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Pharmacist

Licensure Examination 1/25/18


Module 5: Pharmacutics (17.5%)

POINTERS TO REVIEW
Based on PRC Board Resolution no 10 series of 2013

MODULE 5 BLUEPRINT (17.5%)

Pharmacist
PharmacistLicensure Examination
Licensure Examination
PH ARMACEUTICS NO. OF ITEMS
NO. OF EASY
NO. OF
MOD ERATE
NO. OF
D IFFICULT

PHYSICAL PHARMACY
ITEMS
ITEMS ITEMS

PHYSICAL PHARMACY Pharmaceutical


Manufacturing
29 12 12 5

Daryl E. Magno, RPh


Pharmaceutical Dos age
University of the Philippines-Manila 29 12 12 5
Forms
College of Pharmacy
Phys ical Pharmacy 25 10 10 5

Juris prudence and Ethics 17 6 6 5

POINTERS TO REVIEW
Based on PRC Board Resolution no 10 series of 2013

MODULE 5 BLUEPRINT (17.5%)

INTRODUCTION
NO. OF NO. OF
NO. OF EASY
PH ARMACEUTICS NO. OF ITEMS MOD ERATE D IFFICULT
ITEMS
ITEMS ITEMS

Pharmaceutical
25 10 10 5
Manufacturing

TOPICS NO. OF ITEMS

Phys ical Pharmacy Principle 3

Solubility and Dis tribution Phenomena, Buffer and Is otonic


3 (each)
Solutions , Interfacial Phenomena, Micrometics

Colloids , Coars e Dis pers ion, Rheology, Complexation and


2 (each)
Protein Binding, Kinetics

WHAT IS PHYSICAL PHARMACY? DEFINITION OF TERMS


- Physical pharmacy integrates knowledge of mathematics,
Atom
physics and chemistry and applies them to the
- Atoms are the smallest particle into which an
pharmaceutical dosage form development element can be divided
- Basic unit of an element
- Physical pharmacy is the study of the physical and Molecule
chemical properties of drugs and their dosage forms - One or more atoms joined together by chemical
bonds
- Physical pharmacy is the application of physical chemical - Smallest unit of a compound that has the physical
principles to various aspects of pharmacy and chemical properties of that compound

Lecturer: Daryl E. Magno, RPh 1


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

DEFINITION OF TERMS DEFINITION OF TERMS


Electron

C O H - A particle which has a negative charge


Proton
- A particle which has a positive charge
Neutron
ATOM of CARBON H - A particle with no charge
Nucleus
MOLECULE of WATER - At the center of the atom containing both protons
and neutrons

DEFINITION OF TERMS DEFINITION OF TERMS


Nucleon Isotopes
- Collective term for protons and neutrons - Atoms of the same element with the same number
Atomic Number of protons, but differing numbers of neutrons
- Number of protons Example:
Mass Number
ATOMIC MASS NUMBER OF
ISOTOPE FORMULA
- Number of protons and neutrons NUMBER NUMBER NEUTRONS
Protium 1
- Nucleon number 1H 1 1 0
Deuterium 2
1H (D) 1 2 1
Orbital
Tritium 3
1H (T) 1 3 2
- A region within the atom in which electrons have the
highest probability of being found

DEFINITION OF TERMS DEFINITION OF TERMS


Isotones Isobars
- Atoms belonging to different elements having the - Atoms belonging to different elements with the same
same number of neutrons mass numbers but different atomic numbers
Example: Carbon and Nitrogen have the same number Example: Calcium and Argon both have the same mass
of neutrons (7) numbers (40)
13 and 7N14 40 40
6C 20Ca 18Ar

Lecturer: Daryl E. Magno, RPh 2


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

CHECKPOINT

1. Study of the physi cal and chemi cal propertie s of 3. Example of an atom.
drugs and their dosage forms. a. Carbon Dioxide
a. Pharmacokinetics b. Nitric Acid
b. Pharmacotherapeutics c. Sulfur
c. Pharmaceutical Dosage Forms d. All of the above
d. Physical Pharmacy
4. Atoms of the same element with the same number
2. One or more at oms j oined t ogether by che mica l of protons, but differing numbers of neutrons
bonds. a. Isotopes
a. Atom b. Isotones
b. Molecule c. Isobars
c. Both A and B d. None of the above
d. None of the above

5. Number of protons
a. Atomic Number
b. Mass Number
c. Molecular Weight
d. Atomic Weight
FORCES OF ATTRACTION
PHYSICAL PROPERTIES
TYPES OF PROPERTIES

Lecturer: Daryl E. Magno, RPh 3


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

FORCES OF ATTRACTION
INTRAMOLECULAR FORCES
§ Forces that hold atoms together within a molecule
FORCES OF ATTRACTION

INTERMOLECULAR FORCES
§ Forces that exist between molecules

FORCES OF ATTRACTION
INTRAMOLECULAR FORCES
1. Ionic bond
2. Covalent bond
3. Metallic bond
INTERMOLECULAR FORCES
1. Dipole-dipole
2. London forces
3. Hydrogen bond
*Photo grabbed from www.khanacademy.org

FORCES OF ATTRACTION FORCES OF ATTRACTION


INTRAMOLECULAR FORCES INTRAMOLECULAR FORCES
1. Ionic bond 2. Covalent bond
§ Electrostatic attraction between ions that have § Bond is formed between atoms that have
opposite charges similar electronegativities—the affinity or
§ Between metals and nonmetals desire for electrons
§ Complete transfer of valence electron(s) § Sharing of electrons in order to achieve octet
between atoms configuration
§ 2 types of Covalent bond:
i). Nonpolar
ii) Polar

Lecturer: Daryl E. Magno, RPh 4


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

FORCES OF ATTRACTION FORCES OF ATTRACTION


INTRAMOLECULAR FORCES INTRAMOLECULAR FORCES
2. Covalent bond 2. Covalent bond
§ Nonpolar- the difference in electronegativity § Polar- the difference in electronegativity
between bonded atoms is less than 0.5 between bonded atoms is between 0.5 and 1.9

FORCES OF ATTRACTION FORCES OF ATTRACTION


INTRAMOLECULAR FORCES INTERMOLECULAR FORCES
3. Metallic bond 1. Van der Waals Forces
§ Bond exists only in metals § Weakest of the intermolecular forces and exist
§ Valence electrons are free to move through the lattice between all types of molecules
§ The electrons act as a "glue" giving the substance a TYPE DESCRIPTION OTHER TERM
definite structure
KEESOM Dipole-dipole Orientation forces

DEBYE Dipole-induced Induction forces


dipole
LONDON Induced dipole- Dispersion forces
induced dipole

FORCES OF ATTRACTION FORCES OF ATTRACTION


INTRAMOLECULAR FORCES INTRAMOLECULAR FORCES
A. Keesom B. Debye

Lecturer: Daryl E. Magno, RPh 5


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

FORCES OF ATTRACTION FORCES OF ATTRACTION


INTRAMOLECULAR FORCES INTRAMOLECULAR FORCES
C. London Forces 2. Hydrogen bonding
§ Special kind of dipole-dipole interaction that
occurs specifically between a hydrogen atom
bonded to either an oxygen, nitrogen, or
fluorine atom

FORCES OF ATTRACTION FORCES OF ATTRACTION


INTRAMOLECULAR FORCES INTRAMOLECULAR FORCES
3. Ion-dipole 4. Ion-induced dipole
§ Electrostatic attraction between an ion and a § Ion induces a dipole in an atom or a molecule
neutral molecule that has a dipole with no dipole

PHYSICAL PROPERTIES
1. Additive Property
§ Depends on the sum of the individual properties of the
components present in a system
§ Ex. Molecular weight

PHYSICAL PROPERTIES 2. Constitutive Property


§ Depends on the type and arrangement of the
components present in a system
§ Ex. Optical activity
3. Colligative Property
§ Depends on the number of components present in a
system
§ Ex. Boiling point elevation

Lecturer: Daryl E. Magno, RPh 6


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

TYPES OF PROPERTIES
§ Extensive Property
- Depends on the size or the amount of material
- Ex. mass, length, volume
§ Intensive Property
- Does not depend on the size or amount of

TYPES OF PROPERTIES
material
- Ratio of two extensive properties
- Ex. Density, specific gravity

Density Density
§ Measure of mass per unit of volume § Two types:
§ unit: g/mL 1. Bulk Density
§ Two types: ØMeasure of interparticulate interactions
1. Bulk Density ØIndex of the ability of the powder to flow
2. Tapped Density
ØDetermined by measuring the volume of a known
mass of powder sample that has been passed
through a
• Graduated cylinder (Method I)
• Volumeter (Method II)

Density Density
§ Two types: § Measure of mass per unit of volume
2. Tapped Density § unit: g/mL
Ø achieved by mechanically tapping a measuring
cylinder containing a powder sample
Ø Methods:
– Method I – mechanical tapped density tester
(fixed drop: 14 ± 2 mm; nominal rate: 300
drops/min)
– Method II – mechanical tapped density tester
(fixed drop: 3mm (±10%); nominal rate: 250
drops/min

Lecturer: Daryl E. Magno, RPh 7


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

What is the density of a 85 mL liquid if its weight What is the weight of 60 mL of oil whose density
is 38 g? is 0.9645 g/mL?
A. 0.56 g/mL A. 56.0
B. 0.53 g/mL B. .5600
C. 0.45 g/mL C. 57.87
D. 0.41 g/mL D. 54.88

CORRECT ANSWER: C CORRECT ANSWER: C

Density
What is the density of a 3.5 L liquid if its weight
§ Two types:
is 90 g?
§ Bulk density- ratio of the mass of an untapped
A. 0.56 g/mL powder sample and its volume
B. 0.056 g/mL § Tapped density- increased bulk density attained
C. 0.026 g/mL after mechanically tapping a container containing
the powder sample
D. 0.063 g/mL

CORRECT ANSWER: C

Specific gravity Methods of Determining Specific Gravity


§ Dimensionless unit 1. Measurement by Pycnometer
§ Ratio of the density of a substance to the density of 2. Measurement by Sprengel-Ostwald Pycnometer
water at a specified temperature 3. Measurement by Hydrometer
4. Measurement by Oscillator-Type Density Meter

Lecturer: Daryl E. Magno, RPh 8


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

Calculating Specific Gravity Calculating Specific Gravity by Weight


1. Calculating Specific Gravity by Weight 1. Obtain the weight of the liquid in question
2. Calculating Specific Gravity by Density 2. Obtain the weight of an identical volume of water
3. Calculate the ratio of the liquid’s weight to the
weight of water

Calculating Specific Gravity by Weight Calculating Specific Gravity by Weight


1. Obtain the weight of the liquid in question 1. Obtain the weight of the liquid in question
2. Obtain the weight of an identical volume of water 2. Obtain the weight of an identical volume of water
3. Calculate the ratio of the liquid’s weight to the 3. Calculate the ratio of the liquid’s weight to the
weight of water weight of water

Exa mple : If you weighed 10 0 mL of a cetone at 25 Exa mple : If you weighed 10 0 mL of a cetone at 25
degrees C, it w oul d weig h 0 .17 314 pounds. W eighi ng degrees C, it w oul d weig h 0 .17 314 pounds. W eighi ng
the sa me volume of water at the sa me te mperatur e the sa me volume of water at the sa me te mperatur e
give you 0.22 pounds . What is the spe ci fic gravity of give you 0.22 pounds . What is the spe ci fic gravity of
acetone? acetone? Answer: 0.17314/0.22 = 0.787

Calculating Specific Gravity by Density Calculating Specific Gravity by Density


1. Obtain the density of the liquid in question 1. Obtain the density of the liquid in question
2. Obtain the density of an identical volume of water 2. Obtain the density of an identical volume of water
3. Calculate the ratio of the liquid’s density to the 3. Calculate the ratio of the liquid’s density to the
density of water density of water

Exa mple : I f you had a sa mple that was eight gra ms and
nine milliliters, what its specific gravity?

Lecturer: Daryl E. Magno, RPh 9


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

Calculating Specific Gravity by Density


1. Obtain the density of the liquid in question
2. Obtain the density of an identical volume of water
3. Calculate the ratio of the liquid’s density to the
density of water

Exa mple : I f you had a sa mple that was eight gra ms and
nine milliliters, what its specific gravity? CHECKPOINT
Answer: 8g/9mL = 0.89g/mL
0.89g/mL ÷ 1g/mL = 0.89g/mL

1. Weakest type of intermolecular force of attraction. 3. Example of property where it depends on the sum
a. London of the individual properties of the components
b. Debye present in the system.
c. Keesom a. Additive
d. None of the above b. Constitutive
c. Colligative
2. Sharing of ele ctrons in order to a chieve octe t d. All of the above
configuration.
a. Ionic Bond 4. Ratio of untapped powder sample and its volume
b. Covalent Bond a. Bulk Density
c. Metallic Bond b. Tapped Density
d. All of the above c. Both
d. None

5. What is the weight of 0.05 L of oil whose density is


0.8465 g/mL?
a. 42.325
b. 0.042
c. 4.233
d. 423.25

STATES OF MATTER

Lecturer: Daryl E. Magno, RPh 10


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

STATES OF MATTER STATES OF MATTER


1. Solid 3. Gas
§ Fixed volume and shape § Assumes the shape and volume of its container
§ Rigid (particles locked into place) § Particles can move past one another
§ Not easily compressible § Compressible
§ Does not flow easily § Flows easily
2. Liquid 4. Plasma
§ Assumes the shape of the container which it occupies § Hot ionized gas consisting of positively and negatively
§ Particles can move/slide past one another charged electrons
§ Not easily compressible
§ Flows easily

STATES OF MATTER STATES OF MATTER


Property Solid Liquid Gas
Shape Definite Variable Variable

Volume Definite Definite Variable

IFA Strength Strong Strong Weak


Molecular Constant
Vibration Gliding
Motion Random Motion
Fairly closely Widely spaced,
Particle Closely packed,
packed, not fixed moved
Arrangement Fixed position
positions independently
Fairly closely Widely spaced,
Particle Closely packed,
packed, not fixed moved
Arrangement Fixed position
positions independently

STATES OF MATTER STATES OF MATTER


5. Bose-Einstein Condensate Liquid Crystal
§ Forms within a few degrees of absolute zero § Mesophase
§ Formation of “SUPER ATOM” § Intermediate phase
§ Blends the structures and properties of the liquid
and solid states
§ ROPE (Rigid, Organic, Polarizable, Elongated)
§ Thermotropic VS Lyotropic Crystals?

Lecturer: Daryl E. Magno, RPh 11


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

STATES OF MATTER STATES OF MATTER


Types of Liquid Crystals Types of Liquid Crystals
Type 1: Smectic Type 2: Nematic
§ Soap-like § Thread-like
§ Molecules tend to line themselves up § Simplest form of liquid crystal
into layers § Crystal molecules have no orderly
§ More restricted movement than nematic position and are free to move

STATES OF MATTER
Types of Liquid Crystals
Type 3: Cholesteric
§ Chiral nematic
§ Molecules being aligned and at a slight
angle to one another
GASES

GASES GAS LAWS


Kinetic Molecular Theory of Gases Boyle’s Law
1. Gases are composed of a large number of particles that § Mariotte Law
behave like hard, spherical objects in a state of constant,
random motion. § States that “At constant temperature, the
2. These particles are much smaller than the distance between
pressure P of a gas varies inversely with its volume V”
particles. Most of the volume of a gas is therefore empty
space.
3. There is no force of attraction between gas particles or P1V1= P2V2
between the particles and the walls of the container.
4. Collisions between gas particles or collisions with the walls of
the container are perfectly elastic.

Lecturer: Daryl E. Magno, RPh 12


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

BOYLE’S GAS LAWS BOYLE’S GAS LAWS


Sample Problem: Sample Problem:
Calculate the press ure in at mosphere s in an engi ne at Calculate the press ure in at mosphere s in an engi ne at
the e nd of the compres sion stroke. As sume t hat at the the e nd of the compres sion stroke. As sume t hat at the
start of the stroke, the pre ssur e of the mixt ure of start of the stroke, the pre ssur e of the mixt ure of
gasoline and air i n the cyli nder i s 7 45. 8 mm Hg and the gasoline and air i n the cyli nder i s 7 45. 8 mm Hg and the
volume of ea ch cylinder is 246. 8 mL. Ass ume that the volume of ea ch cylinder is 246. 8 mL. Ass ume that the
volume of the cylinder is 24 .2 mL at the end of the volume of the cylinder is 24 .2 mL at the end of the
compression stroke. compression stroke.
Answer: 10 atm

BOYLE’S GAS LAWS BOYLE’S GAS LAWS


Sample Problem: Sample Problem:
A gas tank holds 27 85 L of pr opa ne, C3H8, at 83 0 A gas tank holds 27 85 L of pr opa ne, C3H8, at 83 0
mmHg. W hat is the volume of t he propane at sta ndar d mmHg. W hat is the volume of t he propane at sta ndar d
pressure? pressure?

Answer: 3042 L

GAS LAWS CHARLES’ GAS LAWS


Charles’ Law
§ States that, “At constant pressure, the volume V of a Sample Problem:
gas is directly proportional to its absolute (Kelvin) Assume t hat the volume of a ball oon filled wit h H2 i s
temperature T” 1.00 L at 2 5 degree s C. Cal culate t he v olume of the
balloon whe n it is coole d to -78 degree s C in a low-
temperature bath made by adding dry ice to acetone.
V1/T1= V2/T2

Lecturer: Daryl E. Magno, RPh 13


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

CHARLES’ GAS LAWS CHARLES’ GAS LAWS


Sample Problem: Sample Problem:
Assume t hat the volume of a ball oon filled wit h H2 i s A sample of oxyge n occupies a v olume of 160 dm3 at
1.00 L at 2 5 degree s C. Cal culate t he v olume of the 91° C. W hat will be v olume of oxygen w he n the
balloon whe n it is coole d to -78 degree s C in a low- temperature drops to 0.00° C?
temperature bath made by adding dry ice to acetone.

Answer: 0.65 L

CHARLES’ GAS LAWS CHARLES’ GAS LAWS


Sample Problem: Sample Problem:
A sample of oxyge n occupies a v olume of 160 dm3 at A sample of oxyge n occupies a v olume of 160 dm3 at
91° C. W hat will be v olume of oxygen w he n the 91° C. W hat will be v olume of oxygen w he n the
temperature drops to 0.00° C? temperature drops to 0.00° C? How about in liters?

Answer: 120 dm 3

CHARLES’ GAS LAWS GAS LAWS


Gay-Lussac’s Law
Sample Problem: § States that, “At constant volume, the pressure P of a
A sample of oxyge n occupies a v olume of 160 dm3 at gas is directly proportional to its absolute (Kelvin)
91° C. W hat will be v olume of oxygen w he n the temperature T”
temperature drops to 0.00° C? How about in liters?

P1/T1= P2/T2
Answer: 120 L

Lecturer: Daryl E. Magno, RPh 14


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

GAY-LUSSAC’S GAS LAWS GAY-LUSSAC’S GAS LAWS


Sample Problem: Sample Problem:
A gas has a pressure of 69 9.0 mm Hg at 40.0 °C. W hat A gas has a pressure of 69 9.0 mm Hg at 40.0 °C. W hat
is the temperature at a pressure of 760.0 mm Hg? is the temperature at a pressure of 760.0 mm Hg?

Answer: 340.3 Kelvin

GAY-LUSSAC’S GAS LAWS GAY-LUSSAC’S GAS LAWS


Sample Problem: Sample Problem:
If a gas at 740 mm Hg and 70. 0 ºC has its pre ssur e If a gas at 740 mm Hg and 70. 0 ºC has its pre ssur e
lowered to 72 0 mm Hg, what will its temperature be if lowered to 72 0 mm Hg, what will its temperature be if
volume remains constant? volume remains constant?

Answer: 334K

GAS LAWS GAS LAWS


Avogadro’s Law Amontons’ Law
§ States that, “Volume of a gas is directly proportional § States that, “Given a constant number of mole of a
to the amount of gas at a constant temperature and gas and an unchanged volume, pressure is directly
pressure.” proportional to temperature.”

Lecturer: Daryl E. Magno, RPh 15


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

GAS LAWS COMBINED GAS LAWS


Combined Gas Law
§ Combination of Boyle's Law, Charles' Law and Gay- Sample Problem:
Lussac’s Law A sample of sulfur dioxide occupies a volume of
652 mL at 40.° C and 720 mm Hg. What volume
will the sulfur dioxide occupy at STP?

COMBINED GAS LAWS COMBINED GAS LAWS


Sample Problem: Sample Problem:
A sample of sulfur dioxide occupies a volume of The initial temperature of a 1.00 liter sample of
652 mL at 40.° C and 720 mm Hg. What volume argon is 20.° C. The pressure is decreased from
will the sulfur dioxide occupy at STP? 720 mm Hg to 360 mm Hg and the volume
increases to 2.14 liters. What was the change in
temperature of the argon?
Answer: 538.75mL

COMBINED GAS LAWS GAS LAWS


Ideal Gas Law
Sample Problem: § Combination of Boyle's Law, Charles' Law,
The initial temperature of a 1.00 liter sample of Amontons’ Law and Avogadro's Law
argon is 20.° C. The pressure is decreased from
720 mm Hg to 360 mm Hg and the volume
increases to 2.14 liters. What was the change in PV=nRT
temperature of the argon?

Answer: 313.51 K

Lecturer: Daryl E. Magno, RPh 16


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

GAS LAWS IDEAL GAS LAWS


Ideal Gas Law
§ Combination of Boyle's Law, Charles' Law, Sample Problem:
Amontons’ Law and Avogadro's Law How many mol ecules are t here i n 98 5 mL of nitroge n
§ n is number of moles (mass/molecular weight) at 0.0° C and 1.00 x 10-6 mm Hg?
§ R is the gas constant
- R = 0.0821 liter·atm/mol·K
- R = 8.3145 J/mol·K
- R = 8.2057 m3·atm/mol·K
- R = 62.3637 L·Torr/mol·K or L·mmHg/mol·K

IDEAL GAS LAWS IDEAL GAS LAWS


Sample Problem: Sample Problem:
How many mol ecules are t here i n 98 5 mL of nitroge n at
Calculate the mass of 15.0 L of NH3 (MW = 17.04
0.0° C and 1.00 x 10-6 mm Hg?
g/mol) at 27° C and 900 mm Hg.
Answer: 3.48 X 1013 N2 molecules

IDEAL GAS LAWS GAS LAWS


Sample Problem: Sample Problem:
Calculate the mas s of 15. 0 L of NH3 (MW = 1 7.0 4
Calculate the density in g/L of 478 mL of krypton
g/mol) at 27° C and 900 mm Hg.
(MW=83.798 g/mol) at 47° C and 671 mm Hg.
Answer: 12.3 g

Lecturer: Daryl E. Magno, RPh 17


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

GAS LAWS GAS LAWS


Real Gas Equation
Sample Problem: 2 Factors:
Calculate the de nsity in g /L of 47 8 mL of krypton § As pressure increases, the volume of a gas becomes very
(MW=83.798 g/mol) at 47° C and 671 mm Hg. small and approaches zero. While it does approach a small
number, it will not be zero because molecules do occupy
space (i.e. have volume) and cannot be compressed
Answer: 2.82 g/L
(INCOMPRESSIBI LIT Y )

§ Intermolecular forces do exist in gases


(INTERMOLECULAR FORCES)

GAS LAWS GAS LAWS


Real Gas Equation (Van der Waals Equation) Henry’s Law of Gas Solubility
§ States that “At a constant temperature, the amount
of a gas that dissolves in a liquid is directly
proportional to the partial pressure of that gas in
equilibrium with that liquid”
an2/v2: accounts for the internal pressure per mole
resulting from the intermolecular forces of attraction
between the molecules

nb: accounts for the incompressibility of the molecules

GAS LAWS DALTON’S LAW OF PARTIAL PRESSURE


Dalton’s Law of Partial Pressure Sample Problem:
§ States that “The total pressure in a mixture of gases Let's say that we have one container with 24.0 L of
is equal to the sum of the partial pressure of each gas” nitrogen gas at 2.00 atm, and another container with
12.0 L of oxygen gas at 2.00 atm. The temperature of
both gases is 273 K.
PTOTAL= PA + PB…
If both gases are mixed in a 10L container, what are
the partial pressures of nitrogen and oxygen in the
resulting mixture? What is the total pressure?

Lecturer: Daryl E. Magno, RPh 18


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

DALTON’S LAW OF PARTIAL PRESSURE GAS LAWS


Sample Problem: Graham’s Law
Let's say that we have one container with 24.0 L of nitrogen gas § States that “The rate of effusion of a gaseous
at 2.00 atm, and another container with 12.0 L of oxygen gas at substance is inversely proportional to the square root
2.00 atm. The temperature of both gases is 273 K. of its molar mass.”
§ Empirical relationship stating that the ratio of the
If both gases are mixed in a 10L container, what are the partial rates of diffusion or effusion of two gases is the
pressures of nitrogen and oxygen in the resulting mixture?
What is the total pressure? square root of the inverse ratio of their molar masses
Partial pressure of Nitrogen is 4.79 atm
Partial pressure of oxygen is 2.40 atm
Total Pressure is 7.19 atm

1. Description of solid except


a. Fixed volume
b. Fixed Shame
c. Flow Easily
d. Rigid

2. Formation of condensate

CHECKPOINT a. Plasma
b. Liquid Crystals
c. Bose-Einstein Condensate
d. Any of the above

3. Third type of liquid crystals


5. Factor(s) affecting real gas equation
a. Smectic
a. Incompressibility
b. Nematic
b. Intermolecular forces
c. Cholesteric
c. Both
d. A and B
d. None
4. States that “At constant temperature, the
pressure P of a gas varies inversely with its volume V
a. Gay Lussac’s Law
b. Henry’s Law
c. Graham’s Law
d. Mariotte Law

Lecturer: Daryl E. Magno, RPh 19


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

LIQUIDS
§ Less kinetic energy than do gases
§ Occupy a definite volume
§ Take the shape of container
§ Denser than gases
§ Not compressible
LIQUIDS

LIQUIDS LIQUIDS
Vapor Pressure Vapor Pressure
§ Pressure of the saturated vapor above a liquid § Clausius-Clapeyr on Equation
resulting from the escape of surface liquid - shows the relationship between the
molecules vapor pressure of a liquid and the temperature
§ A measure of the tendency of molecules to escape
from a liquid

LIQUIDS LIQUIDS
Clausius-Clapeyr on Equation Clausius-Clapeyr on Equation

Sample Problem: Sample Problem:


A certain liquid has a vapor pressure of 6.91 mmHg at 0 A certain liquid has a vapor pressure of 6.91 mmHg at 0
°C. If this liquid has a normal boiling point of 105 °C, °C. If this liquid has a normal boiling point of 105 °C,
what is the liquid's heat of vaporization in kJ/mol? what is the liquid's heat of vaporization in kJ/mol?
Given R = 8.31147 J/mol K
Answer: 38445 J/mol or 38.4 kJ/mol

Lecturer: Daryl E. Magno, RPh 20


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

LIQUIDS LIQUIDS
Clausius-Clapeyr on Equation Clausius-Clapeyr on Equation

Sample Problem: Sample Problem:


Determine the vapor pressure of water at 150°C. The Determine the vapor pressure of water at 150°C. The
vapor pressure of water at 110 °C is 1.5atm and molar vapor pressure of water at 110 °C is 1.5atm and molar
heat of vaporization of 9500 cal/mole. Given R = heat of vaporization of 9500 cal/mole. Given R =
1.986cal/mol K 1.986cal/mol K

Answer: 4.88 atm

LIQUIDS LIQUIDS
Dispersed Systems Dispersed Systems
§ Systems in which one substance (dispersed phase) is 1. True Solutions
distributed, in discrete units, throughout a second § A solution is a homogenous mixture (one phase)
substance (continuous phase or vehicle) composed of two or more substances
§ A solute is dissolved in another substance, known
as a solvent
§ Particle size is < 1 nm

LIQUIDS LIQUIDS
Dispersed Systems Dispersed Systems
2. Colloidal Dispersions 3. Coarse Dispersions
§ A system having a particle size intermediate § Size of particle is larger than that of colloids
between that of a true solution and a coarse § Particle size is > 0.5 um
dispersion § Suspensions and emulsions
§ Particle size is 1 nm-0.5 um

Lecturer: Daryl E. Magno, RPh 21


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

SOLUTIONS
Solute and Solvent
Electolyte Nonelectrolyte
• Yields ions • Does not yield ions
• Conduct electricity • Does not conduct
Solute
• NaCl, HCl, CaCl 2 , electricity

SOLUTIONS
CH3 COOH • Sucrose

Solvent: phase of the solution and the largest portion of the


solution

LIQUIDS LIQUIDS
True Solutions Factors that Affect Solubility
SOLUBILITY TERM PARTS OF SOLVENT REQUIRED TO DISSOLVE § Temperature
ONE PART OF SOLUTE
- Endothermic reactions
Very Soluble Less than 1
- Absorb heat
Freely Soluble 1-10
- Increase temperature, increase solubility
Soluble 10-30
- Exothermic reactions
Sparingly Soluble 30-100
- Release heat
Slightly Soluble 100-1000
- Decrease temperature, increase solubility
Very slightly Soluble 1000-10000
Practically Insoluble Greater than 10000

LIQUIDS
Factors that Affect Solubility
§ pH
- Critical pH for weak acid and weak base
§ Presence of Salts
- Salting in (addition of salt, increased solubility)
- Salting out (addition of salt, decreased solubility) COLLIGATIVE PROPERTY
§ Nature of solute and solvent
§ Particle size
OF SOLUTIONS
§ Pressure (for gases)

Lecturer: Daryl E. Magno, RPh 22


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

LIQUIDS LIQUIDS
Colligative Properties of Solutions Colligative Properties of Solutions
1. Vapor Pressure Lowering 1. Vapor Pressure Lowering
§ When a nonvolatile solute is added to a volatile
solvent, the solute decreases the escaping tendency Sample Problem #1: What is the vapor pressure of an
of the solvent aqueous solution that has a solute mole fraction
§ The vapor pressure of the solution is lowered of 0.1000? The vapor pressure of water is 25.756
proportional to the relative number of solute mmHg at 25 °C.
molecules

Psolvent = X solventPosolvent Psolvent = X solventPosolvent

LIQUIDS LIQUIDS
Colligative Properties of Solutions Colligative Properties of Solutions
1. Vapor Pressure Lowering 1. Vapor Pressure Lowering

Sample Problem #1: What is the vapor pressure of an Sample Problem #2: Calculate the vapor pressure of a
aqueous solution that has a solute mole fraction solution made by dissolving 50.0 g
of 0.1000? The vapor pressure of water is 25.756 glucose, C6H12O6 (MW= 180g/mol), in 500 g of
mmHg at 25 °C. water. The vapor pressure of pure water is 47.1
torr at 37°C.
Answer: 23.18 mmHg Psolvent = X solventPosolvent

LIQUIDS LIQUIDS
Colligative Properties of Solutions Colligative Properties of Solutions
1. Vapor Pressure Lowering 1. Vapor Pressure Lowering

Sample Problem #2: Calculate the vapor pressure of a Sample Problem #3: Calculate the vapor pressure
solution made by dissolving 50.0 g of a solution made by dissolving 50.0 g CaCl2
glucose, C6H12O6 (MW= 180g/mol), in 500 g of (MW= 111g/mol) in 500 g of water. The vapor
water. The vapor pressure of pure water is 47.1 pressure of pure water is 47.1 torr at 37°C.
torr at 37°C.

Psolvent = X solventPosolvent
Answer: 46.63 torr

Lecturer: Daryl E. Magno, RPh 23


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

LIQUIDS LIQUIDS
Colligative Properties of Solutions Colligative Properties of Solutions
1. Vapor Pressure Lowering 2. Boiling Point Elevation
§ BP is the temperature at which the vapor pressure
Sample Problem #3: Calculate the vapor pressure of the liquid becomes equal to the external
of a solution made by dissolving 50.0 g CaCl2 in atmospheric pressure (1 atm or 760 mmHg)
500 g of water. The vapor pressure of pure § The BP of the solution containing a nonvolatile
water is 47.1 torr at 37°C. solute would be higher than the pure solvent

ΔT = i K b m
Answer: 46.35 torr

LIQUIDS LIQUIDS
Colligative Properties of Solutions Van’t Hoff Factor
2. Boiling Point Elevation Complete Dissociation

ΔT = i K b m Substance Van’t Hoff Factor


Non-electrolytes 1
§ Ebullioscopic constant (Kb) is the molal boiling
point elevation constant and its unit is degrees
NaCl 2
Celsius per molal (°C/molal) MgCl2 3
§ Van’t Hoff factor (i) is the number of particles
after dissociation
§ m is the molal concentration

LIQUIDS LIQUIDS
Van’t Hoff Factor Colligative Properties of Solutions
Incomplete Dissociation 2. Boiling Point Elevation

ΔT = i K b m
Sample Problem: What is the molecular mass of an
organic compound if 16.00 g of the compound is
dissolved in 225.0 g of carbon tetrachloride raises the
boiling point to 85.36 °C?
Given: BP and Kb of CCl4 is 76.72°C and 5.03°C kg/mol
respectively

Lecturer: Daryl E. Magno, RPh 24


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

LIQUIDS LIQUIDS
Colligative Properties of Solutions Colligative Properties of Solutions
2. Boiling Point Elevation 3. Freezing Point Depression
§ FP is the temperature at which a liquid turns into a
ΔT = i K b m solid when cooled
Sample Problem: What is the molecular mass of an § The FP of the solution containing a nonvolatile
organic compound if 16.00 g of the compound is solute would be lower than the pure solvent
dissolved in 225.0 g of carbon tetrachloride raises the
boiling point to 85.36 °C? Given: BP and Kb of CCl4 is
76.72°C and 5.03°C kg/mol
ΔT = i K f m
Answer: 41.4 g/mol

LIQUIDS LIQUIDS
Colligative Properties of Solutions Colligative Properties of Solutions
3. Freezing Point Depression 3. Freezing Point Depression

ΔT = i K f m ΔT = i Kf m
Sample Problem #1:
§ Cryoscopic constant (Kf) is the molal freezing point When 20.0 grams of an unknown nonelectrolyte
depression constant and its unit is degrees Celsius compound are dissolved in 500.0 grams of benzene,
per molal (°C/molal) the freezing point of the resulting solution is 3.77 °C.
§ Van’t Hoff factor (i) is the number of particles The freezing point of pure benzene is 5.444 °C and the
after dissociation Kf for benzene is 5.12 °C/m. What is the molar mass of
§ m is the molal concentration the unknown compound?

LIQUIDS LIQUIDS
Colligative Properties of Solutions Colligative Properties of Solutions
3. Freezing Point Depression 3. Freezing Point Depression
Sample Problem #1: ΔT = i Kf m
When 20.0 grams of an unknown nonelectrolyte compound are Sample Problem #2:
dissolved in 500.0 grams of benzene, the freezing point of the
resulting solution is 3.77 °C. The freezing point of pure benzene
Lauryl alcohol is obtained from coconut oil and is used
is 5.444 °C and the K f for benzene is 5.12 °C/m. What is the to make detergents. A solution of 5.00 g of lauryl
molar mass of the unknown compound? alcohol in 0.100 kg of benzene freezes at 4.1 °C and
Answer: 122.34 g/mol the Kf for benzene is 5.12 °C kg/m. What is the molar
mass of the lauryl alcohol? Freezing point of pure
benzene is 2.756 °C.

Lecturer: Daryl E. Magno, RPh 25


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

LIQUIDS LIQUIDS
Colligative Properties of Solutions Colligative Properties of Solutions
3. Freezing Point Depression 4. Osmotic Pressure
ΔT = i Kf m § Osmosis is the spontaneous net movement of water
across a semi-permeable membrane from a region
Sample Problem #2: of high to low water concentration
Lauryl alcohol is obtained from coconut oil and is used § The pressure required to prevent osmosis in
to make detergents. A solution of 5.00 g of lauryl solutions
alcohol in 0.100 kg of benzene freezes at 4.1 °C and
the Kf for benzene is 5.12 °C/m. What is the molar
∏ = iMRT
mass of the lauryl alcohol?
Answer: 190 g/mol

LIQUIDS LIQUIDS
Colligative Properties of Solutions Colligative Properties of Solutions
4. Osmotic Pressure 4. Osmotic Pressure

∏ = iMRT ∏ = iMRT
Where Sample Problem #1:
∏ is the osmotic pressure in atm
How much glucose (C6H12O 6) [MW = 180g/mol)
i = van’t Hoff factor of the solute
M = molar concentration in mol/L
per liter should be used for an intravenous
R = universal gas constant (0.0821 liter·atm/mol·K)
solution to match the 7.65 atm at 37 °C
T = absolute temperature in K osmotic pressure of blood?

LIQUIDS LIQUIDS
Colligative Properties of Solutions Colligative Properties of Solutions
4. Osmotic Pressure 4. Osmotic Pressure

∏ = iMRT ∏ = iMRT
Sample Problem #1: Sample Problem #2:
How much glucose (C6H12O6) [MW = 180g/mol) per What is the osmotic pressure of a solution prepared
liter should be used for an intravenous solution to by adding 13.65 g of sucrose (C12H22O11) [MW =
match the 7.65 atm at 37 °C osmotic pressure of 342g/mol) to enough water to make 250 mL of
blood? solution at 25 °C?
Answer: 54.1 g

Lecturer: Daryl E. Magno, RPh 26


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

LIQUIDS
Colligative Properties of Solutions
4. Osmotic Pressure

∏ = iMRT
Sample Problem #2:
What is the osmotic pressure of a solution prepared by ISOTONIC SOLUTIONS
adding 13.65 g of sucrose (C12H22O11) MW = 342g/mol)
to enough water to make 250 mL of solution at 25 °C?
Answer: 3.9 atm

LIQUIDS LIQUIDS
Isotonic Solutions Isotonic Solutions
1. Hypertonic Solutions 2. Hypotonic Solutions
§ A solution with more solute compared to cell § A solution with less solutes compared to cell
concentrations concentrations
§ Solutions that freeze lower that -0.52 °C § Solutions that freeze higher than --0.52 °C
§ Results: crenation of the cell (shrinkage) § Result: swelling and lysis of the cell

LIQUIDS LIQUIDS
Isotonic Solutions Isotonic Solutions
3. Isotonic Solutions
§ Solutions for which a living cell does not gain or
lose water
§ Solutions with similar osmotic pressure as that
of body fluids
§ Similar concentration as 0.9% (w/v) NaCl
solution

Lecturer: Daryl E. Magno, RPh 27


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

LIQUIDS
Methods of Adjusting Isotonicity
Class I: Addition of a tonicity adjusting agent
a. Freezing Point Depression Method/ Cryoscopic
Method
b. Sodium Chloride Equivalent Method/ E Value
METHODS OF Method
Class II. Addition of water and dilution with buffered
ADJUSTING ISOTONICITY isotonic solution
a. White Vincent Method
b. Sprowl’s Method

METHODS OF ADJUSTING ISOTONICITY METHODS OF ADJUSTING ISOTONICITY


Class 1: Addition of a tonicity adjusting agent Class 1: Addition of a tonicity adjusting agent
1. Cryoscopic Method 1. Cryoscopic Method
– Isotonic freezing point depression: 0.52 °C 0.52 − 𝑎
𝑤% =
– Isotonic NaCl concentration: 0.9% (w/v) NaCl 𝑏
0.52 − 𝑎
𝑤% = Sample Problem #1: How much NaCl is required to
𝑏 render 100 ml of a 1% soln. of apomorphin HCL
Where
W% = conc g/100mL of adjusting substance isotonic? Fpd of 1%NaCl=0.52º, Fpd of 1%drug=0.08º
a = freezing point depression of 1% adjusted substance multiple to
the percentage strength
B = freezing point depression of adjusting substance

METHODS OF ADJUSTING ISOTONICITY METHODS OF ADJUSTING ISOTONICITY


Class 1: Addition of a tonicity adjusting agent Class 1: Addition of a tonicity adjusting agent
1. Cryoscopic Method 2. E Value Method
– E value: gram of NaCl equivalent to 1 gram of
Sample Problem #2: Compound the precription:
substance
Freezing point depression of 1% atropine solution is
– Isotonic NaCl concentration: 0.9% (w/v) NaCl
0.07.

Rx Atropine Sulfate 1%
Sodium Chloride q.s.
Purified Water 100
Make isotonic solution.

Lecturer: Daryl E. Magno, RPh 28


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

METHODS OF ADJUSTING ISOTONICITY METHODS OF ADJUSTING ISOTONICITY


Class 1: Addition of a tonicity adjusting agent Class 1: Addition of a tonicity adjusting agent
2. E Value Method 2. E Value Method
Step 1: Calculate the amount of NaCl represented by the
ingredients in the prescription Sample Problem #1: How many grams of NaCl should
Step 2: Calculate the amount of NaCl that would make the be used in compounding the following prescription?
volume of solution specified in the prescription
Rx Pilocarpine nitrate (E = 0.22) 0.3g
Step 3: Subtract the amount of NaCl represented by the
ingredients in prescription from the amount of NaCl that NaCl qs
would make the specific volume in the prescription isotonic Purified Water qs 30mL
Step 4: if the tonicity agent is not NaCl, follow step 1-3 and
Make isotonic solution
the amount of NaCl is divided with the E value of that
chemical Sig for the eye

METHODS OF ADJUSTING ISOTONICITY METHODS OF ADJUSTING ISOTONICITY


Class 1: Addition of a tonicity adjusting agent Class 1: Addition of a tonicity adjusting agent
2. E Value Method 2. E Value Method

Sample Problem #2: How many grams of NaCl should Sample Problem #3: How many grams of boric acid
be used in compounding the following prescription to should be used in compounding the following
obtain an isotonic solution? prescription to obtain an isotonic solution?

Rx Cocaine HCl (E = 0.16) 2% Rx Atropine sulfate (E = 0.13) 1%


NaCl qs Boric Acid (E = 0.52) q.s
Purified Water qs 30mL Purified Water qs 30mL

METHODS OF ADJUSTING ISOTONICITY METHODS OF ADJUSTING ISOTONICITY


Class 1: Addition of a tonicity adjusting agent Class 2: Addition of a water and dilution with buffered
2. E Value Method isotonic solution
1. White Vincent Method
Sample Problem #4: How many grams of boric acid
v= 𝑤 𝑋 𝐸𝑣𝑎𝑙𝑢𝑒 𝑋 111 .1
should be used in compounding the following
prescription to obtain an isotonic solution?
Sample Problem: Using White Vincent Method,
Rx Phenacaine HCl (E = 0.17) 0.6g compute for the required volume to make 0.3 g of
Chlorambutanol (E = 0.18) 0.3g Atropine sulfate (E=0.13) isotonic.
Boric Acid (E = 0.52) q.s
Purified Water qs 60mL

Lecturer: Daryl E. Magno, RPh 29


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

METHODS OF ADJUSTING ISOTONICITY METHODS OF ADJUSTING ISOTONICITY


Class 2: Addition of a water and dilution with buffered Sample Problem
isotonic solution Rx
1. Sprowl’s Method Phenacaine hydrochloride 0.1g (E=0.20)
V= 0.3𝑔 𝑋 𝐸𝑣𝑎𝑙𝑢𝑒 𝑋 111 .1 Boric acid 0.50g (E=0.50)
Distilled water q.s. 100mL

Calculate the amount of water needed to make the


solution isotonic.

LIQUIDS
Acid-Base Equilibria
Theories on Acids and Bases
1. Arrhenius Theory
§ Acids are substances which produce hydrogen
ions in solution
THEORIES ON ACIDS § Bases are substances which produce hydroxide
ions in solution
AND BASES

LIQUIDS LIQUIDS
Acid-Base Equilibria Acid-Base Equilibria
Theories on Acids and Bases Theories on Acids and Bases
2. Bronsted-Lowry Theory 3. Lewis Theory
§ An acid is a proton (hydrogen ion) donor § An acid is an electron pair acceptor
§ A base is a proton (hydrogen ion) acceptor § A base is an electron pair donor

Lecturer: Daryl E. Magno, RPh 30


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

LIQUIDS LIQUIDS
Acid-Base Equilibria Acid-Base Equilibria
pH Sorensen’s pH Scale
§ The negative logarithm of the H+ concentration § pH > 7 is basic
§ Example, [H+] = 5 X 10 -6 , what is the pH? § pH = 0 is neutral
§ pH = 5.3 § pH < 7 is acidic

LIQUIDS LIQUIDS
Acid-Base Equilibria Acid-Base Equilibria
Ionization pH Calculations
§ The complete separation of ions in a crystal lattice when a
salt is dissolved Strong Acids pH = -log [H+]
§ For weak acids
HA + H2 O H3 O+ + A- pOH = -log [OH-]
Strong Base pH = pKw - pOH
§ For weak bases
B + H2 O OH- + BH+
Weak Acids pH = -log ( 𝒌𝒂 𝑿 𝑪𝒂 )
§ For the ionization of water
H20 + H2 0 H3 0+ + OH- pOH = log (√𝒌𝒃𝑿 𝑪𝒃 )
Weak Base

LIQUIDS LIQUIDS
Acid-Base Equilibria Acid-Base Equilibria
Buffer Henderson-Has sel bal ch Equation
• Solutions that have the property of resisting
changes in pH when acids or bases are
added to them pH = pK a + log ([A-]/[HA])
• Consists of either:
ü Weak acid and its conjugate base
ü Weak base and its conjugate acid pH = pK b + log ([B]/[OH -])

Lecturer: Daryl E. Magno, RPh 31


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

LIQUIDS LIQUIDS
Acid-Base Equilibria Acid-Base Equilibria
Henderson-Has sel bal ch Equation % Ionization
§ Acid
Sample Problem: % ionization = 100/ (1+10(pKa - pH))
Calculate the pH of a buffer solution made from 0.20 M § Base
HC2H3O2 and 0.50 M C2H3O2- that has an acid
dissociation constant for HC2H3O2 of 1.8 x 10-5
% ionization = 100/ (1+10(pH - pKa))

LIQUIDS LIQUIDS
Acid-Base Equilibria Acid-Base Equilibria
% Ionization % Ionization

Sample Problem: Sample Problem:


If the pH-pKa=-1, what percentage of weak base is If the pH-pKa=-1, what percentage of weak base is
nonionized? nonionized?

Answer: 9.1%

LIQUIDS
Acid-Base Equilibria
Buffer Capacity
§ Buffer Efficiency
§ Buffer Index
§ Buffer Value
§ The ability of a buffer solution to resist changes in INTERFACIAL
pH upon addition of an acid/alkali
§ Bmax (Maximum Buffer Capacity) = 0.567[C] PHENOMENA

Lecturer: Daryl E. Magno, RPh 32


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

LIQUIDS LIQUIDS
Interfacial Phenomena Interfacial Phenomena
§ Attributed to the effects of molecules found at § Capillary action- water “climb” upwards through
the interface (boundary between 2 phases) thin glass tubes (called capillary tubes) which
§ Interfacial tension if its between two liquids and depends on the attraction between water
surface tension between solids and gas and molecules and the glass walls of the tube
liquid and gas (adhesion), as well as on interactions between
water molecules (cohesion)
§ Surfactants – “surface active agents”, lower the
interfacial/surface tension

LIQUIDS
Interfacial Phenomena
§ Wetting phenomenon- determined by
measuring the contact angle, which the liquid
forms in contact with the solids or liquids
§ Contact Angle– angle which the liquid makes
with the solid surface

WETTABILITY CHANGE

COLLOIDAL
DISPERSION

Lecturer: Daryl E. Magno, RPh 33


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

LIQUIDS LIQUIDS
Colloidal Dispersions Colloidal Dispersions
LYOPHILIC LYOPHOBIC ASSOCIATION Properties of Colloids
(SOLVENT- (SOLVENT-HATING) (AMPHOPHILIC)
LOVING)
1. Optical
DISPERSED Large organic Inorganic particles Aggregates § Tyndall Effect
PHASE molecules (micelles) - ability to scatter light
SOLVATION Solvated Little Hydro or lipo
portion is 2. Kinetic
solvated § Brownian Motion
depending on
the medium - molecules in random constant motion
EFFECT OF STABLE UNSTABLE Salting out may § Diffusion
ELECTROLYTES occur at high
salt conc. - governed by Fick’s Law of Diffusion

LIQUIDS
Colloidal Dispersions
Properties of Colloids
3. Electric
§ Nernst Potential
- electrothermodynamic potential

§
- relate cell potentials
Zeta potential
RHEOLOGY
- Electrokinetic potential
- results to flocculation

LIQUIDS LIQUIDS
Rheology
§ Study of the deformation and flow properties of
matter
§ Viscosity- Measure of resistance to gradual
deformation by shear stress or tensile stress
1. Absolute Viscosity
2. Kinematic Viscosity
§ Elasticity-measure of stickiness or structure
§ Viscoelasticity- materials exhibit both elastic
behavior and viscous flow

Lecturer: Daryl E. Magno, RPh 34


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

LIQUIDS LIQUIDS
Rheology Rheology
1. Newtonian Flow
𝑭 § Constant viscosity with increasing rate
Absolute Viscosity 𝜼 =
𝑮 § Has a linear relationship between shear rate and shear stress
𝜂
Kinematic Viscosity 𝜅=
𝑝
Relative Viscosity Ratio of viscosity of
solutions to viscosity of
solvent

LIQUIDS LIQUIDS
Rheology Rheology
2. Non-Newtonian Flow Non-Newtonia n
A. Shear-dependent Viscosity
A. Shear-dependent Viscosity
1. Plastic
2. Pseudoplastic 1. Plastic
3. Dilatant § Bingham bodies
B. Time-dependent Viscosity § Require a yield stress before they begin to flow,
1. Thixotropy
i.e., the shear stress-strain curve doesn’t pass
2. Rheopexy
through origin

LIQUIDS LIQUIDS
Rheology Rheology
Non-Newtonian Non-Newtonian
B. Time-dependent Viscosity
A. Shear-dependent Viscosity
1. Thixotropy
2. Dilatant
§ show a time-dependent change in viscosity; the longer the
§ Viscosity of the fluid increases when shear is fluid undergoes shear stress, the lower its viscosity
applied (Reversible)
§ Shear-thickening § Time-dependent shear thinning
3. Pseudoplastic 2. Rheopexy
§ the longer the fluid undergoes shear stress, the higher its
§ the more shear applied, the less viscous it becomes viscosity
§ Shear-thinning § Time-dependent shear thickening

Lecturer: Daryl E. Magno, RPh 35


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

LIQUIDS LIQUIDS
Determination of Viscosity

1. Ostwald Glass Capillary Viscometer


2. Rotational Viscometers

LIQUIDS LIQUIDS
Determination of Viscosity Determination of Viscosity
A. Single Point A. Multipoint
1. Capillary Viscometer 1. Cup & Bob Viscometer
2. Falling Sphere Viscometer a. Searle Type
B. Multipoint
1. Cup & Bob Viscometer b. Couette Type
2. Cone & Plate
C. Others
1. Penetrometers

1. The p rocess wh ereby solute molecules mov e from the region


of higher to lower concentration until equilibrium is reached:
a. Osmosis
b. Diffusion
c. Dissolution
d. Distribution

2. E value is defined as

CHECKPOINT a. Equivalent NaCl enough to make a normal solution


b. Equivalent of NaCl to resemble the isotonicity of blood
c. Amount of NaCl theoretic ally equivalen t to 1 gram of a
specific chemical
d. Amount of the chemical theoretic ally equivalent to 0.9
grams of NaCl

Lecturer: Daryl E. Magno, RPh 36


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

3. Shear-thickening
a. Dilatant
5. A solution with less solutes compared to cell
b. Pseudoplastic
concentrations will result into
c. Plastic
a. Lysis
d. Newtonian
b. Swelling
c. Shrinkage
4. Ability of colloids to scatter light
d. A and B
a. Brownian Movement
b. Diffusion
c. Adsorption
d. Tyndall Effect

SOLIDS
§ Fixed shapes
§ Nearly incompressible
§ With strong intermolecular forces
§ With little kinetic energy

SOLIDS

SOLIDS SOLIDS
Crystalline solids Crystalline solids
§ Molecules are arranged in repetitious 3D lattice 6 Common Crystalline Structures
units 1. Cubic (Sodium Chloride)
§ Have sharp melting points 2. Tetragonal (Urea)
§ Have definite geometric forms 3. Hexagonal (Iodoform)
Amorphous solids 4. Rhombic (Iodine)
§ aka Glasses or supercooled liquids 5. Monoclinic (Sucrose)
§ No definite order of molecules 6. Triclinic (Boric acid)
§ No definite and sharp melting points

Lecturer: Daryl E. Magno, RPh 37


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

SOLIDS SOLIDS
Polymorphism Polymorphism
§ Ability of crystalline solids to exist in more than 1 § Enantiotropic
crystalline form Ø The polymorph which can be changed from
§ Polymorphs are solids that have more than 1 one form into another by varying temperature
crystalline form having different physical or pressure (REVERSIBLE)
characteristics (melting points and solubilities) § Monotropic
Ø The polymorph which can not be changed
from one form into another (IRREVERSIBLE)

SOLIDS
Polymorphism
§ Isotropic
Ø The properties of the different polymorphs
are identical
§ Anisotropic
Ø The properties of the different polymorphs
are different
MICROMERITICS

SOLIDS SOLIDS
Micromeritics Micromeritics
§ Study of small particles Fundamental Properties
§ Fundamental VS Derived properties § Particle Size
§ Includes: Coarse > 1000 um
ü Particle Size Conventional 50 to 1000 um
ü Particle Distribution Fine 1 to 50 um
ü Particle Shape Very Fine 0.1 to 1 um
ü Surface Area Ultra Fine <0.1 um
ü Derived Properties

Lecturer: Daryl E. Magno, RPh 38


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

SOLIDS SOLIDS
Methods of Particle Size Determination Methods of Particle Size Determination
1. Optical Microscopy 1. Use of microscope to measure individual particles
2. Sieving § 3 Measurements
3. Sedimentation Two tangents separated by the
Ferret Diameter
4. Particle Surface Area longest distance
Distance that will bisect the
Martin Diameter
particles into halves
Diameter of the circle that will
Projected Area of the Circle
enclose the particle

SOLIDS SOLIDS
Methods of Particle Size Determination Methods of Particle Size Determination
1. Use of microscope to measure individual particles 2. Sieve Analysis
- USP Method
- Mesh (Number of openings per linear inch)
Sample Problem:
20 10 g
40 20 g
60 40 g
80 25 g
Collecting pan 5 g
Solve for the % of particles with size > mesh 40

SOLIDS SOLIDS
Methods of Particle Size Determination Methods of Particle Size Determination
3. Sedimentation Method 4. Automatic Particle Counters
§ Based on the sedimentation rate of particles
§ Principle is Stokes’ Law Type of Counter Principle Involved
v = rate of settling Coulter Counter Electronic resistance
d = diameter
HIAV/ Royco Light
ρ s = density of the particles Light blockage
Blockage Instrument
ρ 0 = density of the dispersion
Photon correlation
medium Beckman Coulter Model
Spectroscopy
g = acceleration due to gravity
Microcomputerized
η = viscosity of the medium Adsorption
mercury porosimetry

Lecturer: Daryl E. Magno, RPh 39


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

SOLIDS SOLIDS
Derived Properties Derived Properties
Porosity Particle Volume

• Measure of total voids present in a particle True/ Particle Volume Vp Volume of particle
Granule Volume Vg V p + intraparticle
pores/spaces/voids
Bulk Volume Vb V g + interparticle
pores/spaces/voids
Void Volume v Volume of the spaces

SOLIDS SOLIDS
Derived Properties Porosity
Density of Particles • ∈ 𝒊𝒏𝒕𝒆𝒓𝒔𝒑𝒂𝒄𝒆 = (Vb
– Vg)/Vb X 100
• ∈ 𝒊𝒏𝒕𝒓𝒂𝒔𝒑𝒂𝒄𝒆 = (Vg – Vp)/Vg X 100
• ∈ 𝒕𝒐𝒕𝒂𝒍 = (Vb – Vp)/Vb X 100
True Density ρ M/Vp
Sample Problem
Granule Density ρg M/Vg
Given: volume of particles = 0.3
intraparticle spaces = 0.1
Bulk Density ρb M/Vb spaces between particles = 1.6

Solve: Vg, Vb, ∈ 𝒊𝒏𝒕𝒆𝒓𝒔𝒑𝒂𝒄𝒆 ,∈ 𝒊𝒏𝒕𝒓𝒂𝒔𝒑𝒂𝒄𝒆 ,∈ 𝒕𝒐𝒕𝒂𝒍

SOLIDS SOLIDS
Properties of Powders for Granulation Methods for Testing Flowability and Compressibility
§ Fluidity or flowability 1. Angle of Repose
§ Compressibility - The angle assumed by a cone-like pile of powder
Methods for Testing Flowability and Compressibility relative to the horizontal base
1. Angle of Repose Angle= Arc tan (H/R)
• The angle assumed by a cone-like pile of powder
relative to the horizontal base Sample Problem: 100g of powdered sample was made to
Angle= Arc tan (H/R) flow from a funnel suspended at a height of of 15cm. A
powder cone 12cm tall from the surface with a diameter
of 5cm was made. Determine the angle of repose.

Lecturer: Daryl E. Magno, RPh 40


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

SOLIDS SOLIDS
Methods for Testing Flowability and Compressibility
1. Carr’s Index or Compressibility Index
CI = (Vi- Vf) / Vi x 100

2. Hausner’s Ratio
HR= Vi / Vf

*Vi= Initial Volume or Untapped Volume


*Vf= Tapped Volume

1. Size and shape are ex amples of what typ e of particl e


properties:
a. Derived
b. Fundamental
c. Both
d. None

2. Measuremen t of particle size through op tical microscopy

CHECKPOINT which is the distance that will bisect the particle into halves
a. Ferret Diameter
b. Martin Diameter
c. Projected Area of the Circle
d. AOTA

3. Triclinic
5. The angle assumed by a cone-like pile of powder
a. NaCl
relative to the horizontal base
b. Urea
a. Angle of Repose
c. Sucrose
b. Carr’s Compressibility Index
d. Boric Acid
c. Hausner’s Ratio
d. NOTA
4. Properties are of polymorphs are identical
a. Enantiotropic
b. Monotropic
c. Isotropic
d. Anisotropic

Lecturer: Daryl E. Magno, RPh 41


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

THERMODYNAMICS
THREE LAWS OF THERMODYNAMICS
1. Law of Conservation of Energy, states that
energy cannot be created or destroyed
2. The second law states that the entropy of any
isolated system always increases
THERMODYNAMICS 3. The third law of thermodynamics states that the
entropy of a system approaches zero as
the temperature approaches absolute zero

THERMODYNAMICS THERMODYNAMICS
Phase Diagram Latent Heat or Molar Heat
• Represents the states of matter that exist as • Heat necessary for 1 mole of gas, solid or liquid
temperature and pressure are varied to change to another phase
Amount of energy that must be added to a mole of
solid at constant pressure to turn it directly into a
Heat of Fusion liquid (melting) or Amount of energy that must be
added to a mole of liquid at constant pressure to turn
it directly into a solid (freezing)

Amount of energy that must be added to a mole of


Heat of Vaporization
liquid at constant pressure to turn it directly into a gas

Amount of energy that must be added to a mole of


Heat of Sublimation
solid at constant pressure to turn it directly into a gas

THERMODYNAMICS THERMODYNAMICS
GIBB’s PHASE RULE GIBB’s PHASE RULE
§ Used to determine the number of § Example: A system comprising of liquid,
independent variables that must be set in water, in equilibrium with its vapor.
order to define a system Determine the degree of freedom.
§ Degree of Freedom
F = C-P + 2 (One-Compone nt System) § Then we cool the liquid water and its vapor
F = C-P + 1 (Two-Compone nt System) until a third phase (ice) separates out.
F = C-P (Three-Component System) Compute for the dree of freedom.

Lecturer: Daryl E. Magno, RPh 42


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

THERMODYNAMICS THERMODYNAMICS
One-Component System One-Component System

THERMODYNAMICS THERMODYNAMICS
Two-Component System containing Liquid Phases Two-Component System containing Liquid Phases
• The maximum temperature at which the two-
phase region exists is termed the critical
solution, or upper consolute temperature.

• In the case of the phenol–water system, this is


66.8°C (point h ).

• All combinations of phenol and water above this


temperature are completely miscible and yield
one-phase liquid systems.

THERMODYNAMICS THERMODYNAMICS
Two-Component System containing Liquid Phases Two-Component System containing Liquid Phases
• The line bc drawn across the region Lever rule is a tool used to determine mole
containing two phases is termed a tie line; fraction of each phase of a binary equilibrium
phase diagram.
• All systems prepared on a tie line, at
equilibrium, will separate into phases of
constant composition. Problem: Prepare a 50-g of mixture of 24%
phenol in water solution. Determine the
• These phases are termed conjugate proportion of component A (water) and
phases. component B (phenol) at 50 degrees celsius.

Lecturer: Daryl E. Magno, RPh 43


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

THERMODYNAMICS THERMODYNAMICS
Two-Component System containing Eutectic Mixtures Two-Component System containing Eutectic Mixtures
• solid–liquid mixtures in which the two
components are completely miscible in the
liquid state and completely immiscible as
solids.

• Examples of such systems are:


üsalol–thymol,
üsalol–camphor,
üacetaminophen–propyphenazone.

THERMODYNAMICS
Three-Component System

CHECKPOINT

1. Maximum temperature at which the two-phase region exists 3. Represents the states of matter that exists as
a. Critical solution temperature temperature and pressure varied
b. Tie Line
c. Conjugate phase
a. Thermodynamics
d. Lever arm b. Chemical Kinetics
c. Phase Diagram
2. Amount of energ y that must be added to a mole of liquid at d. NOTA
constant pressure to turn it directly into a gas
a. Heat of Fusion
4. Point where 3 distinct phases co-exist
b. Heat of Vaporization
c. Heat of Sublimation a. Triple
d. NOTA b. Eutectic
c. Critical
d. Polymorphic

Lecturer: Daryl E. Magno, RPh 44


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

CHEMICAL KINETICS
- Study of the rates of reactions and the mechanism of
which these reactions occur
Order of Reaction
- the way in which the concentration of the drug or
reactant in a chemical reaction affects the rate

CHEMICAL KINETICS

CHEMICAL KINETICS CHEMICAL KINETICS


1. Zero order Reaction 2. First Order Reaction
- Constant amount of drug is eliminated from the - Constant percentage of drug is eliminated from the
body (independent of the concentration in the body (dependent of the concentration in the
body) body)

C= -kt + Co ln C= -kt + ln Co

CHEMICAL KINETICS CHEMICAL KINETICS


Example Problem: Half-life
Initially a drug has concentration of 50mg/mL and after -period of time required for the amount or
20 days, the drug concentration became 24mg/mL. concentration of a drug to decrease by 50%
Compute for 1st order rate constant.
Zero order:
Half life = 0.5 C
First order
Half life= 0.693/K

Lecturer: Daryl E. Magno, RPh 45


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

CHEMICAL KINETICS
Sample Problem:
A drug has a biological half-life of 2 hours. At the end of
eight hours, what percentage of the drug’s original activity

FINAL
will remain?

CHECKPOINT

1. Atoms of the same element with the same number 3. Mixing a hypertonic solution with red blood cell will
of nucleon number, but differing numbers of atomic cause _________ of the red blood cell
number a. Bursting
a. Isotopes b. Crenation
b. Isobars c. Chelation
c. Isotones d. Hemolysis
d. AOTA
4. Dispersed system possess this property
2. Crystal system of sucrose. a. Optical activity
a. Cubic b. Solubility
b. Tetragonal c. Thixotropy
c. Monoclinic d. Tonicity
d. Triclinic

5. A patient diagnosed with type II DM is administered an For nos. 7-8. 6.3 mg of a boron hydride is contained in a flask of 385
oral dose of 0.1 mg chlorpropramide (pKa=2.0). Determine mL at 25.0° C and a pressure of 11 torr.
the amount of drug that can be absorbed in the stomach 7. Determine the molar mass of the hydride.
(pH=5.0) a. 27.70
a. 99.9mcg b. 2760.50
c. 2.706
b. 90mg d. 276.70
c. 10mcg
d. 0.10mcg 8. Which of the following hydrides is contained in the flask?
6. Forces between molecules of similar phases Given: MW B= 10.8110 g/mol
a. Adhesion
a. BH3
b. Cohesion
b. B2 H6
c. Both c. B4 H10
d. None d. None

Lecturer: Daryl E. Magno, RPh 46


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

9. Buffer solution is composed of:


11. States that an acid is a proton donor and base is a
a. Strong acid and strong base
proton acceptor
b. Strong electrolyte and strong base
a. Arrhenius
c. Weak acid and its salt
b. Bronsted-Lowry
d. Strong acid and its salt
c. Lewis
d. AOTA
10. Process whereby solvent moves from higher to lower
concentration until equilibrium is reached
12. USP method for adjusting isotonicity
a. Osmosis
a. E value
b. Diffusion
b. D value
c. Adsorption
c. White Vincent Method
d. Absroption
d. Sprowl Method

13. How much NaCl is needed to adjust the following prescription to 15. A solution of ferrous sulfate was prepared by adding
isotonicity? 50 grams of FeSO4 (MW= 151.9g/mol) to enough water to
Rx make 1000mL of solution. Compute for M.
Pilocarpint Nitrate 1% E = 0.15 a. 0.453
NaCl
b. 0.329
Purified Water q.s. 50mL
a. 0.5g c. 0.555
b. 0.450g d. 0.378
c. 0.375g
d. 0.245g 16. Weakest force of attraction
a. Keesom
14. Vant’ Hoff factor of incomplete dissociated CaCl 2
a. 1
b. Debye
b. 1.8 c. London
c. 2.6 d. NOTA
d. 3.4

For nos. 19-20. 100g powder


17. Formula for intraspace porosity Mesh # Grams of powder that did not pass
a. (Vb-Vg/Vb) X 100 20 15g
b. (Vb + Vp/Vb) X 100 40 25g
c. (Vg-Vp/Vg) X 100 60 10g
d. (Vb-Vp/Vb) X 100 80 35g
Collecting Pan 15g
18. The initial plasma concentration of a drug given IV at 19. What is the % of powder smaller than mesh 40 and larger than mesh 80?
9:00am is 250mg/mL. If the half-life of the drug is 6 hours, a. 70%
perform a calculation to predict the plasma concentration b. 45%
will be at 9:00pm that same day. c. 35%
d. 15%
a. 125mg/mL 20. What is the % powder larger than mesh 40?
b. 62.5mg/mL a. 10%
c. 31.25mg/mL b. 25%
d. 15.62mg/mL c. 35%
d. 40%

Lecturer: Daryl E. Magno, RPh 47


Pharmacist Licensure Examination 1/25/18
Module 5: Pharmacutics (17.5%)

21.Using White-Vincent Method, compute for 22. Solvent loving


the required volume to make 0.2g of a. Lyophobic
b. Lyophilic
atropine sulfate (E=0.13) isotonic. Answer
c. Amphiphilic
is in 2 decimal places. d. NOTA
a. 2.88
b. 2.89 23. Density is a derived quantity from
c. 3.00 a. Mass and Volume
d. NOTA b. Mass and Length
c. Mass and Weight
d. NOTA

24. Period of time where 90% of the original concentration


is left
a. Half-life
b. Shelf-life
c. Both
d. None

25. 322 L of hydrogen occupies a volume of 197 L at STP. If


the initial temperature of the hydrogen was 37° C, what
was its initial pressure?
a. 0.69 END OF PHYSICAL PHARMACY REVIEW
b. 0.79
c. 0.89
d. 0.99

Lecturer: Daryl E. Magno, RPh 48

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