in water.

HCl + H
2
O H
3
O
+
+ Cl
-
often written as:
HCl H
+
+ Cl
-

Strong Acids:
Perchloric HClO4
Chloric, HClO
3

Hydrobromic, HBr
Hydrochloric, HCl
Hydroiodic, HI
Nitric, HNO
3

Sulfuric, H
2
SO
4
Strong Acids:
100% ionized (completely dissociated) in water.

HCl + H
2
O H
3
O
+
+ Cl
-
What is a strong Base?
A base that is completely dissociated in water (highly soluble).
NaOH(s) Na
+
+ OH
-
Strong Bases:

Group 1A metal hydroxides
(LiOH, NaOH, KOH,
RbOH, CsOH)
Heavy Group 2A metal hydroxides
[Ca(OH)
2
, Sr(OH)
2
, and
Ba(OH)
2
]
Strong Acids:
100% ionized (completely dissociated) in water.

HCl + H
2
O H
3
O
+
+ Cl
-
Note the one way arrow.
Weak Acids:
Only a small % (dissociated) in water.

HC
2
H
3
O
2
+ H
2
O H
3
O
+
+ C
2
H
3
O
2
-
Note the 2-way arrow.
Why are they different?
Strong Acids:
HCl HCl
HCl
HCl
HCl
ADD WATER to MOLECULAR ACID
(H
2
O)
Strong Acids:
(H
2
O)
H
3
O
+
H
3
O
+
H
3
O
+
H
3
O
+
H
3
O
+
Cl
-
Cl
-

Cl
-
Cl
-

Cl
-

Note: No HCl molecules remain in
solution, all have been ionized in water.
HC
2
H
3
O
2
HC
2
H
3
O
2
HC
2
H
3
O
2
HC
2
H
3
O
2
HC
2
H
3
O
2

(H
2
O)
Weak Acid Ionization:
Add water to MOLECULES of WEAK Acid
HC
2
H
3
O
2
HC
2
H
3
O
2
HC
2
H
3
O
2
HC
2
H
3
O
2
HC
2
H
3
O
2

H
3
0
+

C
2
H
3
O
2
-

(H
2
O)
Weak Acid Ionization:
Note: At any given time only a small portion of the acid molecules are ionized
and since reactions are running in BOTH directions the mixture composition
stays the same.
This gives rise to an Equilbrium expression, K
a
H
3
0
+

C
2
H
3
O
2
-

HC
2
H
3
O
2
Chemical equilibrium
In a chemical process, chemical equilibrium is the state in which the
chemical activities or concentrations of the reactants and products have
no net change over time. Usually, this would be the state that results
when the forward chemical process proceeds at the same rate as their
reverse reaction.
The reaction rates of the forward and reverse reactions are generally
not zero but, being equal, there are no net changes in any of the
reactant or product concentrations. This process is called as dynamic
equilibrium
Berthollet was one of the first chemists to recognize
the characteristics of a reverse reaction, and hence,
chemical equilibrium.
Potassium chlorate (KClO3), a strong oxidizer, is
known as Berthollet's Salt. Non-stoichiometric
compounds are also named berthollides in his
honor.
Claude Louis Berthollet.
Berthollet was one of several scientists who went with Napoleon to Egypt !
The concept of chemical equilibrium was developed after Berthollet
(1803) found that some chemical reactions are reversible. For any
reaction such as:
A + B === C +D
to be at equilibrium the rates of the forward and backward
(reverse) reactions have to be equal. In this chemical equation
with harpoon arrows pointing both ways to indicate equilibrium, A
and B are reactant chemical species, C and D are product
species, and , , , and are the stoichiometric coefficients of
the respective reactants and products.
Forward reaction rate = K
+
[A]

[B]

Backward reaction rate = K
-
[C]

[D]

where A, B, C and D are active masses and k
+
and k

are rate
constants. Since forward and backward rates are equal:
K
+
[A]

[B]

= K
-
[C]

[D]

and the ratio of the rate constants is also a constant,
now known as an equilibrium constant
K= K
+
/K
-
= [C]

[D]

/[A]

[B]