Acidity and Alkalinity, PH and Pka

Buffers

• Overview
• Understanding the Idea of Equilibrium
• Hydrogen ion and Hydroxyl ion Concentrations
• Meaning of the Term PH
• The Concept of Pka
• Henderson-Hasselbach Equation
• Buffers
• Buffer Action
• Buffer Solution
• Buffer/Buffering Capacity
• Physiological Significance of Buffers
 Understanding the Idea of Equilibrium
• Law of Mass Action

 The law of mass action relates to the state of equilibrium existing in reversible

reaction.

 It states that at equilibrium, the product of the concentrations of substances formed

in a chemical reaction divided by the product of the concentrations of the reactants

in that reaction is a CONSTANT known as the EQUILIBRIUM CONSTANT (Keq).

 It implies that the rate at which a reaction takes place at a fixed temperature is

proportional to the product of the concentrations of the reacting substances.

 Reversible Reaction

A+B C+D
Keq = C.D
A. B
• Example:
Rxn 1: C2H5OH + CH3COOH CH3COOC2H5 + H2O :Rxn 2
Ethanol Ethanoic acid Ethylacetate water

 Rxn 1 is the forward reaction while Rxn (2) is the backward

reaction
• Thus
• V1 α [C2H5OH] x [CH3COOH]
 V1=K1[C2H5OH] x [CH3COOH]

V2 α [CH3COOC2H5]x [H2O]

V2 = K2[CH3COOC2H5]x [H2O]

 At equilibrium, forward reaction is equal to the backward reaction

which implies that:

V1 = V 2
• i.e. K1[C2H5OH] x [CH3COOH] = K2 [CH3COOC2H5]x [H2O]

Thus:
• [CH3COOC2H5]x [H2O] = K1 = K equilibrium (Keq)
• [C2H5OH] x [CH3COOH] K2

 The equilibrium constant is independent of the reactants and is

constant for a given reaction in which equilibrium has been
established.

 It however varies with temperature and ρH

DIFFERENCE BETWEEN CONCENTRATION AND ACTIVITY

 The activity of a substance represents its effective

concentration.

 Particles of reactants in concentrated solutions may exert a

mutual attraction of each other or exhibit interactions with
the solvent in which the interactions occur.

 These interactions are considerably less if not negligible in

dilute solutions.

 Concentrations and activity are related to one another in

the following manner: aA = CA x ϒ

 Where CA = concentration
 aA =Activity
 ϒ = Activity co-efficient
 In very dilute solution, the activity tends towards unity
because solute interaction is negligible.

 At infinite dilute state activity and concentration are the

same.

 The reactants in many biochemical reactions are quite low

in concentration and hydrogen ion concentration in most
biological tissue reactions is very low.

 For convenience, therefore, activity can be equated to

concentration.
 Hydrogen ion and Hydroxyl ion concentrations

 An acid is a substance which when dissolved in water undergoes

dissociation with the formation of H+ ions as the only positive ions.

 A base is a substance which when dissolved in water undergoes

dissociation with the formation of OH- ions as the only negative
ions.

 Note: Strong acids are almost completely ionized in solution

whereas weak acids are only slightly ionized in solution.
 Pure water is slightly dissociated and has a low but measurable
conductivity.

 This process of dissociation is also referred to as ionization (i.e

formation of ions).

 It is also referred to as protolysis (i.e formation of protons).

• [HOH] [H+] + [OH-]

• Normally, protons do not exist free in aqueous solutions but are

always hydrated and predominantly present as H3O+ (hydroxonium
ion)
• At equilibrium:

• [H+] x [OH-] = K
• [HOH]
• The equilibrium constant for dissociation of water at 298K= 1.8 x10-16
• Thus:
[H+] x [OH-] = 1.8 x10-16
[HOH]

But the concentration of HOH in pure water is 55.5 mol/dm3 i.e (1000/18)

• Kw = [H+] x [OH-] = 1.8 x10-16 x 55.5 mol/dm3

Kw = 1.01 x 10-14= 10-14

• Where Kw= ion product of water

• Kw expresses the relationship between the concentration of H+ and OH-

• To calculate the concentration of H+ and OH-:

• In pure water [H+] = [OH-] = [H+]2 = [OH-]2 =10-14

• [H+] = [OH-] =10-7 mol/dm3
 Meaning of the Term ρH

 Recall that [H+] = [OH-] =10-7 mol/dm3

 This value of Kw increases by about 8% for every K rise in

temperature and at 310 K has a value of 2.4 x 10-14.

 The concentrations of H+ and OH- are linked by an inverse

relationship.

 This very small value of H+ and OH- concentration can be

greatly affected by addition of very small amount of acid or
alkali.
• The powers of 10 as an expression of H+ is rather unwieldy
and more convenient form as suggested by Sorensen:

• ρH = -log[H+]
• ρH = log 1
[H+]

• When hydrogen ion concentration is expressed as a power

of n, then the corresponding ρH value is the index of the
exponential term without its negative sign.
 By adding just 0.5 ml of a 2M HCl solution to pure water a
change in concentration of 10 000 fold takes place, the H+
concentration will go up to 10-3 mol/dm3.

 Addition of 0.5 ml of a 2M NaOH solution will give exactly

the opposite effect.

[H+] x [OH-] = 1.0 x 10-14

Take logarithm of this equation:
• log [H+] + log [OH-] = log (1.0 x 10-14)
• log [H+] + log [OH-] = -14
• Multiply by -1
• -log [H+] -log [OH-] = 14
• pH = -log [H+]
• pOH = -log [OH-]
• Thus: pH + pOH = 14
 Measurement of ρH

 Normally ρH is measured by ρH meter.

 The ρH meter measures the activity of change in hydrogen

ion and not its total concentration.

 For example when the ρH of a 0.1 mol/dm3 HCl solution was

measured with a ρH meter, it had a value of 1.09

 Because it measures activity instead of concentration, the

ρH would not be 10-1 i.e 1 but 1.09
• This implies that 1.09 = -log aH+ where aH+ is activity of H+
• aH+ =10-1.09
• aH+ = 8.1 x 10-2 mol/dm3
• [H+] = 10-1
• Activity co-efficient = aH+ = 0.081 = 0.81
[H+] 0.1
 The ρH scale is a convenient arithmetic scale which

variations of a logarithmic nature can easily be read.

Though read as 0, 1, 2, 3… but they are logarithmic i.e

The ρH scale
The ρH of some aqueous fluids
 The Concept of ρKa
 Strong acids and bases are completely ionized in dilute
aqueous solutions.

 In biological systems however, we often encounter weak

acids and bases which are not completely ionized when
dissolved in water.

 For a proper understanding of the behaviours of the

aqueous solutions of weak acids and bases we need to
remember the concept of conjugate acid-base pairs.

 A strong acid has the tendency to lose its protons to

become its conjugate base.
 These two normally have an inverse relationship; i.e the
conjugate base of a strong acid is normally weak, while the
conjugate acid of a strong base is also normally weak.
• HA H + + A-
• Conjugate base (weak)
• B + H+ BH

• Conjugate acid
• (weak)
• The tendency of an acid to lose a proton and form its
conjugate base is defined by the equilibrium constant for the
reversible reaction
• HA H + + A-
• Keq = [H+][ A-]
[HA]
• Equilibrium constant for ionization reactions are commonly
called ionization or dissociation Ka, the higher the value of
dissociation constant Ka, the stronger the acid.
• Weaker acids have lower dissociation constants.
 Values of dissociation constants are analogous to H+
concentrations and their unwieldy values become more
manageable when the term ρKa is introduced.

 ρKa like ρH is defined in terms of the – log10 of the dissociation

constant Ka
• ρKa = -log Ka
• ρH = log 1/Ka
• consequently, a strong acid has a low ρKa value, while a weak
acid has a high ρKa value.
• pKa can be determined experimentally; it is the ρH at the
midpoint of the titration curve for the acid or base.
• Below are the values of Ka and ρKa of some
compounds.
• Compound Ka ρK a
• Ethanoic acid 1.74 x 10-5 4.76
• Phosphoric acid 7.25 x 10-3 2.14
• Carbonic acid 1.70 x 10-4 3.73
• Ammonium ion 5.62 x 10-10 9.25
 The Henderson-Hasselbalch
Equation
• The shape of the titration curve of any weak acid is
described by the Henderson-Hasselbalch equation,
which is important for understanding buffer action
and acid-base balance in the blood and tissues of
vertebrates.
• This equation is simply a useful way of restating the
expression for the dissociation constant of an acid.
For the dissociation of a weak acid HA into H + and
A-, the Henderson-Hasselbalch equation can be
derived as follows:
• This equation fits the titration curve of all weak
acids and enables us to deduce a number of
important quantitative relationships.
• For example, it shows why the pKa of a weak
acid is equal to the pH of the solution at the
midpoint of its titration. At that point, [HA]
equals [A-], and
• ρH = ρKa+ log 1 = ρKa + 0 = ρKa
• i.e at this point ρH= PKa
 Buffers:
Definition of Terms

• Buffer action: it is the ability of a solution to

resist changes in H+ ion concentration upon the
addition of small amounts of acid or base.
• Buffer solution: a buffer solution is one that
possesses buffer action, and usually consists of
a weak acid HA and its sodium or potassium
salt A- or of a weak base and its salt BH+
• A host of chemical reactions in biological systems, in
industry and in the laboratory are sensitive to changes in H+
ion concentration.

• It is known, for example, that the ρH of the medium

influences the growth of micro-organisms and plants, the
reactivity of enzymes, the efficiency of industrial
fermentations, among others.

• As it is, the proper functioning of human blood in carrying

oxygen to the cells from the lungs is dependent on
maintaining a ρH very near to 7.4. The control of ρH is
effected by buffering- that is by the use of a buffer solution.
• Buffer capacity: buffer capacity is the number

of moles of strong base that when added to one

dm3 (1 litre) of a solution will cause a unit

increase of ρH
 Buffering Capacity (Power)

• The titration curve of acetic acid illustrates the

buffering capacity of acetic acid/acetate pair.

• After addition of each increment of NaOH to

the acetic acid solution, the pH of the mixture
is measured. This value is plotted against the
amount of NaOH expressed as a fraction of the
total NaOH required to convert all the acetic
acid to its deprotonated form, acetate.
 Physiological Significance of
Buffers/Important Physiological Buffers
• Almost every biological process is ρH
dependent; a small change in pH produces a
large change in the rate of the process.
• This is true not only for the many reactions in
which the H+ ion is a direct participant, but
also for those in which there is no apparent
role for H+ ions.
• The enzymes that catalyze cellular reactions,
and many of the molecules on which they act,
contain ionizable groups with characteristic
pKa values.
• The protonated amino and carboxyl groups of
amino acids and the phosphate groups of
nucleotides, for example, function as weak
acids; their ionic state depends on the pH of
the surrounding medium
• Ionic interactions are among the forces that
stabilize a protein molecule and allow an enzyme
to recognize and bind its substrate.
• Cells and organisms maintain a specific and
constant cytosolic pH, keeping biomolecules in
their optimal ionic state, usually near pH 7.
• In multicellular organisms, the pH of extracellular
fluids is also tightly regulated. Constancy of pH is
achieved primarily by biological buffers (mixtures
of weak acids and their conjugate bases).
Physilogical Buffers