Buffer solutions.

ass. prof. I. R. Bekus

 Plan

1. Ionization of water.
2. Acid-base theory.
3. Buffer solutions.
4. Buffer in blood.
Water is а neutral
molecule with а slight
tendency to ionize. We
usually express this
ionization as:
Н2О = Н+ + ОН-
There is actually no such
thing as а free proton (Н+) in
solution. Rather, the proton is
associated with а water
molecule as а hydronium
ion, H3O+. The association of
а proton with а cluster of
water molecules also gives
rise to structures with the
formulas Н5О2+, Н7О3+, and
so on. For simplicity,
however, we collectively
represent these ions by H+.
Because the product of [Н+] and [ОН-] is а constant (10-14
М2), [Н+] and [ОН-] are reciprocally related. Solutions with
relatively more Н+ are acidic (рН < 7), solutions with
relatively more ОН- are basic (рН >7), and solutions in which
[Н+] = [ОН-] = 10 -7 М are neutral (рН = 7). Note the
logarithmic scale for ion concentration.
K is the dissociation constant (ionization constant)

Кw = [Н+][ОН-] =10 -14 M2 at 25 0C.

[Н+] = [ОН-] = (Кw)1/2 = 10-7 М
[Н+] = 10-7 М are said to be neutral
[Н+] > 10-7 М are said to be acidic,
[Н+] < 10-7 М are said to be basic.
Most physiological solutions have
hydrogen ion concentrations near
neutrality.
 рН = - log[H+]
The pH of pure water is 7.0,
Acidic solutions have рН < 7.0
Basic solutions have рН > 7.0.
1 М NaOH -14
Household ammonia -12
Seawater – 8
Milk - 7
Blood - 7.4
Saliva - 6.6
Tomato juice - 4.4
Vinegar - 3
Gastric juice - 1.5
1 М НСl - 0
The relationship between the pH of а solution and the concentrations of an acid and
its conjugate base is easily derived.
[НА]
[Н+]= K ----------
[А-]
Taking the negative log of each term
[А-]
рН = - log К + log ---------
[А-]

This relationship known as the Henderson-Hasselbalch equation, that is often used to perform the
calculations required in preparation of buffers for use in the laboratory, or other applications.
 BUFFER SOLUTIONS

Buffers are solutions which can

resist changes in pH by
addition of acid or alkali.
Buffers are mainly classified of two
types:
(а) mixtures of weak acids with their
salt with а strong base
(b) mixtures of weak bases with their
salt with а strong acid.
А few examples are given below:
Н2СО3 / NаНСО3 (Bicarbonate
buffer;carbonic acid and sodium
bicarbonate)
СН3СООН / СН3СОО Na (Acetate
buffer; acetic acid and sodium acetate)
Na2HPO4/ NaH2PO4 (Phosphate buffer)
 Acid–Base Concept
1) The Arrhenius theory
ACID - a substance that provides H+ ions in water

BASE - a substance that provides OH- ions in water

 2) The Brønsted-Lowry Theory

All Brønsted–Lowry bases have one or more lone pairs of

electrons:
3) The Lewis Acids and Base theory
LEWIS ACID An electron-pair acceptor
LEWIS BASE An electron-pair donor
 Acids
There are many acids
present in our
everyday lives.

Lemon juice contains citric acid, and vinegar contains

ethanoic acid.
Some strong acids are hydrochloric acid, sulphuric
acid and nitric acid.
Some weak acids are ethanoic acid, citric acid and
carbonic acid.
 Alkalis
Many everyday substances are alkalis.
They feel soapy.
They are corrosive.

When the oxides of some metals

dissolve in water they make an alkali
solution.
Alkalis react with acids and
neutralise them.
 Alkalis
Alkalis are present in many cleaning
substances in use in our homes.
Kitchen cleaners are alkaline
because they contain ammonia or
sodium hydroxide, which attack
grease.

Calcium hydroxide and sodium hydroxide are strong alkalis.

The most recognisable and common weak alkali is ammonia.
 Buffer Capacity
On the other hand, the buffer capacity is
determined by the actual concentrations of salt
and acid present, as well as by their ratio.
Buffering capacity is the number of grams of
strong acid or alkali which is necessary for а
change in pH of one unit of one liter of buffer
solution.
The buffering capacity of а buffer is, definеd аs
the ability of the buffer to resist changes in pH
when an acid or base is added.
 Definition of buffer capacity
A buffer absorbs strong acid and base through the two reactions shown on the left
side of our diagram:
A- + H3O+ => HA + H2O
HA + OH- => A- + H2O
The buffer will stop working when either one of its components (HA or A-) is
exhausted, and therefore cannot neutralize any more strong acid or strong base. The
most effective buffering solutions are those which have similar concentrations of
HA and A- because then the buffer has the capacity to absorb both acid and base
with the same effectiveness.
Although the pH of a buffer depends only on the ratio [HA]/[A-], the ability of the
buffer to absorb acid or base depends on the overall value of [HA] and [A-]. For
instance, above we found a pH change of -0.02 units (from 7.20 to 7.18) when we
added 0.010 moles of HCl to 1L of a buffer in which [HA] = [A-] = 0.50 M.
Supposed that we had a buffer with [HA] = [A-] = 5.0 M. How
much HCl would we need to add to get a pH change of -0.02
units? The answer is 10x as much as we found above, or 0.10
moles of HCl. This is summarized in this diagram:

A ten-fold increase in the concentration of our buffering agents increased

the ability to absorb acid, i.e. the buffer capacity, ten fold. The buffer
capacity is directly proportional to the concentration of our buffering agents.
 Buffers Act
 When hydrochloric acid is added to the acetate buffer, the salt reacts
with the acid forming the weak acid, acetic acid and its salt. Similarly
when а base is added, the acid reacts with it forming salt and water.
Thus, changes in the pH are minimised.
 СН3СООН + NaOH = СН3COONa + Н2О
 СН3СООNа + HCI = СН3СООН + NaCI
 The buffer capacity is determined by the absolute concentration of the
salt and acid. But the рН of the buffer is dependent on the relative
proportion of the salt and acid (see the Henderson - Hasselbalch's
equation). When the ratio between salt and acid is 10:1, the pH will
be one unit higher than the pKa. When the ratio between salt and acid
is 1:10, the pH will be one unit lower than the pKa.
 Mechanisms for Regulation of pH
 1. Buffers of body fluids,
 2. Respiratory system,

 3. Renal excretion.

These mechanisms are

interrelated.
Acidic solutions have a high H+
concentration. Base solutions have a
low H+ concentration. The pH scale is
used to indicate the acidity or alkalinity
of a solution. Pure water with an equal
number of hydrogen and hydroxide ions
has a pH of 7.
Factors Affecting pH of а
Buffer
The pH of а buffer solution is determined by
two factors:
 1. The value of pK: The lower the value of
pK, the lower is the pH of the solution.
 2. The ratio of salt to acid concentrations:
Actual concentrations of salt and acid in а
buffer solution may be varied widely, with
по change in рН, so long as the ratio of the
concentrations remains the same.
Thank you for attention