Buffers 2020

In aqueous solutions, two ions have dominant roles.
These
ions, the hydronium ion H3O+(or hydrogen ion, H+) and
the hydroxide ion OH−, are available in any aqueous
solution as a result of the autoionization of water, a
reaction of water with itself.
General, Organic, and Biological Chemistry: Structures of Life, 5/e © 2016 Pearson Education, Inc.
Karen C. Timberlake
Autoionization of Water
Although pure water is often considered a nonelectrolyte
(nonconductor of electricity), precise measurements do show a
very small conduction. This conduction results from
autoionization (or self-ionization), a reaction in which two like
molecules react to give ions. In the case of water, a proton from
one H2O molecule is transferred to another H2O molecule,
leaving behind an OH− ion and forming a hydronium ion,
H3O+(aq).
Karen C. Timberlake
The slight extent to which the autoionization of water occurs
by noting the small value of its equilibrium constant, which is
indicated here as Kw.
The concentration of H2O is excluded here because its

concentration remains essentially constant (as an essentially
pure liquid, H2O is excluded from the equilibrium constant).
The Kw is called, the equilibrium value of the ion product
[H3O+] [OH−], the ion-product constant for water.
Karen C. Timberlake
At 25°C, the value of Kw is 1.0 × 10−14. Like any
equilibrium constant, Kw varies with temperature. At body
temperature (37°C), Kw equals 2.5 × 10−14.
Because we often write H+(aq) for H3O+(aq), the ion-product

constant for water can be written Kw = [H+][OH−].
Karen C. Timberlake
pH
The pH of a solution is a measure of the molar concentration
of hydrogen ions in the solution and as such is a measure of
the acidity or basicity of the solution. The letters pH stand for
"power of hydrogen" and the numerical value is defined as the
negative base 10 logarithm of the molar concentration of
hydrogen ions.
Karen C. Timberlake
The pH of a Solution
Whether an aqueous solution is acidic, neutral, or basic depends on the
hydronium-ion concentration. You can quantitatively describe the
acidity by living the hydronium-ion concentration. But because these
concentration values may be very small, it is often more convenient to
give the acidity in terms of pH, which is defined as the negative of the
base 10 logarithm of the molar hydronium-ion concentration:
Karen C. Timberlake
Karen C. Timberlake
Karen C. Timberlake
The pH of a solution can be accurately
measured by a pH meter. A pH meter
measures [H3O+] by means of two electrodes
immersed in the test solution. One electrode
supplies a reference system; the other consists
of a very thin glass membrane that separates
a known internal [H3O+] from the unknown
external [H3O+]. The difference in [H3O+]
creates a voltage difference across the
membrane, which is displayed in pH units.
Karen C. Timberlake
Acid–base indicators are often used to measure pH, because
they usually change color within a small pH range. The color
change of an indicator involves establishment of an equilibrium
between an acid form and a base form that have different colors.
If we denote the acid form as HIn, then the base form is In− and
the equilibrium is
Karen C. Timberlake
Consider the case of phenolphthalein. The acid form is colorless
and the base form is pink. When a base is added to an acidic
solution of phenolphthalein, OH− ion from the base reacts with
H3O+ in the solution. According to Le Châtelier’s principle, the
equilibrium is shifted to the right (to replenish H3O+). Thus, the
colorless acid form of the indicator, HIn, is converted to the pink
base form, In−. A solution of phenolphthalein begins to turn pink
at about pH 8.0. By pH 9.7, the color change is essentially
complete.
Karen C. Timberlake
Color changes of
some acid–base
indicators.
Acid–base indicators
are dyes whose acid
form has one color
and whose base form
has another color.
Karen C. Timberlake
Paper strips
impregnated with several
indicators are often used to
measure pH values. Such
“pH paper” gives a deﬁnite
color for different pH
ranges and can give the pH
to the nearest integer value
or better.
Karen C. Timberlake
A sample of orange juice has a hydronium-ion concentration
of 2.9 x 10-4 M. What is the pH? Is the solution acidic?
Solution
pH = -log [H3O+]
= -log(2.9 x 10-
4 )
= 3.54
The pH is less than 7.00, so the solution is acidic (as you expect for orange
juice).
Exercise What is the pH of a sample of gastric juice (digestive juice

in the stomach) whose hydronium-ion concentration is 0.045 M?
Karen C. Timberlake
Give two important factors that determine the strength of an acid. How
does an increase in each factor affect the acid strength?
What is meant by the autoionization of water? Write the expression for

Kw. What is its value at 25°C?
Karen C. Timberlake
Karen C. Timberlake
11.9 Buffers
A buffer solution maintains the pH by neutralizing small amounts

of added acid or base.
An acid must be present to react with any OH− added, and a
base must be present to react with any H3O+ added.
Learning Goal Describe the role of buffers in maintaining

the pH of a solution; calculate the pH of a buffer.
Karen C. Timberlake
Buffers
When an acid or a base

is added to water, the
pH changes drastically.
In a buffer solution,
the pH is maintained;
pH does not change
when acids or bases
are added.
Karen C. Timberlake
How Buffers Work
Buffers work because

• they resist changes in pH from the addition of an acid or
a base.
• in the body, they absorb H3O+ or OH− from foods and
cellular processes to maintain pH.
• they are important in the proper functioning of cells
and blood.
• they maintain a pH close to 7.4 in blood.
A change in the pH of the blood affects the uptake of

oxygen and cellular processes.
Karen C. Timberlake
Components of a Buffer
The components of a buffer solution
▪ are acid–base conjugate pairs that have nearly equal
concentrations.
▪ can be a weak acid and a salt of its conjugate base.
▪ can also be a weak base and a salt of its conjugate
acid.
An acid must be present to react with any OH−.

A base must also be available to react with any added
H3O+.
© 2013 Pearson Education, Inc. Chapter 10, Section 6 20

Components of a Buffer
A buffer solution
• contains a combination of acid–base
conjugate pairs, a weak acid and a salt of its
conjugate base, such as
HC2H3O2(aq) and C2H3O2−(aq)
• has equal concentrations of a weak acid and

its salt.
Karen C. Timberlake
How Buffers Work
In the buffer with acetic acid (HC2H3O2) and sodium

acetate (NaC2H3O2),
• the salt produces acetate ions and sodium ions.
NaC2H3O2(aq) C2H3O2−(aq) + Na+(aq)
• the salt is added to provide a higher concentration of the
conjugate base C2H3O2− than from the weak acid alone.
HC2H3O2(aq) + H2O(l) C2H3O2−(aq) + H3O+(aq)
Large amount Large amount
Karen C. Timberlake
Buffer Action
An acetic acid/acetate buffer contains acetic acid
(HC2H3O2) and the salt of its conjugate base, sodium
acetate (NaC2H3O2).
▪ Acid dissociation occurs.
▪ The salt provides a higher concentration of the conjugate

base C2H3O2− than provided by the dissociation of the weak
acid by itself.

Function of a Weak Acid in a Buffer
If a small amount of base is added to this same buffer

solution, it is neutralized by the acetic acid, HC2H3O2,
which shifts the equilibrium in the direction of the products
acetate ion and water.
HC2H3O2(aq) + OH−(aq) C2H3O2−(aq) + H2O(l)

Equilibrium shifts in the direction of the products.
Karen C. Timberlake
Function of Conjugate Base in a Buffer
When a small amount of acid is added, the additional H3O+

combines with the acetate ion, C2H3O2−, causing the equilibrium to
shift in the direction of the reactants, acetic acid and water.
The acetic acid produced contributes to the available weak acid.

HC2H3O2(aq) + H2O(l) C2H3O2− (aq) + H3O+(aq)
Equilibrium shifts in the direction of the reactants.
Karen C. Timberlake
Working Buffers
The buffer described here consists of about equal concentrations of

acetic acid (HC2H3O2) and its conjugate base, acetate ion (C2H3O2−).
• Adding H3O+ to the buffer reacts with the salt, C2H3O2−, whereas
adding OH− neutralizes the acid HC2H3O2.
• The pH of the solution is maintained as long as the added
amounts of acid or base are small compared to the
concentrations of the buffer components.
Karen C. Timberlake
Buffer Calculations
Consider the equilibrium constant
expression for the dissociation of a generic
acid, HA:
HA + H2O H3O+ + A−
[H3O+] [A−]
Ka =
[HA]
© 2009, Prentice-Hall, Inc.

Buffer Calculations
Rearranging slightly, this becomes

[A −]
Ka = [H3O+]
[HA]
Taking the negative log of both side, we get
base
[A−]
−log Ka = −log [H3O+] + −log
[HA]
pKa
acid
pH
Buffer Calculations
• So
[base]
pKa = pH − log
[acid]
• Rearranging, this becomes
[base]
pH = pKa + log
[acid]
• This is the Henderson–Hasselbalch equation.

Calculating the pH of a Buffer
By rearranging the Ka expression to give [H3O+], we can obtain

the ratio of the acetic acid/acetate buffer and calculate the pH.
Solving for H3O+ gives
Weak acid
Conjugate base
Core Chemistry Skill Calculating the pH of a Buffer
Karen C. Timberlake
Study Check
The Ka for acetic acid, HC2H3O2, is 1.8 × 10–5. What is the pH

of a buffer prepared with 1.0 M HC2H3O2 and 1.0 M C2H3O2−?
Karen C. Timberlake
Solution

STEP 1 State the given and needed quantities.
ANALYZE Given Need

THE [HC2H3O2] = 1.0 M pH of solution
PROBLEM [C2H3O2−] = 1.0 M
Equation
Karen C. Timberlake
Solution

STEP 2 Write the Ka expression and rearrange for [H3O+].
Karen C. Timberlake
Solution
The Ka for acetic acid, HC2H3O2, is 1.8  10–5. What is the pH

STEP 3 Substitute [HA] and [A−] into the Ka expression.
Karen C. Timberlake
Solution
The Ka for acetic acid, HC2H3O2, is 1.8  10–5. What is the pH

STEP 4 Use [H3O+] to calculate pH.
Karen C. Timberlake
Calculating the pH of a Buffer
The [H3O+] in the Ka expression is used to determine
the pH of a buffer.

Guide to Calculating pH of a
Buffer

Calculating Buffer pH
The weak acid H2PO4− in a blood buffer, H2PO4−/HPO42−
has a . What is the pH of the buffer if
Analyze the Problem.

Step 1 Write the Ka expression.
Step 2 Rearrange Ka for [H3O+].

Step 3 Substitute Ka, [HA] and [A−].
Step 4 Use [H3O+] to calculate pH.

Learning Check
What is the pH of a H2CO3 buffer that is 0.20 M
H2CO3 and 0.10 M HCO3−?
A. 6.66
B. 6.36
C. 6.07

Solution
What is the pH of a H2CO3 buffer that is 0.20 M H2CO3
and 0.10 M HCO3−?
Analyze the Problem.

Solution
What is the pH of a H2CO3 buffer that is 0.20 M H2CO3
and 0.10 M HCO3−?
Step 1 Write the Ka expression.
Step 2 Rearrange Ka for [H3O+].

Solution
Step 3 Substitute Ka, [HA] and [A−].
Step 4 Use [H3O+] to calculate pH.

Titration
Primary standard substances
Secondary standard substances
Primary and secondary standard solution properties
Types of titration

46
Characteristics of primary standard substances:
A primary standard should satisfy the following requirements:
1. Purity:
It should be available in highly pure form. It should also preserve in a pure state.
2. Stability:
It should be stable (at 110˚c- 120˚c). There is no chemical change occurred.
3. Unaltered:
The substance should be unaltered in air during weighing, this condition implies that it should be
hygroscopic, oxidized by air, or affected by CO2.The standard should maintain an unchanged composition
during storage.
4. Test procedure:
The substance should be capable of being tested for impurities by qualitative and other tests of known
sensitivity. (The total amount of impurities should not exceed 0.01%-0.02%)
5. Molecular weight:
It should have a high molecular weight so that the weighing errors may be negligible.
6. Solubility:
It must be readily soluble in the solvent.
7. Titration error:
The reaction with the standard solution should be stoichiometric and practically instantaneous. The titration
error should be negligible, or easy to determine accurately by experiment.

Amount of oxalic acid needed to prepare 0.1 N oxalic acid solution:
The molecular formula of oxalic acid is COOH-COOH. 2H2O

The molecular weight of oxalic acid is (1×2 + 12×2 + 16×4 + 2×18) g = 126 g
The equivalent weight of oxalic acid is 126 g / 2 = 63 g
Therefore,
1000 mL 1 N solution requires 63 g of oxalic acid

1 mL 1N ˶ ˶ (63 g×1 mL) / 1000 mL of oxalic acid
250 mL 0.1 N ˶ ˶ (63 g0.1 N250 mL)  (1 N  1000 mL)
= 1.575 g of oxalic acid
So, 1.575 g oxalic acid is required to prepare 250 mL of 0.1 N solution.

Amount of conc. H2SO4 needed to prepare 0.1 N H2SO4 solution:
Molecular weight of H2SO4 is (1×2 + 32 + 16×4) g = 98g

Equivalent weight of H2SO4 is (98 g /2) = 49 g
Therefore,
1000 mL 1 N solution requires 49 g sulfuric acid
1000 mL 0.1 N ˶ ˶ (49 g  0.1 N / 1 N) = 4.9 g sulfuric acid
So, 4.9 g sulfuric acid is required to prepare 1000 mL of 0.1 N solution
Sulfuric acid is a hygroscopic substance. Commercially available conc. H 2SO4 is present in

98% w/w pure form.
98 g pure acid presents in 100 g conc. H2SO4

4.9 g ˶ ˶ (100 g  4.9 g  98 g)
= 5 g conc. H2SO4
Since, H2SO4 is liquid substance, it is measured by volume.
We know,
Mass, M
Density, d =
Volume, V
Here,
Density of sulfuric acid is 1.84 gcm-3
Mass of the sulfuric acid needed is 5 g
Therefore, the required volume of sulfuric acid is (5 g / 1.84 gcm-3) = 2.7 mL (approx.)
So, 2.7 mL sulfuric acid is required to prepare 1000 mL of 0.1 N solution.


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In aqueous solutions, two ions have dominant roles.

ions, the hydronium ion H3O+(or hydrogen ion, H+) and

the hydroxide ion OH−, are available in any aqueous

solution as a result of the autoionization of water, a

reaction of water with itself.

The concentration of H2O is excluded here because its

Because we often write H+(aq) for H3O+(aq), the ion-product

The pH of a solution is a measure of the molar concentration

of hydrogen ions in the solution and as such is a measure of

the acidity or basicity of the solution. The letters pH stand for

"power of hydrogen" and the numerical value is defined as the

negative base 10 logarithm of the molar concentration of

Exercise What is the pH of a sample of gastric juice (digestive juice

What is meant by the autoionization of water? Write the expression for

A buffer solution maintains the pH by neutralizing small amounts

Learning Goal Describe the role of buffers in maintaining

When an acid or a base

Buffers work because

A change in the pH of the blood affects the uptake of

An acid must be present to react with any OH−.

© 2013 Pearson Education, Inc. Chapter 10, Section 6 20

• has equal concentrations of a weak acid and

In the buffer with acetic acid (HC2H3O2) and sodium

▪ The salt provides a higher concentration of the conjugate

© 2013 Pearson Education, Inc. Chapter 10, Section 6 23

If a small amount of base is added to this same buffer

HC2H3O2(aq) + OH−(aq) C2H3O2−(aq) + H2O(l)

When a small amount of acid is added, the additional H3O+

The acetic acid produced contributes to the available weak acid.

The buffer described here consists of about equal concentrations of

© 2009, Prentice-Hall, Inc.

Rearranging slightly, this becomes

© 2009, Prentice-Hall, Inc.

By rearranging the Ka expression to give [H3O+], we can obtain

Solving for H3O+ gives

Core Chemistry Skill Calculating the pH of a Buffer

The Ka for acetic acid, HC2H3O2, is 1.8 × 10–5. What is the pH

The Ka for acetic acid, HC2H3O2, is 1.8 × 10–5. What is the pH

STEP 1 State the given and needed quantities.

ANALYZE Given Need

The Ka for acetic acid, HC2H3O2, is 1.8 × 10–5. What is the pH

STEP 2 Write the Ka expression and rearrange for [H3O+].

The Ka for acetic acid, HC2H3O2, is 1.8  10–5. What is the pH

STEP 3 Substitute [HA] and [A−] into the Ka expression.

The Ka for acetic acid, HC2H3O2, is 1.8  10–5. What is the pH

STEP 4 Use [H3O+] to calculate pH.

© 2013 Pearson Education, Inc. Chapter 10, Section 6 36

© 2013 Pearson Education, Inc. Chapter 10, Section 6 37

Analyze the Problem.

© 2013 Pearson Education, Inc. Chapter 10, Section 6 38

Step 1 Write the Ka expression.

Step 2 Rearrange Ka for [H3O+].

© 2013 Pearson Education, Inc. Chapter 10, Section 6 39

Step 3 Substitute Ka, [HA] and [A−].

Step 4 Use [H3O+] to calculate pH.

© 2013 Pearson Education, Inc. Chapter 10, Section 6 40

© 2013 Pearson Education, Inc. Chapter 10, Section 6 41

Analyze the Problem.

© 2013 Pearson Education, Inc. Chapter 10, Section 6 42

Step 1 Write the Ka expression.

Step 2 Rearrange Ka for [H3O+].

© 2013 Pearson Education, Inc. Chapter 10, Section 6 43

Step 3 Substitute Ka, [HA] and [A−].

Step 4 Use [H3O+] to calculate pH.