The Ionization of Water

and Acid-Base
Chemistry

Lemon tree in blossom, Jose Escofet 1989

Water ionizes to positively and negatively charged ions

electron-rich molecules are called nucleophiles and they react with electron-poor
molecules called electrophiles
the oxygen atom in a water molecule is a nucleophile because of its two pairs
of un-bonded (un-shared) electrons.
the lone-pair electrons of the oxygen of one H2O molecule can attack the
hydrogen atom of another H2O molecule. This results in the breaking of
existing bonds and forming of new bonds in the reacting molecules.
the movement of a pair of
electrons (arrow) results in
new O-H bond forming the
Hydronium molecule (the
new H atom comes from
the second H2O molecule).
the original electron pair in
the second H2O molecule
remains associated with the
resulting hydroxide ion.

the dissociation of water can be simplified to:

H+

H2O

OH

and may be written as:

Keq

[H+][OH-]

where Keq is the equilibrium constant for the reaction.

The concentration of water is essentially unchanged.
Therefore the constants can be combined and
re-written as:

[H2O]

Keq [H2O]

[H+][OH-]

[H+][OH-]

Kw

[H+]

= [OH ]

Keq [H2O] is referred to as Kw so:

the Kw for pure H2O at 25oC and 1 atm pressure is 1 x 10-14

Since the concentrations of H+ and OH- are equal:
1/2

(Kw)

(1 x

10-14)

1/2

1 x 10-7 M

Any solution that contains equal concentrations of H+ and OH- (like pure water) is said
to be neutral.
Solutions with [H+] > [OH-] are acidic.
Solutions with [H+] < [OH-] are basic.

since for any solution:

[H+][OH-]

1 x 10-14 M2

we can calculate the concentration of one ion

if the concentration of the other is known.

if a solution has a [H+] of 1 x 10-3 M then:

[H+][OH-]

1 x 10-14 M2

(1 x 10-3 M) [OH-]

1 x 10-14 M2

[OH-]

1 x 10-14 M2
(1 x 10-3 M)

[OH-]

1 x 10-11 M

note that the [H+] (1 x 10-3 M) is much higher than the [OH-] (1 x 10-11).
A hundred million times higher to be exact!
Because these number range so widely, we convert them to a logarithmic scale, called pH

Strong Acids and Bases completely dissociate in water

The strong acid hydrochloric acid and the strong base sodium hydroxide completely
dissociate in water

H+

HCl
NaOH

Cl-

Na+ + OH-

This means that in an aqueous solution of 0.1 M HCl:

[H+]

= [Cl-] = 0.1 M =

1 x 10-1 M H+

and the [OH-] will be 1 x 10-13 M

What is the pH of this solution? The pH is the negative log of the hydrogen ion concentration.

pH = -log10[H+]
pH = -log (1 x 10-1M)
pH = -(-1) = 1

Conversely, one can calculate the [H+] from the pH:

pH = -log[H+]
[H+] = antilog (-pH)
[H+] = antilog (-1)
[H+] = 1 x 10-1 M

The pH scale
pH, which is defined as the negative logarithm of the
Hydrogen ion concentration, is a convenient scale
turning small and awkward numbers into
whole numbers

Moran p43

Practice Questions (Solutions will be posted on D2L).

1. What is the concentration of OH- in an aqueous solution if the H+ concentration
is 1 x 10-8M? Is this solution acidic or basic?

2. What is the [H+] in an aqueous solution of 0.2 M HCl. What is the pH?
3. You add 10 ml of 0.1 M HCl to 990 ml water. What are the [H+] and [OH-]
in this solution? What is the pH of the solution?

Note, for examinations, it is your responsibility to:

-bring a calculator
-ensure it is a functional calculator
-know how to use the calculator

Weak Acids and Bases partially dissociate in water

Organic acids (which are the kind that are most important to biological systems) do not
completely dissociate like HCl.
The dissociation of a weak acid can be represented by the following equation:

HA

H+

+ Aconjugate base of HA

weak acid

For example, acetic acid (CH3COOH) dissociates to the conjugate base CH3COO- and H+

H+
weak acid, acetic acid
(CH3COOH)

conjugate base, acetate ion

(CH3COO- )

The strength of a weak acid (its ability to release H+ ions) can be determined using
following expression:

Ka

[H+][A-]

where Ka is the acid dissociation constant. The larger

the Ka, the stronger the acid.

[HA]

for acetic acid, where Ka = 1.76 x 10-5 M we can calculate the [H+] in a 0.1 M solution
of acetic acid and also its pH:

1.76 x 10-5

1.76 x 10-5

Ka

[H+][CH3OO-]
[CH3COOH]

[H+][CH3OO-]
[CH3COOH]

x2
0.1 M

x = 1.33 x 10-3 M = [H+]

pH = -log (1.33 x 10-3M) = 2.88

simplifying assumption:
concentration of acid remains
nearly constant.

Because Ka values vary over a wide range, they are expressed using a log scale:

pKa = -log10Ka

The lower the pKa the stronger the acid.

McKee p87

Practice Questions (Solutions will be posted on D2L).

4. What is the pH of a 0.2 M acetic acid solution where the Ka for acetic acid
is 1.33 x 10-5 M.
5. What is the pH of a 0.1 M formic acid solution where the pKa for formic acid is 3.77.

Buffers
Buffers are solutions that resist changes in pH

Regulating pH is a universal and essential activity in living organisms

Human blood has a pH of 7.4 and can vary only between pH 7.35 and 7.45.
pH below 7.35 results in acidosis, eventual CNS depression, coma, death.
pH above 7.45 (alkalosis) results in muscle spasms, convulsions.
There are 3 main buffering system in the body and in cells
Bicarbonate buffer
Phosphate buffer
Protein buffer (see later).
Buffers are also often used in the lab and are made by mixing appropriate
concentrations of a weak acid with its conjugate base.

A Solution that resists changes in pH is said to be buffered

A buffered solution can resist pH changes because an equilibrium exists between the
weak acid and its conjugate base.
Consider a buffer composed of the weak acid acetic acid (CH3COOH)
and its conjugate base, the acetate ion (CH3COO-), which is initially at equilibrium.
If more H+ ions are added
to this solution, it drives
the equilibrium in the
direction of acetic acid
formation and the pH
changes little.

Ka

Ka

McKee p89

If OH- ions are added

to this solution, they combine
with the H+ ions forming
water and this drives
the equilibrium in the
opposite direction. The pH
changes little.

This is why, when we titrate (in the example below) a conjugate base by adding acid
this kind of curve is obtained:

Notice the pH changes

less rapidly where
pH = pKa (4.73) and
+/- one unit.

acid

Water itself is weakly buffered

H2O

Kw

H+

OH-

H+
if we add extra H+ ions to water
they will combine with OH- ions
to form water, driving the equilibrium
towards H2O formation.

the problem is that the dissociation constant of water is so low, there are few OHions available to react with H+ ions. Thus when acid is added to
pure water, the pH plummets immediately (we therefore view water as
unbuffered).
Chemical reactions often produce or consume H+ ions. When we study these
reactions in the lab, we do not want the pH of the reaction liquid to change.
Thus we add a buffer: a mixture of weak acid and its conjugate base to resist the
change in pH that would otherwise occur and perhaps ruin (or confound)
the experiment.

The Henderson-Hasselbalch Equation

When choosing or making a buffer in the laboratory, pH and pKa are useful concepts
The relationship between these quantities is expressed in the
Henderson-Hasselbalch equation which is derived as below.

Ka

[H+][A-]

solving for [H+] gives

[HA]

taking the -log of each side gives

remembering the definitions of

pH and pKa gives

-log [H+]

[H+]

Ka

[HA]
-log Ka -log
[A-]

[HA]
pH = pKa -log
[A-]

inverting the log term thus changing

pH
its sign, the H-H equation is
obtained.

[HA]
[A-]

-]
[A
= pKa + log
[HA]

-]
[A
pH = pKa + log
[HA]
A titration curve reveals that the best buffering situation (where a solution best
resists changes in pH when acid or base is added) occurs when the
concentrations of the acid [HA] and its conjugate base [A-] are equal.
This situation occurs when the pH of the solution equals the pKa of the acid:

pH = pKa + log [A ]
[HA]
pH = pKa + log (1)

since log(1) = 0, then

pH = pKa
the most effective buffering occurs 1 pH unit above and below an acids pKa

Synthetic and naturally occurring chemicals can be used to make buffers

if the experimental conditions demand that the solution be buffered between
pH 3.5 and 5.5, then an acetate buffer (acetic acid pKa 4.73) would be good.
if the solution needs to be buffered between pH 6 and 8 ( a typical pH range
when dealing with biological systems), the acetate buffer would be unsuitable and
one would look for a buffer system with a pKa around 7

Using the Henderson-Hasselbalch equation to formulate buffer

Acetic acid has a pKa of 4.8. How many ml of 0.1 M acetic acid and 0.1 M Na acetate are
required to prepare 1 litre of 0.1 M buffer solution having a pH of 5.8?

pH = pKa + log

[A ]

5.8 = 4.8 + log

[HA]
[A-]

antilog (1) =

[HA]
[A-]
[HA]

substitute desired pH and pKa into H-H

equation
solve for ratio of [A-]/[HA]

-]
[A
10 =
[HA]

= 10
1

10 volumes of acetate ion (Na acetate) must be added for every 1 volume of acetic acid
equaling a total of 11 volumes.

acetic acid needed

acetate needed

1
11
10
11

x 1000 ml = 91 ml
x 1000 ml = 909 ml

Practice Questions (Solutions will be posted on D2L).

6. You are studying a enzyme in the laboratory that is only active between pH 5 and 8. You
wish to study the activity in a buffer of pH 7. Pick the best buffer system for making your
buffer:
Buffer system
pKa
Tris/HCl
8.1
Acetic acid/acetate
4.8
Lactic acid/lactate
3.9
Carbonate
6.4
Bicarbonate
10.2
Phosphate
7.2
7. Formic acid has a pKa of 3.8. How many ml of 0.2 M formic acid and 0.2 M Na formate
would you need to mix to make 0.5 litres of 0.2 M buffer solution having a pH of 3.8?
8. Lactic acid has a pKa of 3.9. How many ml of 0.4 M lactic acid and 0.2 M Na lactate
would you need to mix to make 0.5 litres of 0.2 M buffer solution having a pH of 3.9?

Some acids have multiple ionizable H atoms

Acetic acid has one ionizable H atom:

CH3COOH

H+

+ CH3COO-

pKa = 4.8

Phosphoric acid has 3 ionizable H atoms:

H3PO4

H+

H2PO4-

H+

2
HPO4

H+

H2PO4-

pKa1 = 2.2

HPO42-

pKa2 = 7.2

+ PO4

3-

pKa3 = 12.7

Many important biological acids

and bases have 2 or more
ionizable groups including
the amino acids, which can
also act as buffers.
Phosphoric acid (H3PO4) is
called a polyprotic acid.

Moran p48

Naturally occurring buffer systems in biology

Bicarbonate buffer - used to regulate the pH of blood, which must be very
strictly controlled. Involves the bicarbonate ion HCO3- and CO2. The amount
of CO2 in the blood is strictly controlled by the amount exhaled when
breathing.
Phosphate buffer - used to regulate the pH inside of cells.
Protein buffers - since there is a high concentration of protein in the body and
in cells, the amino acids that make up proteins have a considerable buffering
effect on pH. All amino acids have at least two ionizable groups, the amino
group and the carboxylate group (as shown in this Aa below).
CH3
H3N+

C
H

CH3

pKa1 = 2.3

H3N+

C
OH

C
H

O
C
O

CH3

pKa2 = 9.7

H2N

C
H

Some amino acids also have ionizable side chains as well, as we will see later.

O
C
O

Hints to get started on becoming familiar with Amino acids

All possess:

H2N C C
OH
H

-an Carbon to which is attached

-an amino group
-a carboxylic acid group
-a hydrogen atom

-a unique sidechain (R)

The amino and carboxyl group can be ionized depending on the surrounding pH.
At the pH typical of cytoplasm (pH 6.8 7.4, physiological pH) the amino group will be
protonated and the carboxyl group will be deprotonated.
Thus we typically draw amino acids in this form:

H3N C C
O
H

The
zwitterionic form of
an amino acid

non-ionized form of amino acid

does not exist in appreciable amounts

H2N C C
OH
H

R
+

fully ionized form of amino acid

-major form at physio pH (6.8-7.2)

H3N C C
O
H
note all amino acids
have ionized carboxyl
group above pH 2
and ionized amino
group below
pH 9-10

Key Concepts
Water itself ionizes to a very small degree into H+ (H3O+) ions and OH- ions
pH (a logarithmic scale) is used because the H+ concentrations can vary over such
a vast range.
pKa (a logarithmic scale) is a measure of the ability of a weak acid to dissociate
into H+ ions and the conjugate base of the weak acid
Buffers are mixtures of weak acids and their conjugate bases. They resist changes
in pH.
The Henderson-Hasselbalch equation relates pH and pKa and is useful for creating
buffers in the laboratory.
Naturally occurring buffers regulate pH in the blood, in cells, and other body fluids.
pH influences the ionization state of many biomolecules and thus influences their
chemical characteristics and the chemistry of the cell.
H+ ions participate ( are produced and consumed) in many chemical reactions in
the cell.