HOMOGENEOUS SYSTEMS:

Colligative Properties | Acid-Base Equilibria

Buffer Systems | Isotonic Solutions
Learning Objectives
• Solve problems utilizing concentration expressions

• Define and demonstrate an understanding of the colligative properties of

nonelectrolyte and electrolyte solutions

• Identify the role of isotonic solutions in biological systems

• Demonstrate understanding on the concepts of acids and bases

• Perform calculations on buffer and isotonic solutions

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Outline
1. Homogeneous Systems 4. Isotonic Solutions
1. Definitions 1. Definition
2. Physical Properties of Substances 2. Determination of Tonicity
3. Concentration expressions 3. Adjusting Tonicity
2. Ideal Solutions 4. Calculations
1. Properties 5. Ionic Equilibria
2. Raoult’s Law 1. Importance
3. Aerosols 2. Calculations
4. Henry’s Law
3. Colligative Properties of Solutions
1. Vapor Pressure Lowering
2. Boiling Point Elevation
3. Freezing Point Depression
4. Osmotic Pressure

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HOMOGENEOUS SYSTEMS
1. Definitions
2. Physical Properties of Substances
3. Concentration expressions
HOMOGENEOUS SYSTEMS
• System • True solution
• Dispersion • Coarse dispersions
• Phase • Colloidal dispersions

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Physical Properties of Substances

Extensive mass, volume

temperature, pressure, density, surface tension,
Intensive
viscosity of a pure liquid
osmotic pressure, vapor pressure lowering,
Colligative
freezing point depression, boiling point elevation

Additive molecular weight

refraction of light*, electric properties*, surface
Constitutive
tension*, interfacial characteristics*

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Concentration Expressions
1. Molarity
2. Normality
3. Molality
4. Mole fraction
5. Mole percent
6. Percent by weight
7. Percent by volume
8. Percent weight-in-volume

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IDEAL SOLUTIONS
1. Properties
2. Raoult’s Law
3. Aerosols
4. Henry’s Law
Properties of Ideal Solutions
• No change in the physical properties of the components other than dilution when they
are mixed
• No heat is given off or takin in
• The volume does not shrink or expand
Alcohol and water
• Not an ideal mixture
• Mixture gets warm, heat is given off, and the final volume of the solution is less than that
of the sum of the two components

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Raoult’s Law
• In an ideal solution, the partial vapor pressure of
each volatile constituent is equal to the vapor
pressure of the pure constituent multiplied by its
mole fraction in the solution

• Relationship between the vapor pressure for a liquid

and its mole fraction in solution

• The vapor pressure of each volatile constituent is

equal to the vapor pressure of the pure constituent
multiplied by its mole fraction in the solution

𝑝𝐴 = 𝑝𝐴° 𝑋𝐴

𝑝𝐵 = 𝑝𝐵° 𝑋𝐵
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Raoult’s Law in Aerosols
• An aerosol contains the drug concentrated in a solvent or a carrier liquid and a propellant
mixture of the proper vapor characteristics
• Since propellants represent the vast majority (>99%) of the dose delivered by a metered
dose inhaler, it must be nontoxic to the patient

11
Henry’s Law
• At a constant temperature, the amount of a given gas that dissolves in a given type and
volume of liquid is directly proportional to the partial pressure of that gas in equilibrium
with that liquid

12
COLLIGATIVE PROPERTIES OF SOLUTIONS
1. Vapor Pressure Lowering
2. Boiling Point Elevation
3. Freezing Point Depression
4. Osmotic Pressure
COLLIGATIVE PROPERTIES
• When a nonvolatile solute is combined with a volatile solvent, the vapor above the
solution is provided solely by the solvent.
• The solute reduces the escaping tendency of the solvent, and based of Raoult’s Law,
lowers the vapor pressure of a solution.

Several assumptions are operating in the application of colligative properties to

pharmaceutical systems
1. Solute is nonvolatile, and the solvent is water
2. For nonelectrolytes, values of colligative properties are the same for different solutes at
the same molar concentration
3. For strong electrolytes, values of colligative properties, depend on the number of ions
4. For weak electrolytes, values of colligative properties depend on ionization
5. Solutions are dilute

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Vapor Pressure Lowering
• Vapor pressure of a solution is less than that of the pure solvent

Raoult’s Law
𝑃1 = 𝑋1 𝜌1°
• P1 is the vapor pressure of the solvent above the solution
• X1 is the solvent mole fraction
• ρ1° is the vapor pressure of the pure solvent
• It is more convenient to express the vapor pressure of the solution in terms of the
concentration of the solute rather than the mole fraction of the solvent

15
Vapor Pressure Lowering
Raoult’s Law
𝑃1 = 𝑋1 𝜌1°

𝑋1 + 𝑋2 = 1
𝑃1 = (1 − 𝑋2 )𝜌1°
𝜌1° − 𝑃1 = 𝑋2 𝜌1°
∆𝑃 = 𝑋2 𝜌1°
• ΔP is the lowering of vapor pressure from pure solvent to solution, it is directly
proportional to the mole fraction of the solute
• The lowering of vapor pressure depends on the number of solute particles in a definite
volume of solution

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Boiling Point Elevation
• The normal boiling point is the temperature at which the vapor pressure of the liquid
becomes equal to the external pressure of 760 mmHg
• A solution will boil at a higher temperature than will the pure solvent

∆𝑇𝑏 = 𝐾𝑏 𝑚

• ΔTb is the absolute value of the increase in boiling point in degrees, boiling point
elevation
• Kb is the molal elevation constant, ebullioscopic constant of the solvent
• m is the molal concentration of solute
• Boiling point elevation is usually small and subject to barometric pressure therefore
measurement of this property is not practical

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Freezing Point Depression
• The normal freezing point or melting point of a pure compound is the temperature at
which the solid and the liquid phases are in equilibrium under a pressure of 1 atm
• The freezing point of a solution is always lower than that of the pure solvent

∆𝑇𝑓 = 𝐾𝑓 𝑚
• ΔTf is the absolute value of the decrease in melting point in degrees, freezing point
depression
• Kf is molal depression constant, cryoscopic constant of the solvent
• m is the molal concentration of the solute

18
Freezing Point Depression
For weak and strong electrolytes, the ionization factor must also be considered
∆𝑇𝑓 = 𝑖𝐾𝑓 𝑚

• The relationship between the actual number of moles of solute added to form a solution
and the apparent number as determined by colligative properties is called the van’t Hoff
factor (i)
𝑎𝑝𝑝𝑎𝑟𝑒𝑛𝑡 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑖𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑖=
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑
Nonelectrolytes and substances of slight dissociation 1.0
Substances that dissociate into 2 ions 1.8
Substances that dissociate into 3 ions 2.6
Substances that dissociate into 4 ions 3.4
Substances that dissociate into 5 ions 4.2

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Freezing Point Depression
A modification of the van’t Hoff equation, uses the Liso value for the iKf term

∆𝑇𝑓 = 𝐿𝑖𝑠𝑜 𝑚

Compound Type by Valence Liso value

Nonelectrolyte 1.86
Weak electrolyte 2.0
Di-divalent electrolyte
2.0
Divalent cation and divalent anion
Uni-univalent electrolyte
3.4
Single charge on each
Uni-divalent electrolyte 4.3
Di-univalent electrolyte 4.8

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Osmotic Pressure
• Semipermeable membrane: a barrier that permits only the molecules of one of the
components (usually water) to pass through
• Osmosis: passage of the solvent into a solution through a semipermeable membrane

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ISOTONIC SOLUTIONS
1. Definition
2. Determination of Tonicity
3. Adjusting Tonicity
4. Calculations
Isotonic Solutions
• Pharmaceutical solutions that are meant for application to delicate membranes of the
body should also be adjusted to approximately the same osmotic pressure as that of the
body fluids.
• Isotonic solutions cause no swelling or contraction of the tissues with which they come in
contact and produce no discomfort when instilled in the eye, nasal tract, blood, or other
body tissues. (isotonic sodium chloride)

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Determination of Tonicity
1. Hemolytic Method
• Effect of various solutions of drug is observed on the appearance of red blood cells
suspended in solution.
• RBCs are suspended in various solutions and the appearance of RBC is observed
for swelling, bursting, shrinking and wrinkling of the blood cells
• In hypotonic solutions, the oxyhemoglobin released is proportional to the number of
cells hemolysed; in case of hypertonic solutions, the cells shrink and become
wrinkled or crenated whereas in case of isotonic solutions the cells do not change
their morphology

2. Crysocopic Method
• Isotonicity values can be determined from the colligative properties of the solutions.
For this purpose, freezing point depression property is most extensively used

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Adjusting Tonicity
• Used to determine the amount of adjusting agents to be added to a preparation
• Helps to overcome the side effects caused from administering solutions which contain
adjusting agents less or more than isotonic solutions

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Adjusting Tonicity
Class I Method
NaCl or some other substances is added to the solution of the drug to lower the freezing point of the
solution to -0.52ᵒC and thus make the solution isotonic
1. Cryoscopic Method
2. Sodium Chloride Equivalent Method

Class II Method
Water is added to the drug in a sufficient amount to make it isotonic, then the preparation is brought to
its final volume with an isotonic or buffered isotonic solution
1. White Vincent Method

Class III Method

Freezing point depression and Liso values for number of drugs are estimated theoretically from the
molecular weight of the drug and can be used to calculate the amount of adjusting substance to be
added in order to make the solution isotonic
1. Liso Method

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TONICITY

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 TONICITY
CALCULATIONS INVOLVED IN PREPARING ISOTONIC SOLUTIONS
• Relate data from colligative properties of solutions
• FREEZING POINT data is usually used

-0.52°C
freezing point of both blood serum and lacrimal fluid

1.86°C below the freezing point of pure water

freezing point when one gram molecular weight of any nonelectrolyte (substance with
negligible dissociation such as boric acid) is dissolved in 1000 g of water

Therefore, we can calculate the weight of any nonelectrolyte that should be dissolved in
each 1000 g of water if the solution is to be isotonic with body fluids

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 TONICITY - NONELECTROLYTES
CALCULATIONS INVOLVED IN PREPARING ISOTONIC SOLUTIONS
The weight of any nonelectrolyte that should be dissolved in each 1000 g of water if the solution is
to be isotonic with body fluids
Boric Acid
MW = 61.8 g
In theory, 61.8 g in 1000 g of water should produce a freezing point of -1.86°C

1.86°𝐶 61.8 𝑔
=
0.52°𝐶 𝑥
x = 17.3 g

Therefore, 17.3 g of boric acid in 1000 g of water, having a weight-in-volume strength of

approximately 17.3%, should make a solution isotonic with lacrimal fluid

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 TONICITY - ELECTROLYTES
CALCULATIONS INVOLVED IN PREPARING ISOTONIC SOLUTIONS
• Osmotic pressure depends more on the number than on the kind of particles,
substances that dissociate have a tonic effect that increases with the degree of
dissociation
• The greater the dissociation, the smaller the quantity required to produced any given
osmotic pressure

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 TONICITY - ELECTROLYTES
CALCULATIONS INVOLVED IN PREPARING ISOTONIC SOLUTIONS
NaCl in weak solutions is about 80% dissociated, then 100 molecules yields 180 particles, or 1.8
times as many particles as are yielded by 100 molecules of nonelectrolyte.

DISSOCIATION FACTOR commonly symbolized by the letter i, must be included in the proportion
when we seek to determine the strength of an isotonic solution of sodium chloride (mw 58.5).

1.86°𝐶 𝑥 1.8 58.5𝑔

=
0.52°𝐶 𝑥

x = 9.09 g
Hence, 9.09 g of sodium chloride in 1000 g of water should make a solution isotonic with blood or
lacrimal fluid.

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 TONICITY - ELECTROLYTES
CALCULATIONS INVOLVED IN PREPARING ISOTONIC SOLUTIONS
In practice, a 0.90% w/v sodium chloride solution is considered isotonic with body fluids.
Simple isotonic solutions may then be calculated by using this formula:

0.52 𝑥 𝑀𝑊 𝑔𝑠𝑜𝑙𝑢𝑡𝑒
=
1.86 𝑥 𝑖 1000 𝑔𝐻2𝑂

The value of i should be experimentally determined, but most medicinal salts approximate the
dissociation of sodium chloride in weak solutions. If the number of ions is known, we may use the
following values, lacking better information: (i values).
If the number of ions is known…
Nonelectrolytes and substances of slight dissociation i=1
Substances that dissociate into 2 ions i = 1.8
Substances that dissociate into 3 ions i = 2.6
Substances that dissociate into 4 ions i = 3.4
Substances that dissociate into 5 ions i = 4.2

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 MAKE A SOLUTION ISOTONIC BY ADDING THE PROPER
AMOUNT OF SUBSTANCE OTHER THAN THE ACTIVE INGREDIENT
Given a 0.5% w/v solution of NaCl, we may easily calculate that

0.9 g - 0.5 g = 0.4 g

0.4 g of additional sodium chloride that should be contained in each 100 mL if the solution is to be
made isotonic with a body fluid

But how much sodium chloride should be used in preparing 100 mL of a 1% w/v solution of
atropine sulfate, which is to be made isotonic with lacrimal fluid?

The answer depends on how much sodium chloride is in effect represented by the atropine sulfate.

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 MAKE A SOLUTION ISOTONIC BY ADDING THE PROPER
AMOUNT OF SUBSTANCE OTHER THAN THE ACTIVE INGREDIENT

The answer depends on how much sodium chloride is in effect

represented by the atropine sulfate.

The relative tonic effect of two substances, quantity of one that is

equivalent in tonic effects to a given quantity of the other may be
calculated if the quantity of one having a certain effect in a specified
quantity of solvent is divided by the quantity of the other having the
same effect in the same quantity of solvent.

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 MAKE A SOLUTION ISOTONIC BY ADDING THE PROPER
AMOUNT OF SUBSTANCE OTHER THAN THE ACTIVE INGREDIENT
For example, we calculated that 17.3 g of boric acid per 1000 g of water and 9.09 g of
sodium chloride per 1000 g of water are both instrumental in making an aqueous
solution isotonic with lacrimal fluid.

If, however, 17.3 g of boric acid are equivalent in tonicity to 9.09 g of sodium chloride,
then 1 g of boric acid must be the equivalent of 9.09 g / 17.3 g or 0.52 g of sodium
chloride.
9.09 𝑔 𝑁𝑎𝐶𝑙
1𝑔 𝐻3𝐵𝑂3 =
17.3 𝑔 𝐻3𝐵𝑂3

Similarly, 1 g of sodium chloride must be the ‘‘tonicic equivalent’’ of 17.3 g / 9.09 g or

1.90 g of boric acid.
17.3 𝑔
= 𝟏. 𝟗𝟎 𝒈 𝒃𝒐𝒓𝒊𝒄 𝒂𝒄𝒊𝒅
9.09 𝑔
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 MAKE A SOLUTION ISOTONIC BY ADDING THE PROPER
AMOUNT OF SUBSTANCE OTHER THAN THE ACTIVE INGREDIENT
RULE
quantities of two substances that are tonicic equivalents are proportional to the
molecular weights of each multiplied by the i value of the other

NaCl: MW = 58.5; i = 1.8

atropine sulfate: MW = 695; i = 2.6
695 𝑥 1.8 1
=
58.5 𝑥 2.6 𝑥
x = 0.12g sodium chloride represented by 1g atropine

Because a solution isotonic with lacrimal fluid should contain the equivalent of 0.90 g of
sodium chloride in each 100 mL of solution, the difference to be added must be

0.90 g - 0.12g = 0.78 g NaCl

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 MAKE A SOLUTION ISOTONIC BY ADDING THE PROPER
AMOUNT OF SUBSTANCE OTHER THAN THE ACTIVE INGREDIENT

E VALUE. calculated by the rule,

If the number of grams of a substance included in a prescription

is multiplied by its sodium chloride equivalent, the amount of
sodium chloride represented by that substance is determined.

37
 MAKE A SOLUTION ISOTONIC BY ADDING THE PROPER
AMOUNT OF SUBSTANCE OTHER THAN THE ACTIVE INGREDIENT
STEP 1.
Calculate the amount (in grams) of sodium chloride represented by the ingredients in the
prescription. Multiply the amount (in grams) of each substance by its sodium chloride
equivalent.

STEP 2.
Calculate the amount (in grams) of sodium chloride, alone, that would be contained in an
isotonic solution of the volume specified in the prescription, namely, the amount of
sodium chloride in a 0.9% solution of the specified volume. (Such a solution would
contain 0.009 g/mL.)

38
 MAKE A SOLUTION ISOTONIC BY ADDING THE PROPER
AMOUNT OF SUBSTANCE OTHER THAN THE ACTIVE INGREDIENT
STEP 3.
Subtract the amount of sodium chloride represented by the ingredients in the
prescription (Step 1) from the amount of sodium chloride, alone, that would be
represented in the specific volume of an isotonic solution (Step 2). The answer represents
the amount (in grams) of sodium chloride to be added to make the solution isotonic.

STEP 4.
If an agent other than sodium chloride, such as boric acid, dextrose, or potassium nitrate,
is to be used to make a solution isotonic, divide the amount of sodium chloride (Step 3)
by the sodium chloride equivalent of the other substance.

39
 #1 – I FACTOR
Zinc sulfate is a 2-ion electrolyte, dissociating 40% in a certain
concentration. Calculate its dissociation (i) factor.

SAMPLE PROBLEMS 40
 #1 – I FACTOR
On the basis of 40% dissociation, 100 particles of zinc sulfate will yield:
40 zinc ions
40 sulfate ions
60 undissociated particles +
140 particles

Because 140 particles represent 1.4 times as many particles as were

present before dissociation, the dissociation (i) factor is 1.4, answer.

SAMPLE PROBLEMS 41
 #2 – I FACTOR
Zinc chloride is a 3-ion electrolyte, dissociating 80% in a certain
concentration. Calculate its dissociation (i) factor.

SAMPLE PROBLEMS 42
 #2 – I FACTOR
On the basis of 80% dissociation, 100 particles of zinc chloride will yield:
80 zinc ions
80 chloride ions
80 chloride ions
20 undissociated particles +
260 particles

Because 260 particles represents 2.6 times as many particles as were

present before dissociation, the dissociation (i) factor is 2.6, answer.

SAMPLE PROBLEMS 43
 SODIUM CHLORIDE EQUIVALENT
The sodium chloride equivalent of a substance may be calculated as
follows:

𝑴𝑾𝑵𝒂𝑪𝒍 𝒊𝒔𝒖𝒃𝒔
𝒙 = 𝑵𝒂𝑪𝒍 𝑬𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕 (𝑬)
𝒊𝑵𝒂𝑪𝒍 𝑴𝑾𝒔𝒖𝒃𝒔

44
 #3 – E VALUE
Papaverine hydrochloride (MW 376) is a 2-ion electrolyte, dissociating 80%
in a given concentration. Calculate its sodium chloride equivalent.

SAMPLE PROBLEMS 45
 #3 – E VALUE
Because papaverine hydrochloride is a 2-ion electrolyte, dissociating 80%,
its i factor is 1.8.

𝟓𝟖. 𝟓 𝟏. 𝟖
𝒙 = 𝟎. 𝟏𝟓𝟔 𝒐𝒓 𝟎. 𝟏𝟔
𝟏. 𝟖 𝟑𝟕𝟔

SAMPLE PROBLEMS 46
 #4 – E VALUE
Calculate the sodium chloride equivalent for glycerin, a nonelectrolyte with
a molecular weight of 92.2
Glycerin, i factor = 1.0

SAMPLE PROBLEMS 47
 #4 – E VALUE
MW = 92.2; i = 1.0

𝟓𝟖. 𝟓 𝟏. 𝟎
𝒙 = 𝟎. 𝟑𝟓
𝟏. 𝟖 𝟗𝟐

SAMPLE PROBLEMS 48
 #5 – E VALUE
Calculate the sodium chloride equivalent for timolol maleate, which
dissociates into two ions and has a molecular weight of 432.2
Timolol maleate, i factor = 1.8

SAMPLE PROBLEMS 49
 #5 – E VALUE
MW = 432.2; i = 1.8

𝟓𝟖. 𝟓 𝟏. 𝟖
𝒙 = 𝟎. 𝟏𝟒
𝟏. 𝟖 𝟒𝟑𝟐

SAMPLE PROBLEMS 50
 #6 – E VALUE
Calculate the sodium chloride equivalent for fluorescein sodium, which
dissociates into three ions and has a molecular weight of 376.2
Fluorescein sodium, i factor = 2.6

SAMPLE PROBLEMS 51
 #6 – E VALUE
3 ions; MW = 367.2; i = 2.6

𝟓𝟖. 𝟓 𝟐. 𝟔
𝒙 = 𝟎. 𝟐𝟑
𝟏. 𝟖 𝟑𝟔𝟕

SAMPLE PROBLEMS 52
 #7 – CALCULATIONS OF TONICIC AGENT REQUIRED
How many grams of sodium chloride should be used in compounding the
following prescription?

Rx Pilocarpine Nitrate 0.3 g

Sodium Chloride q.s.
Purified Water ad 30 mL
Make isoton. sol.
Sig. For the eye.

SAMPLE PROBLEMS 53
 #7 – CALCULATIONS OF TONICIC AGENT REQUIRED
Step 1.
0.23 x 0.3 g = 0.069 g of sodium chloride represented by the pilocarpine
nitrate

Step 2.
30 x 0.009 = 0.270 g of sodium chloride in 30 mL of an isotonic sodium
chloride solution

Step 3.
0.270 g (from Step 2) - 0.069 g (from Step 1) = 0.201 g of sodium chloride
to be used, answer.

SAMPLE PROBLEMS 54
 #8 – CALCULATIONS OF TONICIC AGENT REQUIRED
How many grams of boric acid should be used in compounding the
following prescription?

Rx Phenacaine Hydrochloride 1%
Chlorobutanol 1/2%
Boric Acid q.s.
Purified Water ad 60
Make isoton. sol.
Sig. One drop in each eye.

The prescription calls for 0.6 g of phenacaine hydrochloride and 0.3 g of

chlorobutanol.

SAMPLE PROBLEMS 55
 #8 – CALCULATIONS OF TONICIC AGENT REQUIRED
STEP 1.
0.20 x0.6 g = 0.120 g of sodium chloride represented by phenacaine hydrochloride
0.24 x 0.3 g = 0.072 g of sodium chloride represented by chlorobutanol
Total: 0.192 g of sodium chloride represented by both ingredients

STEP 2.
60 x 0.009 = 0.540 g of sodium chloride in 60 mL of an isotonic sodium chloride solution

STEP 3.
0.540 g (from Step 2) - 0.192 g (from Step 1) = 0.348 g of sodium chloride required to make the solution
isotonic

But because the prescription calls for boric acid:

STEP 4.
0.348 g / 0.52 (sodium chloride equivalent of boric acid) = 0.669 g of boric acid to be used, answer.

SAMPLE PROBLEMS 56
 #9 – CALCULATIONS OF TONICIC AGENT REQUIRED
How many grams of potassium nitrate could be used to make the following
prescription isotonic?

Rx Sol. Silver Nitrate 60

1:500 w/v
Make isoton. sol.
Sig. For eye use.

The prescription contains 0.12 g of silver nitrate.

SAMPLE PROBLEMS 57
 #9 – CALCULATIONS OF TONICIC AGENT REQUIRED
STEP 1.
0.33 x 0.12 g = 0.04 g of sodium chloride represented by silver nitrate

STEP 2.
60 x 0.009 = 0.54 g of sodium chloride in 60 mL of an isotonic sodium chloride solution

STEP 3.
0.54 g (from step 2) - 0.04 g (from step 1) = 0.50 g of sodium chloride required to make
solution isotonic

Because, in this solution, sodium chloride is incompatible with silver nitrate, the tonic agent of
choice is potassium nitrate. Therefore,

STEP 4.
0.50 g / 0.58 (sodium chloride equivalent of potassium nitrate) = 0.86 g of potassium nitrate
to be used, answer.

SAMPLE PROBLEMS 58
 #10 – CALCULATIONS OF TONICIC AGENT REQUIRED
How many grams of sodium chloride should be used in compounding the
following prescription?

Rx Ingredient X 0.5
Sodium Chloride q.s.
Purified Water ad 50

Make isoton. sol.

Sig. Eye drops.

SAMPLE PROBLEMS 59
59
 #10 – CALCULATIONS OF TONICIC AGENT REQUIRED
Let us assume that ingredient X is a new substance for which no sodium chloride
equivalent is to be found in Table 11.1, and that its molecular weight is 295 and its
i factor is 2.4. The sodium chloride equivalent of ingredient X may be calculated as
follows:

(58.5/1.8) x (2.4/295) = 0.26, the sodium chloride equivalent for ingredient X

Step 1. 0.26 x 0.5 g = 0.13 g of sodium chloride represented by ingredient X

Step 2. 50 x 0.009 = 0.45 g of sodium chloride in 50 mL of an isotonic sodium

chloride
solution

Step 3. 0.45 g (from Step 2) - 0.13 g (from Step 1) = 0.32 g of sodium chloride to
be used, answer.

SAMPLE PROBLEMS 60
60
 USING ISOTONIC SODIUM CHLORIDE SOLUTION TO PREPARE
OTHER ISOTONIC SOLUTIONS
A 0.9% w/v sodium chloride solution may be used to compound isotonic solutions of
other drug substances as follows:

STEP 1.
Calculate the quantity of the drug substance needed to fill the prescription or medication
order.

STEP 2.
Use the following equation to calculate the volume of water needed to render a solution
of the drug substance isotonic:

𝑔𝑑𝑟𝑢𝑔 𝑥 𝐸 𝑣𝑎𝑙𝑢𝑒𝑑𝑟𝑢𝑔
0.009
= 𝑚𝐿 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑛𝑒𝑒𝑑𝑒𝑑 𝑡𝑜 𝑚𝑎𝑘𝑒 𝑎𝑛 𝑖𝑠𝑜𝑡𝑜𝑛𝑖𝑐 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑒 𝑑𝑟𝑢𝑔
the volume of the drug substance is considered negligible
61
 USING ISOTONIC SODIUM CHLORIDE SOLUTION TO PREPARE
OTHER ISOTONIC SOLUTIONS
STEP 3.
Add 0.9% w/v sodium chloride solution to complete the required volume of the
prescription or medication order.

62
 #11 –
Using this method, determine the volume of purified water and 0.9% w/v
sodium chloride solution needed to prepare 20 mL of a 1% w/v solution of
hydromorphone hydrochloride (E = 0.22).

SAMPLE PROBLEMS 63
 #11 –
STEP 1. 20 mL x 1% w/v = 0.2 g hydromorphone needed

STEP 2. (0.2 g x 0.22) / 0.009 = 4.89 mL purified water required to make an

isotonic solution of hydromorphone hydrochloride, answer.

STEP 3. 20 mL - 4.89 mL = 15.11 mL 0.9% w/v sodium chloride solution

required, answer.

SAMPLE PROBLEMS 64
64
 #11 –
Proof:
20 mL x 0.9% = 0.18 g sodium chloride or equivalent required

0.2 x 0.22 = 0.044 g (sodium chloride represented by 0.2 g hydromorphone

hydrochloride)

15.11 mL x 0.9 % = 0.136 g sodium chloride present

0.044 g + 0.136 g = 0.18 g sodium chloride required for isotonicity

SAMPLE PROBLEMS 65
65
 USE OF FREEZING POINT DATA IN ISOTONICTY CALCULATIONS

Freezing point data (ΔTf) can be used in isotonicity calculations when the
agent has a tonicic effect and does not penetrate the biologic membranes
in question (e.g., red blood cells).

The freezing point of both blood and lacrimal fluid is -0.52°C.

Thus, a pharmaceutical solution that has a freezing point of -0.52°C is

considered isotonic.

66
66
Freezing point depression data may be
used in isotonicity calculations as
shown by the following:

67
67
 #12 – CALCULATIONS USING FREEZING POINT DATA
How many milligrams each of sodium chloride and dibucaine
hydrochloride are required to prepare 30 mL of a 1% solution of dibucaine
hydrochloride isotonic with tears?

SAMPLE PROBLEMS 68
68
 #12 – CALCULATIONS USING FREEZING POINT DATA
To make this solution isotonic, the freezing point must be lowered to -0.52 °C. From Table
11.2, it is determined that a 1% solution of dibucaine hydrochloride has a freezing point
lowering of 0.08 °C.
Thus, sufficient sodium chloride must be added to lower the freezing point an additional
0.44 °C (0.52 °C - 0.08 °C).

Also from Table 11.2, it is determined that a 1% solution of sodium chloride lowers the
freezing point by 0.58 °C. By proportion:

1% 𝑁𝑎𝐶𝑙 0.58°𝐶
=
𝑥% 𝑁𝑎𝐶𝑙 0.44°𝐶

x = 0.76% (the concentration of sodium chloride needed to lower the freezing point by
0.44, required to make the solution isotonic)

SAMPLE PROBLEMS 69
69
 #12 – CALCULATIONS USING FREEZING POINT DATA
Thus, to make 30 mL of solution,
30 mL x 1% = 0.3 g = 300 mg dibucaine hydrochloride, and
30 mL x 0.76% = 0.228 g = 228 mg sodium chloride, answers.

Note: Should a prescription call for more than one medicinal and/or
pharmaceutic ingredient, the sum of the freezing points is subtracted from
the required value in determining the additional lowering required by the
agent used to provide isotonicity.

SAMPLE PROBLEMS 70
IONIC EQUILIBRIA
1. Importance
2. Calculations
pH-Partition Hypothesis
The absorption of a weak electrolyte is determined mainly by the extent to which the drug
exists in its unionized form at the site of absorption
The pH – Partition Hypothesis
The absorption of a weak electrolyte is determined mainly by the extent to
which the drug exists in its unionized form at the site of absorption

For drugs of molecular weight greater than 100 which are primarily
transported across the membranes by passive diffusion, the process is
governed by

1. The dissociation constant (Ka) of the drug

2. The lipid solubility of the unionized drug (a function of drug Ko/w)
3. The pH at the absorption site

72
The Ionization of Water
One molecule of water can be thought of as a weak electrolytic solute that reacts
with another molecule of water as the solvent

𝐻2 𝑂 + 𝐻2 𝑂 ↔ 𝐻3 𝑂+ + 𝑂𝐻 −

The law of mass action is then applied to give the equilibrium expression
𝐻3 𝑂+ [𝑂𝐻 − ]
𝑘=
[𝐻2 𝑂]2

73
The Ionization of Water
𝐻3 𝑂+ [𝑂𝐻 − ]
𝑘=
[𝐻2 𝑂]2

Since molecular water exists in great excess relative to the concentrations of

hydrogen and hydroxyl ions, [H2O]2 is considered as a constant and is combined
with k to give a new constant, Kw, known as the dissociation constant, the
autoprotolysis constant, or the ion product of water.

𝐾𝑤 = 𝑘 × [𝐻2 𝑂]2

The value of the ion product is approximately 𝟏 × 𝟏𝟎−𝟏𝟒 at 25°C.

74
Relationship between Ka and Kb
𝐾𝑤
𝐾𝑏 =
𝐾𝑎

𝐾𝑤
𝐾𝑎 =
𝐾𝑏

𝐾𝑤 = 𝐾𝑎 × 𝐾𝑏

75
Conversion of [H+] to pH
[H3O+] [OH-]
pH
moles/liter moles/liter
0 100 = 1 10-14
1 10-1 10-13
2 10-2 10-12
3 10-3 10-11
4 10-4 10-10
5 10-5 10-9
6 10-6 10-8
7 10-7 10-7
8 10-8 10-6
9 10-9 10-5
10 10-10 10-4
11 10-11 10-3
12 10-12 10-2
13 10-13 10-1
14 10-14 10-0 = 1
76
pK and pOH
𝒑 𝑖𝑠 𝑢𝑠𝑒𝑑 𝑡𝑜 𝑒𝑥𝑝𝑟𝑒𝑠𝑠 𝑡ℎ𝑒 𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒 𝑙𝑜𝑔𝑎𝑟𝑖𝑡ℎ𝑚 𝑜𝑓 𝑡ℎ𝑒 𝑡𝑒𝑟𝑚 𝑓𝑜𝑙𝑙𝑜𝑤𝑖𝑛𝑔 𝑝

𝑝𝑂𝐻 = −log[𝑂𝐻 − ]
𝑝𝐾𝑎 = −𝑙𝑜𝑔𝐾𝑎
𝑝𝐾𝑤 = −𝑙𝑜𝑔𝐾𝑤

Thus, the following expressions can be expressed:

𝑝𝐻 + 𝑝𝑂𝐻 = 𝑝𝐾𝑤
𝑝𝐾𝑎 + 𝑝𝐾𝑏 = 𝑝𝐾𝑤

77
pK and pOH
If the pH of a solution is 4.72, what is the hydronium ion concentration?

𝑝𝐻 = −log[𝐻3 𝑂+ ]

78
pK and pOH
If the pH of a solution is 4.72, what is the hydronium ion concentration?

𝑝𝐻 = − log 𝐻3 𝑂+

𝑯𝟑 𝑶+ = 𝟏. 𝟗𝟏 × 𝟏𝟎−𝟓 𝒎𝒐𝒍𝒆/𝒍𝒊𝒕𝒆𝒓

79
 #1 – PH AND POH
For a 0.001 M solution of HCl, what are
(a) the H+ concentration,
(b) the pH,
(c) the OH- concentration and
(d) pOH?

SAMPLE PROBLEMS 80
 #1 – PH AND POH
HCl is a strong inorganic acid (100% ionized in dilute solution). Therefore,
when 0.001 mole of HCl is introduced into 1 L of water, it immediately
dissociates to produce 0.001 M H+ and 0.0001 M Cl-.
H+ concentration

[𝐻 + ] = 𝟎. 𝟎𝟎𝟏 𝑴

SAMPLE PROBLEMS 81
 #1 – PH AND POH
• pH
𝑝𝐻 = − log 𝐻 + = − log 0.001 = −𝑙𝑜𝑔10−3 = 𝟑
• OH- concentration
[𝐻 + ][𝑂𝐻 − ] = 𝐾𝑤
𝐾 1 × 10 −14
𝑤
[𝑂𝐻 − ] = + = −3
= 𝟏 × 𝟏𝟎 −𝟏𝟏
𝑴
[𝐻 ] 1 × 10
• pOH
𝑝𝑂𝐻 = − log 𝑂𝐻 − = − log 10−11 = 𝟏𝟏
𝑜𝑟 𝑝𝐻 + 𝑝𝑂𝐻 = 14

SAMPLE PROBLEMS 82
 #2 – KB AND KA
The Kb for triethanolamine at 25°C is 5.3 x 10-5. Calculate (a) its Ka and (b)
its pKa

SAMPLE PROBLEMS 83
 #2 – KB AND KA
• Ka
𝐾𝑤 1 × 10−14 −𝟏𝟎
𝐾𝑎 = = = 𝟏. 𝟗 × 𝟏𝟎
𝐾𝑏 5.3 × 10−5
• pKa
𝑝𝐾𝑎 = − log 𝐾𝑎 = − log 1.9 × 10−10 = 𝟗. 𝟕𝟐

SAMPLE PROBLEMS 84
 #3 – BUFFER
A solution contains phenobarbital and sodium phenobarbital. Describe
what will happen if acetic acid is added to the solution.

The solution containing phenobarbital and its sodium salt is a buffer

system. Since acetic acid is going to yield protons in the solution, sodium
phenobarbital will react with the added protons and produce more
phenobarbital according to the equation

𝐻𝐴 + 𝑂𝐻 − → 𝐴− + 𝐻2 𝑂

𝑨− + 𝑯𝟑 𝑶+ → 𝑯𝑨 + 𝑶𝑯−

SAMPLE PROBLEMS 85
The Buffer Equation
The Henderson-Hasselbalch Equation or the buffer equation can be used to
calculate the pH of a buffer solution.

For weak acids

[𝐴− ]
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔
[𝐻𝐴]

For weak bases

[𝐵]
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔
[𝐵𝐻 + ]

86
 #4 - BUFFER EQUATION
Calculate the pH of the buffer solution described in the previous problem if
the molar concentration of phenobarbital is 0.03 M and that of sodium
phenobarbital is 0.02 M. The pKa for phenobarbital is 7.4

𝐴− + 𝐻3 𝑂+ → 𝐻𝐴 + 𝑂𝐻 −

[𝐴− ]
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔
[𝐻𝐴]

SAMPLE PROBLEMS 87
 #4 - BUFFER EQUATION
Calculate the pH of the buffer solution described in the previous problem if
the molar concentration of phenobarbital is 0.03 M and that of sodium
phenobarbital is 0.02 M. The pKa for phenobarbital is 7.4

𝐴− + 𝐻3 𝑂+ → 𝐻𝐴 + 𝑂𝐻 −

[𝐴− ]
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔
[𝐻𝐴]
[𝑠𝑜𝑑𝑖𝑢𝑚 𝑝ℎ𝑒𝑛𝑜𝑏𝑎𝑟𝑏𝑖𝑡𝑎𝑙]
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔
[𝑝ℎ𝑒𝑛𝑜𝑏𝑎𝑟𝑏𝑖𝑡𝑎𝑙]
0.02 𝑀
𝑝𝐻 = 7.4 + 𝑙𝑜𝑔 = 𝟕. 𝟐
0.03 𝑀

SAMPLE PROBLEMS 88
The Buffer Capacity
The buffer capacity is a function of the ionic dissociation constant, the hydronium
ion concentration, and the total molar concentration (C) of the components (i.e.
the weak acid and the conjugate base)

𝐾𝑎 × [𝐻3 𝑂+ ]
𝛽 = 2.3𝐶[
𝐾𝑎 + [𝐻3 𝑂+ ]2

89
The Buffer Capacity
It is also defined approximately as the ratio of the change in the gram equivalent
weight per liter (Eq/L) of an acid or a base (B) needed to produce a particular
change in the pH.
𝑩
𝜷=
𝒑𝑯

When β values are expressed, no units usually are stated; however, the number
represents the Eq/L for a unit pH change.

The value of β reaches its maximum when the hydronium ion concentration in the
solution is equal to the dissociation constant for the weak acid. The maximum
buffer capacity is defined as
𝜷𝒎𝒂𝒙 = 𝟎. 𝟎𝟓𝟕𝟓𝑪

90
 #5 – BUFFER CAPACITY
If the addition of 0.1 mole of HCl (MW = 36.5) to 1 L of a buffer solution
caused a drop in the pH by 0.4 unit, calculate the capacity of the buffer.

SAMPLE PROBLEMS 91
 #5 – BUFFER CAPACITY
If the addition of 0.1 mole of HCl (MW = 36.5) to 1 L of a buffer solution
caused a drop in the pH by 0.4 unit, calculate the capacity of the buffer.

Since one equivalent weight of HCl is 36.5 g,

0.1
𝛽= = 𝟎. 𝟐𝟓
0.4

SAMPLE PROBLEMS 92
 #6 – BUFFER CAPACITY
The buffer capacity of a solution is 0.02. How much 1 N solution of NaOH
(MW = 40) must be added to 1 L of this solution to change its pH by 1 unit?

SAMPLE PROBLEMS 93
 #6 – BUFFER CAPACITY
The buffer capacity of a solution is 0.02. How much 1 N solution of NaOH
(MW = 40) must be added to 1 L of this solution to change its pH by 1 unit?

Since β is 0.02 and pH is 1, β is 0.02. Thus, 20 mL of the NaOH solution is

needed to bring about this change (assume that the addition of 20 mL of
solution to 1 L will not cause a great change in the volume or
concentration)

SAMPLE PROBLEMS 94
Preparation of Buffers
1. Decide for what pH the buffer is needed.

2. Choose a conjugate acid-base pair so that the ionization constant for the weak
acid is as close as possible to the hydronium ion concentration desired (from
step 1). This will guarantee that β will be at its maximum value.

3. Apply the Henderson-Hasselbalch equation and calculate the ratio of proton

acceptor to proton donor.

4. Choose the concentration of the proton acceptor and the proton donor so that
β is within the range of 0.01 to 0.1.

5. Verify the pH of the resulting buffer by using a pH meter.

95
 #7 – BUFFER PREPARATION
Prepare a pharmaceutical buffer with pH 4.76.
Acetic acid has pKa = 4.76. An acetic acid-sodium acetate buffer will be
prepared.

SAMPLE PROBLEMS 96
 #7 – BUFFER PREPARATION
Prepare a pharmaceutical buffer with pH 4.76.
Acetic acid has pKa = 4.76. An acetic acid-sodium acetate buffer will be
prepared.
According to the Henderson-Hasselbalch equation, the ratio of salt to acid
is 1. Choose the salt and acid concentration that makes β between 0.01
and 0.1
𝐾𝑎 × 𝐻3 𝑂+ −5
𝛽 = 2.3𝐶[ ; 𝐾 = 1.75 × 10
𝐾𝑎 + 𝐻3 𝑂+ 2 𝑎
1.75 × 10−5 × 10−4.67
0.05 = 2.3𝐶[ −5 −4.67 2
]
1.75 × 10 + 10 ]
C = 0.088M or 0.044 M acetic acid and 0.044 M sodium acetate, since the
ratio of the salt to acid is 1

SAMPLE PROBLEMS 97
 #8 – BUFFER PREPARATION
At a hydrogen ion concentration of 1.75 x 10-5 (pH = 4.76), what is the
capacity of a buffer containing 0.10 mole each of acetic acid and sodium
acetate per liter of solution? The total concentration, C = [acid] + [salt], is
0.20 mole/liter, and the dissociation constant is 1.75 x 10-5.

SAMPLE PROBLEMS 98
 #8 – BUFFER PREPARATION
At a hydrogen ion concentration of 1.75 x 10-5 (pH = 4.76), what is the
capacity of a buffer containing 0.10 mole each of acetic acid and sodium
acetate per liter of solution? The total concentration, C = [acid] + [salt], is
0.20 mole/liter, and the dissociation constant is 1.75 x 10-5.
𝐾𝑎 × 𝐻3 𝑂+
𝛽 = 2.3𝐶[
𝐾𝑎 + 𝐻3 𝑂+ 2

1.75 × 10−5 × 1.75 × 10−5

𝛽 = 2.3 × 0.20[ −5 −5 2
]
1.75 × 10 + 1.75 × 10 ]
β = 0.115

SAMPLE PROBLEMS 99
 #9 – BUFFER CAPACITY
For a buffer solution containing 0.1 M of a weak base and 0.06 M of its
conjugate acid, calculate its buffer capacity if the pH of the solution equals
the pKa of the conjugate acid.

SAMPLE PROBLEMS 100

 #9 – BUFFER CAPACITY
For a buffer solution containing 0.1 M of a weak base and 0.06 M of its
conjugate acid, calculate its buffer capacity if the pH of the solution equals
the pKa of the conjugate acid.

Since pKa = pH, β is at its maximum value

𝛽𝑚𝑎𝑥 = 0.575𝐶 = 0.575 0.1 + 0.06 = 𝟎. 𝟎𝟗𝟐

SAMPLE PROBLEMS 101

HENDERSON – HASSELBALCH EQUATION
[𝑏𝑎𝑠𝑒]
𝑝𝐻 = 𝑝𝐾𝑎 + log
[𝑎𝑐𝑖𝑑]
 #10 – MOLAR RATIO
What is the molar ratio (salt/acid), required to prepare an acetate buffer of
pH 5.0 Express the result in mole percent. (pKa= 4.76)
a. Mole ratio?
b. Mole percent?

SAMPLE PROBLEMS 103

 #10 – MOLAR RATIO (A)
Given: pH = 5.0, pKa= 4.76
[𝑠𝑎𝑙𝑡]
𝒑𝑯 = 𝒑𝑲𝒂 + log
[𝑤𝑒𝑎𝑘 𝑎𝑐𝑖𝑑]

[𝑠𝑎𝑙𝑡]
𝟓 = 𝟒. 𝟕𝟔 + log
[𝑤𝑒𝑎𝑘 𝑎𝑐𝑖𝑑]

The mole ratio of salt to acid is 1.74/1.

SAMPLE PROBLEMS 104

 #10 – MOLAR RATIO (B)
Mole ratio of salt to acid is 1.74/1
Salt: 1.74
Acid: + 1____
salt + acid 2.74
Mole fraction of salt in salt-acid mixture = 1. 74 = 0.635
1 + 1.74
Mole percent = mole fraction X 100
= 0.635 x 100
= 63.5 %

SAMPLE PROBLEMS 105

 #11 – BUFFER COMPOSITION
A buffer solution was prepared by mixing 0.25M CHOONa and 0.125M
HCOOH (pKa =3.75).
a. Determine the pH of the buffer solution
b. If the same composition is to be used in preparing a buffer solution
with a pH of 4.5. What will be the molar ratio of the salt to acid?
i. What is the percentage of the ionized species in the buffer system?
ii. What is the percentage of the unionized species in the buffer
system ?

SAMPLE PROBLEMS 106

 #11 – BUFFER COMPOSITION (A)
[𝑠𝑎𝑙𝑡]
𝒑𝑯 = 𝒑𝑲𝒂 + log
[𝑤𝑒𝑎𝑘 𝑎𝑐𝑖𝑑]
[𝐶𝐻𝑂𝑂𝑁𝑎]
𝒑𝑯 = 𝟑. 𝟕𝟓 + log
[𝐻𝐶𝑂𝑂𝐻]
[0.25 𝑀]
𝒑𝑯 = 𝟑. 𝟕𝟓 + log
[0.125 𝑀]
𝒑𝑯 = 𝟑. 𝟕𝟓 + log 𝟐
𝒑𝑯 = 𝟑. 𝟕𝟓 + 𝟎. 𝟑𝟎
pH = 4.05

SAMPLE PROBLEMS 107

 #11 – BUFFER COMPOSITION (B)
[𝑠𝑎𝑙𝑡]
𝒑𝑯 = 𝒑𝑲𝒂 + log
[𝑤𝑒𝑎𝑘 𝑎𝑐𝑖𝑑]
[𝐶𝐻𝑂𝑂𝑁𝑎]
𝟒. 𝟓 = 𝟑. 𝟕𝟓 + log
[𝐻𝐶𝑂𝑂𝐻]
[𝑠𝑎𝑙𝑡]
= 𝟓. 𝟔
[𝑎𝑐𝑖𝑑]

SAMPLE PROBLEMS 108

 #11 – BUFFER COMPOSITION (B)
B(i) percentage of the ionized species in the buffer system
The ratio of salt to acid is 5.6 : 1.
Salt (ionized) : 5.6
Acid ( unionized) : 1 +
6.6
% of ionized species = ionized x 100
ionized + unionized
= 5.6 x 100
6.6
= 84.85 %
B(ii)
% of unionized species = unionized x 100
ionized + unionized
= 1 x 100
6.6
= 15. 15 %

SAMPLE PROBLEMS 109

 #12 - BUFFER
A buffer was prepared containing 5 x 10-2 M sodium borate with 5 x 10-7 M
boric acid.
Determine the Ka of the acid if the solution has a pH of 14.24.

SAMPLE PROBLEMS 110

 #12 - BUFFER
Given: pH = 14.24 LOGARITHMIC FUNCTIONS
[𝑠𝑎𝑙𝑡] logab = c
𝒑𝑯 = 𝒑𝑲𝒂 + log
[𝑤𝑒𝑎𝑘 𝑎𝑐𝑖𝑑]
5𝑥10−2
ac = b
𝟏𝟒. 𝟐𝟒 = 𝒑𝑲𝒂 + log
5𝑥10−7
9.24 = pKa

Since
pKa = -log10Ka (log is base 10)
Ka = 10-pKa
Ka = 10-9.24
Ka = 5.75 x 10-10
SAMPLE PROBLEMS 111
 #13 - BUFFER
What is the pH of a solution containing 0.10 moles of ephedrine and 0.01
mole of ephedrine hydrochloride per liter of solution? The pKb of
ephedrine is 4.64.

SAMPLE PROBLEMS 112

 #13 - BUFFER
[𝑤𝑒𝑎𝑘 𝑏𝑎𝑠𝑒]
𝒑𝑯 = 𝒑𝑲𝒘 − 𝒑𝑲𝒃 + log
[𝑠𝑎𝑙𝑡]
0.10
𝒑𝑯 = 𝟏𝟒 − 𝟒. 𝟔𝟒 + log
0.01
= 10.36

SAMPLE PROBLEMS 113

 #14 - BUFFER
The Kb of pilocarpine is found to be 6.34 x 10 -7 at 25°C.
a. Determine the mole ratio (salt/base) present at pH of 9
b. Determine the mole percent of the base
c. Determine the mole percent of the salt

SAMPLE PROBLEMS 114

 #14 - BUFFER
mole ratio (salt/base) present at pH of 9
pKb = - log Kb
= - log (6.34 x l0 -7)
= 6.20

SAMPLE PROBLEMS 115

 #14 - BUFFER
[𝑤𝑒𝑎𝑘 𝑏𝑎𝑠𝑒]
𝒑𝑯 = 𝒑𝑲𝒘 − 𝒑𝑲𝒃 + log
[𝑠𝑎𝑙𝑡]
[𝑤𝑒𝑎𝑘 𝑏𝑎𝑠𝑒]
𝟗 = 𝟏𝟒 − 𝟔. 𝟐𝟎 + log
[𝑠𝑎𝑙𝑡]
[𝑤𝑒𝑎𝑘 𝑏𝑎𝑠𝑒]
𝟏. 𝟐 = log
[𝑠𝑎𝑙𝑡]
[𝑤𝑒𝑎𝑘 𝑏𝑎𝑠𝑒]
15.85 =
[𝑠𝑎𝑙𝑡]

The mole ratio of salt to base is 1: 15.85

SAMPLE PROBLEMS 116

 #14 - BUFFER
mole percent of the base
salt : 1
base : 15.85 +
16.85

mole percent (base) = 15.85 x 100 = 94.07%

16.85

SAMPLE PROBLEMS 117

 #14 - BUFFER
mole percent of the salt

mole percent (salt) = 1 x 100 = 5.93%

16.85

SAMPLE PROBLEMS 118

 #15 - BUFFER
βmax = 0.576 C
where C is the total buffer concentration

What is the maximum buffer capacity of an acetate buffer with a total

concentration of 0.020 mole/liter?

SAMPLE PROBLEMS 119

 #15 - BUFFER
βmax = 0.576 C
where C is the total buffer concentration

What is the maximum buffer capacity of an acetate buffer with a total

concentration of 0.020 mole/liter?

βmax = 0.576 X 0.020

= 0.01152 or 0.012

SAMPLE PROBLEMS END.