Lesson 3.

2: pH and Buffer System

Lesson Summary
In this lesson, the measure of acidity will be discussed. This will also include a discussion on
buffer system and its importance in living organisms.

Learning Outcomes
At the end of this lesson, the students will be able to;

1. Calculate pH from the given concentration of hydrogen ion,

2. Correlate the relationship of pH and acid/base ionization constant, and

3. Discuss the importance of buffer system in the living organism.

Motivation Questions
What is the pH of the fluids inside our body? How do we maintain the pH of our body even if we
eat sour foods?

Discussion
Acids and bases have distinct characteristics that sets the two apart such as the taste and feel.
However, to properly distinguish the two, and to look into how strong a certain acid or base is a
certain parameter must be observed and that is what we called pH (power of hydrogen ion).

Measure of Acidity

Technically, acidity can be measured using its pH, which is mathematically expressed as, pH =
–log[H+]. If you remember, Arrhenius describe acid as substance that release H+ in water thus
this is the one being considered in calculating pH. On the other hand, if a certain substance has
a given pH, the [H+] is can be calculated by manipulating pH equation leading to a working
equation of [H+] = antilog(–pH).

The pH value technically will depend on the hydrogen ion concentration. If the [H+] = [OH-] the
solution is neutral and at 25°C the hydrogen ion concentration is experimentally determined to
be 1.00 x 10-7. Taking the – log of this value will give a pH value of 7. So, neutral solutions have
a pH value of 7. If the [H+] is greater than [OH-] the solution is acidic and has a hydrogen ion
concentration greater than 1.00 x 10-7, taking the – log of this will have values lower than 7. So,
acids have pH values lower than 7. Lastly, if the [H+] is lower than the [OH-], the solution is said
to be basic. The hydrogen ion concentration in this condition is lower than 1.00 x 10-7 so it has a
pH value higher than 7 upon taking the –log of those hydrogen ion concentration (< 1.00 x 10-7).
To summarize, neutral solutions has a pH of 7, acids have pH lower than 7 and bases have pH
higher than 7 up to 14. With respect to the relationship of [H+] and pH we can say that it is
inversely related. The higher the [H+] the lower will be the pH value, the solution is an acid. Also,
the lower the [H+] the higher will be the pH value, then the solution is a base.

Shown in figure 25 are some of the common fluids and its corresponding pH or pH range. The
gastric juice in our stomach has a pH range value of 1.0 – 2.0 and this is design for digestion of
foodstuffs aside from the pure enzymatic digestion. Fruit juices has a pH range values from 2.4
to 4.0 categorizing it as acidic. Milk is also quite acidic with a pH value of 6.5 and this may be
due to the presence of amino acids and very small amount of lactic acid.

Urine has a wide pH range value and this is cause by the nature of the food intake of a person.
Blood is slightly basic with a pH range of 7.35 – 7.45, and this pH is maintained by a very
sophisticated buffer system which will be discussed in the next pages.

Milk of magnesia and household ammonia are the most basic common fluids that can be found
at home.

Pure water has a pH value of 7, thus a neutral substance. However, upon the exposure to the
atmosphere, it will become acidic and will have a pH value of 5.5. This id due to the absorption
of CO2 from the atmosphere forming a small amount of carbonic acid, H2CO3.

In the laboratory, pH values can be determined using a pH meter or a multimeter apparatus.

Table 1. pH of some common fluids

Measure of Basicity

If pH is the measure of acidity, pOH is the measure of basicity and it is mathematically

expressed as –log[OH-]. The pH value is measured using a pH meter by looking into the
concentration of hydrogen ion, however no such apparatus can measure the concentration of
hydroxide ion.

To calculate pOH, we will consider the Kw expression of water. Rearranging the equation, we
will have the product of the concentrations of H+ and OH- ion is equivalent to the Kw at 25°C
which is 1.00 x 10-14. Taking the –log on both sides the equation will become –log[H+]–log[OH-]
= –log 1.0 x 10-14. The –log[H+] is pH, then –log[OH-] is pOH and –log 1.0 x 10-14 is 14.

So, pH + pOH is equivalent to 14, thus to calculate pOH we can manipulate this relationship
leading to a working equation of pOH = 14 – pH. Likewise, pH can also be calculated from pOH
value using the equation pH = 14 – pOH.
Strong Acids and Bases

The pH of strong acids and bases will be determined primarily from the amount of hydrogen ion
concentration produce from the total ionization of the acids or bases. Say for example if we
determine the pH of a 2.0 x 10-3 M HNO3 solution, we need to look into its ionization and its
ability to produce the hydrogen ion in water.

Take note that HNO3 is a strong acid and thus exhibits a complete ionization; 0.002 M HNO3 will
ionize to 0.002 M H3O+ and 0.002M NO3- leaving 0.00M of the acid at the end of the process.
The pH then can be calculated from the value of the hydronium ion concentration which is just
equal to the concentration of the strong acid. (Note: If the acid or base is strong, the
concentration of the acid or base at the start will also be the concentration of the ions generated
at the end of the ionization but consider the coefficient of the ions in its balanced chemical
equation.)

From the calculations, the pH then of the 2.00 x 10-3 M HNO3 solution is 2.70.
Weak Acids and Bases

Weak acids and bases exhibit partial ionization in water only so it’s uncertain how much of the
hydrogen ion or hydroxide ion is generated in water from a weak acid or base with specific
concentration unlike to a strong one.

To help us evaluate the ionization of weak acid or base, its ionization constant, or the acid
ionization constant (Ka) must be used. Ka is still an equilibrium constant expression similar to Kw.
Consider a hypothetical weak acid (HA) in water, it will dissociate partially forming the
hydronium ion (or hydrogen ion) and its conjugate base A-, with a Ka equivalent to the product of
the concentrations of the hydrogen ion and conjugate base ion over the concentration of weak
acid.

The higher the Ka value of a weak acid the higher is the strength of that weak acid. Table 2
shows the Ka and Kb (Kb is base ionization constant) of some of the weak acids and bases at a
certain temperature. Ka and Kb values are experimentally obtained and are relative to a certain
temperature. The ionization constant values will help in determining the concentrations of ions
formed upon the dissociation of a weak acid or base.
Table 2. Ka and Kb values of some weak acids and bases at 25°C

For example, to find the pH of a 0.5 M HF solution at 25°C we need to evaluate its ionization. A
balanced chemical equation of the dissociation reaction should be established first to have the
Ka expression.

The concentrations of the chemical species must then be evaluated at initial and at equilibrium
condition considering the unknown amount of weak acid that dissociates to its corresponding
ions.
At the start, 0.50 M of the acid is present and none of its corresponding ions. Considering it to
be a weak acid, let X be the amount of this acid that dissociates (-x) partially to form the H+ (+x)
and F- (+x). Then at equilibrium, 0.50 – x is present for HF, X for H+ and X for F-. substituting the
equilibrium concentration to the Ka expression, the equation below will be obtained.

if

If the Ka is very small than 1 we can assume that 0.50 – x is equal to 0.50 leading to a new Ka
expression equation written below.

From this equation, the terms can be cross multiplied to get X2 equivalent to 3.55 x 10–4. Getting
the square root on both sides, X then is equal to 0.019. Since X is the concentration of the ions
at equilibrium, the concentration then of H+ is 0.019M.

With the concentration of hydrogen ion being calculated, the pH value can now be determined
following the process below.

The pH of a weak acid HF solution with a concentration of 0.5 M is 1.72. The process in
obtaining the said pH involves an assumption and to see if the assumption is correct the value
of the calculated x should be less than 5% of the value from where it is subtracted. In the
example, the calculated x which is 0.019 is subtracted from 0.50.

The calculated x, which is 0.019, is just 3.8% of 0.5 where it is being subtracted. The condition
for the approximation is met there the approximation is valid. If the approximation is not valid,
the value of x must be calculated using the quadratic equation (Note: Remember you General
Chemistry lecture on Chemical Equilibrium).
To solve weak ionization problems, remember the following key points;

1. Identify the major species that can affect the pH such as the concentration of hydrogen ion.
2. USE the ICE to evaluate the changes in concentrations of the species involve in the balanced
chemical equation and to express the equilibrium concentration in terms of one unknown such
x. Take into consideration the coefficients.

3. Established Ka expression in terms of equilibrium concentrations and solve the value of X

using approximation. If approximation is not valid, use the quadratic equation.

4. Substitute the value of X to the concentration it represents and solve for the value of pH.

Buffer System

Buffer is a solution that contains a weak acid or weak base and the salt of the weak acid or
weak base and the two components must be present. For example, is the solution of acetic
acid, CH3COOH a weak acid, and its salt sodium acetate, CH3COO-Na+. A buffer solution will
resist drastic changes in the pH of a system upon the addition of either a strong acid or a strong
base. Consider an equimolar solution of acetic acid and sodium acetate, upon the addition of
strong acid, the acetate ion, CH3COO- will counteract the H+ forming a molecule of acetic acid.

If a strong base will be added, the acetic acid will counter act the hydroxide ion forming an
acetate ion and water.

Buffer could be acidic or basic. Acidic buffer is made of a weak acid and its salt and basic buffer
is made with weak base and its salt.
Henderson-Hasselbalch Equation

Suppose you want to prepare a buffer of known pH, how will achieve it? The answer lies on the
use of the Henderson-Hasselbalch equation. Consider a mixture of a hypothetical weak acid HA
and its salt Na+A-, the weak acid will dissociate partially while the salt exhibits complete
ionization following the reaction equation below,

The Ka expression for the hypothetical weak acid dissociation is as follow,

Manipulating the Ka expression to get the concentration of hydrogen ion we will have the
following equation,

Now taking the – log on both side we can have the following equation,

Or,

Take note that – log[H+] is pH, so – logKa is pKa. Simplifying the above equation, we can now
have the Henderson-Hasselbalch equation.

Or, more generically known as,

The Henderson-Hasselbalch equation is use to prepare a buffer with known pH. Usually a weak
acid with pKa close to the desired pH will be choose and make the concentration of the weak
acid and the salt equal. So, [conjugate base]/[acid] will be equal to 1 and log of 1 is 0. With that,
pH will be equal to pKa. The Henderson-Hasselbalch equation is also use to calculate the pH of
a buffer system.

Consider this example; what is the pH of a buffer system consisting of 0.30M NH3 and 0.36M
NH4Cl (Ka of NH+ = 5.6 x 10–10). The first thing to do is established a balanced chemical
equation involving the key species in the buffer system.

Using the Henderson-Hasselbalch equation and the given Ka values, the pH of the buffer
system can be calculated.
The components of the buffer are basic in nature; therefore, the pH is expected to be above 7.
From the Henderson-Hasselbalch equation it is calculated to be 9.17.
Common-Ion Effect

Common-ion effect is the shift in equilibrium as a result of the addition of a substance having a
common ion with the existing dissolved substance. The presence of common ion somehow
weakens the ionization of a weak acid or base. Say for example a mixture of a weak acid
CH3COOH and a strong electrolyte CH3COO-Na+.

The acetic acid exhibited partial dissociation since it’s a weak acid. On the other hand, sodium
acetate as a strong electrolyte exhibited complete dissociation. The added acetate ion from
sodium acetate will cause a shift of the formation of the acetic acid lowering its ionization. This
is a common-ion effect and this is prevalent among buffer solutions.