Back to Basics

For thousands of years people have known that vinegar,

lemon juice and many other foods taste sour.
However, it was not until a few hundred years ago
that it was discovered why these things taste sour -
because they are all acids. The term acid, in fact,
comes from the Latin term acere, which means "sour".
While there are many slightly different definitions of
acids and bases, in this lesson we will introduce the
fundamentals of acid/base chemistry.
Distinction
 Acids taste sour, are corrosive to metals, change
litmus (a dye extracted from lichens) red, and become
less acidic when mixed with bases.
 Bases feel slippery, change litmus blue, and become
less basic when mixed with acids.
Boyle’s definition
While Boyle and others tried to explain why acids and
bases behave the way they do, the first reasonable
definition of acids and bases would not be proposed
until 200 years later.
Arrhenius definition
In the late 1800s, the Swedish scientist Svante
Arrhenius proposed that water can dissolve many
compounds by separating them into their individual
ions. Arrhenius suggested that acids are compounds
that contain hydrogen and can dissolve in water to
release hydrogen ions into solution. For example,
hydrochloric acid (HCl) dissolves in water as follows:
HCl +H2O H+(aq) + Cl-(aq)
Arrhenius definition
Arrhenius defined bases as substances that dissolve in
water to release hydroxide ions (OH-) into solution.
For example, a typical base according to the
Arrhenius definition is sodium hydroxide (NaOH):
NaOH + H2O Na+(aq) + OH-(aq)
Arrhenius definition
The Arrhenius definition of acids and bases explains a
number of things. Arrhenius's theory explains why all
acids have similar properties to each other (and,
conversely, why all bases are similar): because all
acids release H+ into solution (and all bases release
OH-). The Arrhenius definition also explains Boyle's
observation that acids and bases counteract each
other. This idea, that a base can make an acid weaker,
and vice versa, is called neutralization.
Neutralization
As you can see from the equations, acids release H+
into solution and bases release OH-. If we were to mix
an acid and base together, the H+ ion would combine
with the OH- ion to make the molecule H 2O, or plain
water:
H+(aq) + OH-(aq) H 2O
Neutralization
The neutralization reaction of an acid with a base will
always produce water and a salt, as shown below:
Acid Base Water Salt
HCl + NaOH H 2O + NaCl
HBr + KOH H2O + KBr
Arrhenius definition
Though Arrhenius helped explain the fundamentals
of acid/base chemistry, unfortunately his theories
have limits. For example, the Arrhenius definition
does not explain why some substances, such as
common baking soda (NaHCO3), can act like a base
even though they do not contain hydroxide ions.
Brønsted-Lowry definition
In 1923, the Danish scientist Johannes Brønsted and
the Englishman Thomas Lowry published
independent yet similar papers that refined
Arrhenius' theory. In Brønsted's words, "... acids and
bases are substances that are capable of splitting off
or taking up hydrogen ions, respectively." The
Brønsted-Lowry definition broadened the Arrhenius
concept of acids and bases.
Brønsted-Lowry definition
The Brønsted-Lowry definition of acids is very similar
to the Arrhenius definition, any substance that can
donate a hydrogen ion is an acid (under the Brønsted
definition, acids are often referred to as proton donors
because an H+ ion, hydrogen minus its electron, is
simply a proton).
Brønsted-Lowry definition
The Brønsted definition of bases is, however, quite different
from the Arrhenius definition. The Brønsted base is
defined as any substance that can accept a hydrogen ion. In
essence, a base is the opposite of an acid. NaOH and KOH,
as we saw above, would still be considered bases because
they can accept an H+ from an acid to form water.
However, the Brønsted-Lowry definition also explains why
substances that do not contain OH- can act like bases.
Baking soda (NaHCO3), for example, acts like a base by
accepting a hydrogen ion from an acid as illustrated below:
Acid Base Salt
HCl + NaHCO3 H2CO3 + NaCl
Brønsted-Lowry definition
In this example, the carbonic acid formed (H2CO3)
undergoes rapid decomposition to water and gaseous
carbon dioxide, and so the solution bubbles as CO2
gas is released.
pH
Under the Brønsted-Lowry definition, both acids and
bases are related to the concentration of hydrogen
ions present. Acids increase the concentration of
hydrogen ions, while bases decrease the
concentration of hydrogen ions (by accepting them).
The acidity or basicity of something therefore can be
measured by its hydrogen ion concentration.
pH
In 1909, the Danish biochemist Sören Sörensen
invented the pH scale for measuring acidity. The pH
scale is described by the formula:
pH
pH = -log [H+] Note: concentration is commonly
abbreviated by using square brackets, thus [H+] =
hydrogen ion concentration. When measuring pH,
[H+] is in units of moles of H+ per liter of solution.
pH
For example, a solution with [H+] = 1 x 10-7
moles/liter has a pH equal to 7 (a simpler way to
think about pH is that it equals the exponent on the
H+ concentration, ignoring the minus sign). The pH
scale ranges from 0 to 14. Substances with a pH
between 0 and less than 7 are acids (pH and [H+] are
inversely related - lower pH means higher [H+]).
pH
Substances with a pH greater than 7 and up to 14 are
bases (higher pH means lower [H+]). Right in the
middle, at pH = 7, are neutral substances, for
example, pure water. The relationship between [H+]
and pH is shown in the table below alongside some
common examples of acids and bases in everyday life.
pKa
An acid dissociation constant, Ka, (also known as
acidity constant, or acid-ionization constant) is a
quantitative measure of the strength of an acid in
solution. It is the equilibrium constant for a chemical
reaction known as dissociation in the context of acid-
base reactions. The equilibrium can be written
symbolically as:
pKa
HA is in equilibrium with A- + H+,
where HA is a generic acid that dissociates by
splitting into A-, known as the conjugate base of the
acid, and the hydrogen ion or proton, H+, which, in
the case of aqueous solutions, exists as a solvated
hydronium ion. In the example shown in the figure,
HA represents acetic acid, and A- the acetate ion.
pKa
The chemical species HA, A- and H+ are said to be in
equilibrium when their concentrations do not change
with the passing of time. The dissociation constant is
usually written as a quotient of the equilibrium
concentrations (in mol/L), denoted by [HA], [A-] and
[H+]:
pKa
K_a equals the equilibrium concentration of the
deprotonated form A-, times the equilibrium
concentration of H+, all divided by the equilibrium
concentration of the acid AH.
pKa
Due to the many orders of magnitude spanned by Ka
values, a logarithmic measure of the acid dissociation
constant is more commonly used in practice. pKa,
which is equal to -log10 Ka, may also be referred to as
an acid dissociation constant:
pKa
The larger the value of pKa, the smaller the extent of
dissociation. A weak acid has a pKa value in the
approximate range -2 to 12 in water. Acids with a pKa
value of less than about -2 are said to be strong acids;
a strong acid is almost completely dissociated in
aqueous solution, to the extent that the concentration
of the undissociated acid becomes undetectable.
pKa
 pKa values for strong acids can, however, be
estimated by theoretical means or by extrapolating
from measurements in non-aqueous solvents in which
the dissociation constant is smaller, such as
acetonitrile and dimethylsulfoxide.
pKa
The acid dissociation constant for an acid is a direct
consequence of the underlying thermodynamics of
the dissociation reaction; the pKa value is directly
proportional to the standard Gibbs energy change for
the reaction. The value of the pKa changes with
temperature and can be understood qualitatively
based on Le Chatelier's principle:
Le Chatelier's principle
when the reaction is endothermic, the pKa decreases
with increasing temperature; the opposite is true for
exothermic reactions. The underlying structural
factors that influence the magnitude of the acid
dissociation constant include Pauling's rules for
acidity constants, inductive effects, mesomeric effects,
and hydrogen bonding.
pKa
The quantitative behaviour of acids and bases in
solution can be understood only if their pKa values
are known. In particular, the pH of a solution can be
predicted when the analytical concentration and pKa
values of all acids and bases are known; conversely, it
is possible to calculate the equilibrium concentration
of the acids and bases in solution when the pH is
known.
pKa
These calculations find application in many different
areas of chemistry, biology, medicine, and geology.
For example, many compounds used for medication
are weak acids or bases, and a knowledge of the pKa
values, together with the water–octanol partition
coefficient, can be used for estimating the extent to
which the compound enters the blood stream. Acid
dissociation constants are also essential in aquatic
chemistry and chemical oceanography, where the
acidity of water plays a fundamental role.
pKa
 In living organisms, acid-base homeostasis and
enzyme kinetics are dependent on the pKa values of
the many acids and bases present in the cell and in
the body. In chemistry, a knowledge of pKa values is
necessary for the preparation of buffer solutions and
is also a prerequisite for a quantitative understanding
of the interaction between acids or bases and metal
ions to form complexes.
pKa
Experimentally, pKa values can be determined by
potentiometric (pH) titration, but for values of pKa
less than about 2 or more than about 11,
spectrophotometric or NMR measurements may be
required due to practical difficulties with pH
measurements.
pH for BioChem
pH is a measure of the acidity or basicity of a
solution. It approximates but is not equal to p[H], the
negative logarithm (base 10) of the molar
concentration of dissolved hydrogen ions (H+).
Crudely, this matches the number of places behind
the decimal point, so for example 0.1 molar
hydrochloric acid should be near pH 1 and 0.0001
molar HCl should be near pH 4.
pH for BioChem
Pure water is neutral, neither a base or an acid, giving
it a pH of 7, or 0.0000001 M H+. For an aqueous
solution to have a higher pH, a base must be dissolved
in it, which binds away many of these rare hydrogen
ions. Hydrogen ions in water can be written simply as
H+ or as hydronium (H3O+) or higher species (e.g.
H9O4+) to account for solvation, but all describe the
same entity.
pH for BioChem
However, pH is not precisely p[H], but takes into
account an activity factor, which represents the
tendency of hydrogen ions to interact with other
components of the solution, which affects among
other things the electrical potential read using a pH
meter. As a result, pH can be affected by the ionic
strength of a solution - for example, the pH of a 0.05
M potassium hydrogen phthalate solution can vary by
as much as 0.5 pH units as a function of added
potassium chloride, even though the added salt is
neither acidic nor basic.
pH for BioChem
Unfortunately, hydrogen ion activity coefficients
cannot be measured directly by any
thermodynamically sound method, so they are based
on theoretical calculations. Therefore the pH scale is
defined in practice as traceable to a set of standard
solutions whose pH is established by international
agreement. Primary pH standard values are
determined by the Harned cell, a hydrogen gas
electrode, using the Bates-Guggenheim Convention.
pH for BioChem
Pure water is said to be neutral, with a pH close to 7.0
at 25 °C (77 °F). Solutions with a pH less than 7 are
said to be acidic and solutions with a pH greater than
7 are said to be basic or alkaline. pH measurements
are important in medicine, biology, chemistry, food
science, environmental science, oceanography and
many other applications.
Buffers
A buffer solution is an aqueous solution consisting of a
mixture of a weak acid and its conjugate base or a weak
base and its conjugate acid. It has the property that the pH
of the solution changes very little when a small amount of
strong acid or base is added to it. Buffer solutions are used
as a means of keeping pH at a nearly constant value in a
wide variety of chemical applications. Many life forms
thrive only in a relatively small pH range; an example of a
buffer solution is blood.
Buffer solutions are used to maintain a certain level on the
pH scale.
In a solution there is an equilibrium between a weak
acid, HA, and its conjugate base, A- : [1] [2]

 HA + H2O is in equilibrium with H3O+ + A-

When hydrogen ions (H+) are added to the solution,
equilibrium moves to the left, as there are hydrogen ions
(H+ or H3O+) on the right-hand side of the equilibrium
expression.
When hydroxide ions (OH-) are added to the solution,
equilibrium moves to the right, as hydrogen ions are
removed in the reaction (H+ + OH- ? H2O).

Thus, in both cases, some of the added reagent is

consumed in shifting the equilibrium in accordance with
Le Chatelier's principle and the pH changes by less than it
would if the solution were not buffered.
pOH
This is basically (no pun intended) the same as pH
but from the point of view of the OH- ions

Thus the negative logarithm of the OH- ions gives the

pOH

Note that at 25ºC ... pH + pOH = 14 it is therefore a

simple matter to obtain one from the other.
pKw
As you can probably guess from the previous two
definitons, pKw is the negative logarithm of Kw

And as... Kw = [H+][OH-]

Then... pKw = pH + pOH = 14 (at 25ºC)

Difference of ph and pOH
pH is a measure of the hydrogen ion concentration,
[H+]
pH is calculated using the following formula:
pH = -log10[H+]

pOH is a measure of the hydroxide ion concentration,

[OH-]
pOH is calculated using the following formula:
pOH = -log10[OH-]
Rough Definitions
pOH = -log[OH-]
the negative log of the hydroxide ion molarity

pKw = -log Kw
the negative log of the water ion product , Kw

pKa = -log Ka
the negative log of the acid dissociation constant, Ka

pKb = -log Kb
the negative log of the base dissociation constant, Kb
The End