Beruflich Dokumente
Kultur Dokumente
Neutral
Basic
ACID-BASE CHEMISTRY
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)
ACID-BASE CHEMISTRY
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
ACID-BASE CHEMISTRY
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
In short, acids are proton donors, bases are proton acceptors and acid-base reactions are protontransfer reactions.
ACID-BASE CHEMISTRY
ACID-BASE CHEMISTRY
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-
HA + H2O
H3O+ + A-
ACID-BASE CHEMISTRY
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-
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-
10-2
10-2 - x
therefore
Ka = 1.8 x 10-5 =
[H3O+] x [A-]
[HA]
x2
10-2 - x
ACID-BASE CHEMISTRY
and
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 +
10-2
10-2 - x
H 2O
H3O+
A-
x2
as
Ka = 1.8 x
10-5
ACID-BASE CHEMISTRY
10-2 - x
and
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-
B + H2O
B-H+ + OH-
ACID-BASE CHEMISTRY
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, on top of acting as an acid or as a base, can also (partially) self dissociate into the H+ and
OH- ions.
H2O (l)
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
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-
H 2O
H3O+
acid
(weak)
A-
conjugated base
(strong)
ACID-BASE CHEMISTRY
H 2O
H3O+
A-
conjugated base
(weak)
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
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+
ACID-BASE CHEMISTRY
no reaction
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-
ACID-BASE CHEMISTRY
no reaction
NH4+ + Ac-
and then
H2O + NH4+
H3O+ + NH3
conjugated acid
(strong)
H2O + Ac-
OH- + HAc
The final acidity (or basicity) of the solution will depend on the comparative strength of both ions.
ACID-BASE CHEMISTRY
ACID-BASE CHEMISTRY
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-
H2PO4- + H2O
H3O+ + HPO42-
HPO42- + H2O
H3O+ + PO43-
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
- 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-BASE CHEMISTRY
ACID-BASE CHEMISTRY
H
H
H
H
ACID-BASE CHEMISTRY
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.
Buffered Solution
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.
3 + [ ]
=
[]
+
[3 ] =
[]
[ ]
Henderson-Hasselbalch Equation
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
ACID-BASE CHEMISTRY
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
In order that the reaction runs to completion (100% of protons neutralized) it is necessary that
the base is strong enough.
ACID-BASE CHEMISTRY
ACID-BASE CHEMISTRY
ACID-BASE CHEMISTRY
[CH3COOH] = 0.7576 M
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-BASE CHEMISTRY
ACID-BASE CHEMISTRY
ACID-BASE CHEMISTRY
ACID-BASE CHEMISTRY
Lewis Base
ACID-BASE CHEMISTRY
Lewis Acid
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 Base
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
Bronsted acid
Bronsted base
Lewis acid
ACID-BASE CHEMISTRY
ACID-BASE CHEMISTRY