Acid-base Equilibria in

Aqueous Solutions
Salts
A salt is an ionic compound containing an anion
other than OH- or O2-.
 Almost all salts dissolve completely in water at
concentrations commonly used in biological
research.
 A salt consists of ions both when in the solid form
and when dissolved in water.
 Salts
 Product of neutralization reactions eg NaCl.

 They are also strong electrolytes.

 One mole of NaCl will generate one mole of sodium ions

and one mole of chloride ions.

 Salts
from weak acids and weak bases will also ionize
completely when placed in aqueous solution.
 Salts
 For many salts dissolved in water, one more of the ions
react with water to form significant amounts of either
H3O+ or OH-, i.e, the ions act as weak acids or bases or
both.
 The reaction is termed a hydrolysis.
 eg, when NH4Cl is dissolved in water the ions, NH4+ &
Cl- react with water.
Salts
 A small fraction of the NH4+ reacts as follows:

 Although only a small fraction reacts, it is

sufficient to make the solution acidic.

 Cl- does not react to any significant extent.

Salts
 Solutions of salts are very common in chemistry,
biological systems, environmental matrices, etc.

 We can now predict in a qualitative sense (and in some

cases quantitatively) the pH of solutions of acids, bases
& salts.
Salts
 Salts of strong acids/strong bases
 Salts
 Salt of Strong Acid/Weak Base
Salts
 Salt of Weak Acid/Strong Base
Salts of Weak Acids & Bases—They Aren’t Neutral
 The salt of a weak acid, eg, NaOAc, is a strong electrolyte,
like (almost) all salts, & completely ionizes.
 the anion of the salt of a weak acid is a Brønsted base,
which will accept protons.
OAc- = CH3COO-
 It
partially hydrolyzes in water (a Brønsted acid) to form
OH- & the corresponding undissociated acid. eg,
Salts of Weak Acids & Bases—They Aren’t Neutral
 The HOAc here is undissociated and therefore does not
contribute to the pH.

 This ionization is also known as hydrolysis of the salt ion.

 Because it hydrolyzes, sodium acetate is a weak base (the

conjugate base of acetic acid).
Salts of Weak Acids & Bases—They Aren’t Neutral
 We can write an equilibrium constant:

 KH is called thehydrolysis constant of the salt and is the

same as the basicity constant.
 We will use Kb to emphasize that these salts are treated
the same as for any other weak base
Salts of Weak Acids & Bases—They Aren’t Neutral
 The value of Kb can be calculated from Ka of acetic acid
and Kw

 The product of the acid dissociation constant of any acid

and the base dissociation constant of its conjugate base is
K w.
Salts of Weak Acids & Bases—They Aren’t Neutral
 For any salt of a weak acid HA that hydrolyzes in water,
Salts of Weak Acids & Bases—They Aren’t Neutral
 The pH of such a salt (a Brønsted base) is calculated in the
same manner as for any other weak base.
 When the salt hydrolyzes, it forms an equal amount of HA
and OH−.
 If the original concentration of A− is CA−, then
Salts of Weak Acids & Bases—They Aren’t Neutral
 The quantity x can be neglected compared to CA−

….if CA− > 100Kb, which will generally be the case for such
weakly ionized bases. we can solve for the OH− conc using
Eq
 This equation holds only if CA− > 100Kb, and x can be
neglected compared to CA−.

 Ifthis is not the case, then the quadratic formula must

be solved as for other bases in this situation.
Example
 Calculate the pH of a 0.10 M solution of sodium acetate.
Salts of Weak Acids & Bases—They Aren’t Neutral
 Similar equations can be derived for the cations of
salts of weak bases (the salts are completely
dissociated).
 These are Brønsted acids and ionize (hydrolyze) in
water:
 Acid-base Equilibria in Aqueous
Solutions

Mixtures of Salts of Weak Acids and Bases and buffer systems

Mixtures of Salts of Weak Acids and Bases and buffer systems

 A salt
is a product of the reaction of a base and an acid.
The anion of the salt of a weak acid is a B-L base.

 Consider acetate(OAc-) ion from (NaOAc; Na ethanoate

or acetate, a salt of a weak acid CH3COOH).

 Mixtures of salts of weak acids & bases or acids &

their conjugate base form buffer systems.
Buffers:Keeping the pH Constant (or Nearly So)

A buffer is a solution that resists changes in pH when small

amount of acid or base are added to it when the solution is
diluted.
Buffers:Keeping the pH Constant (or Nearly So)
 Consider an acetic acid–acetate buffer.
 The equilibrium that governs this system is:

 Ifwe add the acetate ions to the system (e.g., from

sodium acetate), the H ion conc is no longer equal to
the acetate ion conc.
Buffers:Keeping the pH Constant (or Nearly So)
 The H ion conc is
Buffers:Keeping the pH Constant (or Nearly So)
 The H-H eq is useful for calculating the pH of a weak
acid solution containing its salt.

 The pH of a buffer is determined by the ratio of the

conjugate acid–base pair concentrations
Buffers:Keeping the pH Constant (or Nearly So)
A general form can be written for a weak acid HA that
ionizes to its salt, A−, and H+
Example
 Calculatethe pH of a buffer prepared by adding 10 mL of
0.10 M acetic acid to 20 mL of 0.10 M sodium acetate.
 the amount of acid dissociated is very small, particularly in
the presence of the added salt (ionization suppressed by
the common ion effect), and can be neglected.
 Hence, we can assume the added concentrations to be the
equilibrium concentrations:
 We could have shortened the calculation by recognizing
that in the log term the volumes cancel.
 So we can take the ratio of millimoles only:
  A buffer works through thecommon-ion effect.
Buffers and the Common-ion Effect

 Acetic acid in water dissociates slightly to produce

some acetate ion:
The buffering mechanism
 Adding small amounts of acid: The H+ ions added react
with the excess ethanoate ions (from the salt) and are
removed from the solution as ethanoic acid molecules..
 … (there is a very marginal decrease in pH observed as
some acid molecules do dissociate to give H+).

 Nevertheless, the pH stays virtually the same.

The buffering mechanism
 Adding base: the OH- ions react with the hydrogen
ions from (ethanoic acid) removing them from the
right hand side.
The Effect of Dilution
 If the solution is diluted, the ratio remains constant, and so
the pH of the solution does not change.
 On dilution, both the weak acid and the weak base can
dissociate more to compensate for the dilution:

CH3COOH(aq) + H2O(l)  CH3COO-(aq) + H3O+(aq)

CH3COO-(aq) + H2O(l)  CH3COOH(aq) + OH-(aq)

 NH4+(aq) + H2O(l)  NH3(aq) + H3O+(aq)

NH3(aq) + H2O(l)  NH4+(aq) + OH-(aq)
The Effect of Dilution
 The pH of a buffer solution remains essentially
independent of dilution until the concentrations of
the species it contains are decreased.
 However, it decreases the buffering capacity,
since the concentration has been reduced
Buffer Capacity
 A buffer must protect against large pH changes.
 The ability of a buffer to protect against such changes is
described by a term known as the buffer capacity!
 It is a measure of the efficiency of a buffer, in resisting
changes in pH.
 It is also known as buffer efficiency, buffer index and
buffer value.
Buffer Capacity

 Conventionally, the buffer capacity (β), is defined as the

mole of strong acid or base that must be added to one
liter of buffer to produce a pH change of 1.0 units in the
buffer.
Buffer Capacity
 The buffer capacity β, can now be approximately
calculated  using the following equation:

 Where, ΔB is the molar amount of the base/acid added to

the buffer to introduce a pH change of ΔpH
 The equation only gives the average buffer capacity over
the increment of base/acid added
Buffer Capacity

 This equation permits one to compute the buffer capacity

at any hydrogen ion concentration—for example, at the
point where no acid or base has been added to the buffer.
 The higher the buffer capacity the less the buffer solution
changes its pH!!
 Applications of Buffers in biological systems and industries
 Body fluids contain buffering agents and buffer systems
that maintain pH at or near 7.4.
 Important endogenous buffer systems include Primary

buffers present in plasma are  –  Carbonic acid-

bicarbonate system and acid alkali salts of  phosphoric
acid systems
 Secondary buffers that are present in erythrocytes are
 –  hemoglobin/ oxyhemoglobin system & acid salts of
phosphoric acid system
bicarbonate buffer
• The bicarbonate buffer system is present in blood in
great amounts and maintains the pH of blood.

• HCO3- =0.02M & H2CO3=0.00125M their ratio

being 20/1 and pKa value=6.1 giving a pH=7.4.
 Applications of Buffers in biological systems and industries

 An in vivo value of pH<6.9 (for example the pH of the

blood in diabetic coma is as low as about 6.8) or pH>7.8
can be life threatening.

 Pharmaceutical solutions should have low buffer capacity

in order to prevent overwhelming the body’s own buffer
systems
 Applications of Buffers in biological systems and industries
 A variety of factors affect blood pH including what is
ingested, vomiting, diarrhea, lung function, endocrine
function, kidney function, and urinary tract infection.
 Industrially, buffer solutions are used in fermentation
processes and in setting the correct conditions for dyes
used in colouring fabrics
 In calibration of pH meters.
 Applications of Buffers in biological systems and industries

 Other buffer solutions

 A buffer does not have to a mixture of a weak acid and
its conjugate base; any mixture of a weak acid and a
weak base will have the same effect.
  Substances which can behave as both weak acids and
weak bases can also behave as buffers.
Other buffer solutions

 sodium hydrogencarbonate; the HCO3- ion can behave

as either an acid or a base:

HCO3-(aq) + H3O+(aq)  CO2(g) + 2H2O(l)

HCO3-(aq) + OH-(aq)  CO32-(aq) + H2O(l)
Other buffer solutions

 Amino acids can also behave as buffers:

Eg CH3CH(NH2)COOH - 2-aminopropanoic acid

CH3CH(NH2)COOH(aq) + OH-(aq)  CH3CH(NH2)COO-(aq) + H2O(l)

CH3CH(NH2)COOH(aq) + H3O+(aq)  CH3CH(NH3+)COOH(aq) +

H2O(l)