AUF CAMP – PHARMACY DEPARTMENT

PHYSICAL PHARMACY (LABORATORY)

Exercise 8: Interfacial Phenomena
Lecturer: Patrick Ian Ortega

SURFACE AND INTERFACE Surface tension depends on the strength of the cohesive forces. Molecules
at the surface do not have their attractive forces balanced. They experience
Interface an inward force (side or lower) which causes the water molecules at the
 Boundary between any two phases surface to adhere together, hence, the rationale why it hurts when we land
 The properties of molecules forming the interface are often on water.
sufficiently different from those in the bulk of each phase  Surface molecule pulled inward
 Liquid-liquid, liquid-solid, solid-solid  Interior molecule pulled equally in all directions
 Property between any two (2) substances
EXPERIMENTS
Surface SURFACE TENSION MEASUREMENT
 Liquid-gas, solid-gas
 Surface tension – property of the liquid in contact with the gas Reagents/Materials
phase, usually the air  Liquid detergent  Analytical balance
 Sulfur powder  Pipette
Classification of Interfaces  Talc  Capillary tube
Phase Types and Examples of Interfaces  Tween 80  Ruler
Gas-Gas No interface possible  Water  Beaker
Gas-Liquid Liquid surface  Alcohol  Dropper
Gas-Solid Solid surface
 Mineral oil
Liquid-Liquid Liquid-liquid interface
Liquid-Solid Liquid-solid interface
Solid-Solid Solid-solid interface Capillary Rise Method
 Most accurate way of measuring surface tension, although it is
COHESION AND ADHESION not suitable for measuring interfacial tension because the walls
of the narrow tube can be efficiently wetted by the liquid
Cohesion 1. Liquid wets walls of tube, increasing surface area.
 Interaction between like molecules (e.g., water to water) 2. Surface tension acts to decrease area, pulling liquid up.
3. Wetting continues from higher level, causing liquid to continue
 Cohesive forces – intermolecular forces which cause a material
rising.
or substance to resist separation
4. Eventually, the liquid reaches a height at which its weight is
 Example: hydrogen bond in water – strong
 Cohesive force is stronger in solids exactly balanced by surface tension, resulting in a constant
height.
 Water has both cohesive and adhesive force

Adhesion
 Interaction between unlike molecules
 Adhesive forces – caused by forces that is acting between two
substrates such as mechanical and electrostatic forces
Procedure – Measuring the Surface Tension
1. Measure the diameter of the capillary tube (1mm).
2. Fill the beaker with water and dip the capillary tube just below
the surface of the liquid.
3. Note the rise of liquid in the capillary tube. Measure the height
of rise from the surface of the liquid to the lower meniscus
(meniscus – “curve”; water – 13mm).
4. Record the data and compute the surface tension using the
Water (polar) on a plastic (nonpolar) Water on a glass (and other polars) equation: surface tension = ½ (r)(h)(p)(g)
Cohesive > Adhesive Adhesive > Cohesive 5. Repeat the same procedure with alcohol (ethanol – 8mm) and
mineral oil (12mm).
If the liquid is clear, measure using the
lower meniscus (water is attracted to
the glass)

If the fluid is not clear, measure using

the upper meniscus

Mercury: cohesive, convex

Water – adhesive, concave 1 2 2 3

SURFACE AND INTERFACIAL TENSION

4 5 5 5

Formula

Surface tension = ½ (r)(h)(p)(g), where

 r = radius of the capillary tube
 h = height of the liquid

Renhart M. Salas, fRPh 1|Pa ge

 AUF CAMP – PHARMACY DEPARTMENT
PHYSICAL PHARMACY (LABORATORY)
Exercise 8: Interfacial Phenomena
Lecturer: Patrick Ian Ortega

 p = density of the liquid SURFACTANTS

 g = acceleration of gravity (981cm/sec2)
Surfactants, generally, are organic compounds which are amphiphilic,
Example meaning that it possesses both hydrophobic and hydrophilic properties.
Surface tension = ½ (r)(h)(p)(g) Due to tis amphiphilic nature, the surfactant can adsorb onto the surface
Surface tension = ½ (0.1cm)(1.3cm)(1g/cm3)(981cm/sec2) and lower the tension of interfaces.
Surface tension = 63.765 dyne/cm
Hydrophilic head – water-loving
Solve
Diameter = 0.12cm, height = 6.6in, density = 0.81g/cm3
Surface tension = ½ (0.06cm)(16.764cm)(0.81g/cm3)(981cm/sec2)
Surface tension = 399.6253 dyne/cm Hydrophobic tails – water-hating

Diameter = 2cm, height = 2ft, density =0.84g/cm3

Surface tension = ½ (1cm)(60.96cm)(0.84g/cm3)(981cm/sec2)
Surface tension = 25116.7392 dyne/cm
Procedure – Interfacial Properties of Surfactant
OTHER METHOD OF SURFACE TENSION MEASUREMENT Procedure A
1. Prepare 4 concentrations of detergent solution as follows: 25%,
Drop Count Method 50%, 75%, 100%.
 Stalagmometer: water gradually falls, similar to “gripo” 2. Make 2 markers on the pipette, approximately 1mL. Fill the
pipette with water up to the mark.
3. Allow the liquid to drain slowly up to the lower mark counting
the drops.
4. Record the number of drops and repeat one more time.
5. Repeat the same procedure with detergent solutions prepared
previously.

Wilhelmy Plate Method

 Uses a paper made from either glass, platinum, or mica attached
to a balance
 Principle: slowly dip the paper in the water and observe how
strong the water is to detach the paper from the balance
Ring Detachment Method (du Nuoy Tensiometer)
 Dip the ring on the surface of the water and then, observe how
high the water will rise
1 2
Procedure B
1. Prepare 2 beakers filled with water. Sprinkle sulfur powder.
Observe.
 The sulfur powder floats because the particles are
very small and sulfur itself is hydrophobic.
2. In beaker 1, add 1-2 drops of detergent solution.
3. In beaker 2, add 1-2 drops of tween 80. Observe.
4. Repeat the same procedure using talc powder.
 Talc floats also on the water surface because of its
hydrophobicity.
5. In beaker 1, add 1-2 drops of detergent solution.
6. In beaker 2, add 1-2 drops of tween 80. Observe.

1 1 4

Spinning Drop Method

 Use of special devices and machines – very expensive
 Useful for determining very low interfacial tension

5 6

In one beaker sprinkled with sulfur powder, a drop of detergent solution

caused the sulfur powder at the surface of the water to sink due to the ability
of the detergent, which is a surfactant, to break surface tensions. On the
other hand, with tween 80, the sulfur powder did not move at all nor sink

Renhart M. Salas, fRPh 2|Pa ge

 AUF CAMP – PHARMACY DEPARTMENT
PHYSICAL PHARMACY (LABORATORY)
Exercise 8: Interfacial Phenomena
Lecturer: Patrick Ian Ortega

from the water surface. Only the tween 80 itself sank through the water
after dropping.

In one beaker sprinkled with talc, a drop of detergent solution caused the
talc powder to spread on water surface. The effect of the soap is to break
the film of surface tension at the place where soap touches the water. The
molecules of water attract molecules of soap, which breaks apart the talcum
powder. The same is true with tween 80.

Renhart M. Salas, fRPh 3|Pa ge

 AUF CAMP – PHARMACY DEPARTMENT
PHYSICAL PHARMACY (LABORATORY)
Exercise 9: Powders
Lecturer: Patrick Ian Ortega

POWDERS  In general, particles in the size range of 250-2000 micron flow

Flowability
 Ability of a powder to flow in a desired manner
 Importance: manufacturing process of tablets and capsules,
powder-filling
 Powder handling steps: blending of powder, transfer of powder
from one container to another, storage, and feeding of powder
in presses (tablet) and punches
 Inability to achieve this reliability or failure to have a good
powder flow  may have significant adverse effect in the
manufacture and release of powder in the body
freely if the shape is agreeable. Particles in the size range of 75-
250 micron may flow freely or cause problems, depending on
shape and other factors. With particles less than 100 micron in
size, flow is a problem.
 Smaller particle size, more difficult to flow  directly
proportional (high particle size, high flowability)
DENSITY
 Particles with density and low porosity tend to possess free
flowing properties  denser, more difficult to flow

 Free flowing – if the particles does not stick together
 Non-flowing – if the particles are cohesive, they stick to one
another and form aggregates  bigger powder particle
 Cohesion increases as powder size decreases
Flow Patterns
 Develop when the powder flows inside the container
 Funnel flow – “core flow,” center moves faster while powder
at the side is stuck/stagnant unless tapped but this cannot be
done in the manufacturing pharmacy because the machines are
big
 Tendency is powder added at the top will flow first
than the powder stuck at the sides  expire
 Mass flow – all particles move at the same speed and follows
FIFO (first in, first out)  desired
PARTICLE SHAPE
 Rough irregular particles present more points of contact than
smooth spherical particles, thus, spherical particles flow better
than needles.
PARTICLE SIZE DISTRIBUTION
 Larger amount of fines can inhibit poor flowing
MOISTURE CONTENT
 Drying the powders will reduce the cohesiveness
 Dry  easier to flow; moist  slower to flow
Powder Flow Problem

Arching (Bridging) Rat-holing

 Rat-holing – similar to funnel flow; old powders on the side
 Arching or Bridging – build-up of powder near the exit 
cannot pass through; prick to reestablish flow

MEASUREMENT OF FLOW PROPERTIES

Powder may be subjected to storage, transportation, handling, processing,

Factors Affecting Powder Flow and manufacturing. During storage, powders may consolidate and
 Flow properties depend on: aggregate.
1. Powder variable  Caking – solid aggregation of powder, either at the top or
2. Environmental factors bottom  more resistant to flow
*Collective forces acting on individual particles  “Nahanginan”  particles separate, “tumigas,” or oxidized
 It is essential to generate relevant data in testing powders under
POWDER VARIABLES / PARTICLE VARIABLES conditions that we can stimulate or mimic the environment and
specific stresses that is associated with the process or
 Particle size  Wear or attrition application (e.g., such as in room temperature)  to know the
 Shape  Hardness best storage condition as an example
 Surface texture  Stiffness
 Cohesive forces  Strength Angle of Repose
 Surface coating  Fracture toughness  The internal angle between the surface of the pile and the
 Particle interaction horizontal surface (of the table, as an example)
 Depends on density, surface area, shapes of the particles, and
ENVIRONMENTAL FACTORS friction of the material
 Angle of Repose of 25-30°  move through the hopper, feed
 Flow rate  Aeration frame, die table, and die boards smoothly
 Compaction condition  Container surface effects
 Humidity  Storage time Flow Property Angle of Repose (degrees)
Excellent 25-30
 Electrostatic charge
Good 31-35
Fair – aid not needed 36-40
PARTICLE SIZE Passable – may hang up (may bridge) 41-45
Poor – must agitate, vibrate 46-55
 Frictional and cohesive forces (resistance to flow) are increased Very poor 56-65
as the particle size is reduced. Very fine particles do not flow as Very, very poor (bridge, rat-hole) >66
large particles  Johnson’s baby powder vs salt or sugar

Renhart M. Salas, fRPh 1|Pa ge

 AUF CAMP – PHARMACY DEPARTMENT
PHYSICAL PHARMACY (LABORATORY)
Exercise 9: Powders
Lecturer: Patrick Ian Ortega

Starch
 Synonym: Amylum
 Empirical formula: (C6H10O5)n
 Description: Soft, white, tasteless powder that is insoluble in
cold water, alcohol, or other solvents
EXPERIMENT
Procedure
Effects of Glidants on the Flowability of Powders
Procedure
1. Prepare three (3) vessels, each containing 5g of salicylic acid
Angle of Repose
powder
1. Prepare 5g of salicylic acid powder
2. Add 0.5g of magnesium stearate, 0.5g of starch, and 0.5g of talc
2. Allow the powder to flow through a funnel and fall freely into
to powder A, B, and C, respectively
the surface
3. Allow each powder mixture to flow through a funnel until a
3. Measure the height and diameter of the resulting cone
cone is formed
4. Compute for the angle of repose using the following equation:
4. Measure the height and width of the resulting cone
Tan θ = h/r
5. Compute the angle of repose and compare the results in
procedure 1

1 2 3
1 2 3

3 4

Computation
 Given: h = 18.5mm, d = 40mm 4 4
 θ = tan-1(h/r)  “shift” + “tan” for tan-1
 θ = tan-1(18.55mm/20mm)  42.77° passable – may hang up Computation
 Talc: h = 15mm, d = 50mm  30.96° good
GLIDANT  Magnesium stearate: h = 17mm, d = 55mm  31.72° good
 Starch: h = 16mm, d = 49mm  33.15° good
 A substance that is added to a powder to improve its flowability
by reducing inter-particle friction, cohesion, and surface charge COMPRESSIBILITY INDEX
 decreasing angle of repose
 Will only work at a certain range of concentration  above  Are measures of the propensity of a powder to be compressed
certain concentration, the glidants will impact function to  Are measures of the powder’s ability to settle and they permit
inhibit flowability an assessment of the relative importance of inter-particulate
 Often incorporated to dry powders before direct compression interactions
for tablet production  Both Carr and Hausner proposed to measure the bulk and
 Examples: magnesium stearate, starch, talc tapped density of a bulk material and calculate a ratio in order
 Functions: to estimate how the material will flow
 To improve powder flow
 To reduce inter-particle friction Carr’s Index
 To reduce cohesion  CI% = [(tapped – bulk) x 100] / tapped density

Talc Hausner’s Index

 Synonym: Talcum powder  HR = tapped density / bulk density
 Empirical formula: Mg3Si4O10(OH)2
 Chemical name: Magnesium silicate hydroxide Carr’s Index Flow Property Haussner Ratio
 Description: Very fine, white to grayish-white, odorless, ≤10 Excellent 1.00-1.11
crystalline powder 11-15 Good 1.12-1.18
16-20 Fair 1.19-1.25
21-25 Passable 1.26-1.34
Magnesium Stearate 26-31 Poor 1.35-1.45
 Synonym: Dibasic magnesium stearate 32-37 Very poor 1.46-1.59
 Empirical formula: Mg(C18H35O2)2 >38 Very very poor >1.60
 Description: Very fine, light white powder of low bulk density, Angle of Slide
faint odor of stearic acid and characteristic taste

Renhart M. Salas, fRPh 2|Pa ge

 AUF CAMP – PHARMACY DEPARTMENT
PHYSICAL PHARMACY (LABORATORY)
Exercise 9: Powders
Lecturer: Patrick Ian Ortega

Bulk Density 1. Talc

 Used to determine the amount of powder that can be fitted into a. Bulk density = 2
a capsule and that can fit in a space such as a blender, hopper, b. Tapped density = 2.11
tablet press, or capsule filler c. Carr’s = 5.2133 excellent
 Essential parameter for process development and in solid d. Hausner’s = 1.055 excellent
dosage manufacturing
 Bulk density = mass / bulk volume 2. Starch
a. Bulk density = 1.5
 Density – is defined as weight per unit volume b. Tapped density = 1.8
 Bulk density – obtained by dividing its mass by the bulk volume c. Carr’s = 16.6667 fair
it occupies; very difficult to measure because the beaker should d. Hausner’s = 1.2 fair
not be disturbed as the powder may move and fill in gaps
 Bulk volume – is the volume of a powder as poured into a
measuring vessel and includes both inter- and intra-particulate
spaces between and of the particles
 Tapped density – ratio of the mass of the powder to the volume
occupied by the powder after it has been tapped for a defined
period of time

Procedure
Bulk Density of Powders
1. Get approximately 50g of each powder, bismuth sub-carbonate,
magnesium carbonate, and talc
2. Allow each type of powder to pass through sieve no.20
3. Carefully add the powder into three separate 100mL graduated
cylinder; ensure to reach the 50mL mark
4. Drop each graduated cylinder into a hard wood surface three
times at a height of one inch with a two-second interval
5. Note the final volume obtained and calculate the bulk density
of each powder using the equation below
 Tapped density = weight of the sample (g) / final
volume (mL)

1 2 3

4 5 Others

Computation
1. Talc
a. Weight = 100g
b. Initial volume = 50mL
c. Final volume = 47.5mL

2. Starch
a. Weight = 45g
b. Initial volume = 30mL
c. Final volume = 25mL

Renhart M. Salas, fRPh 3|Pa ge

 AUF CAMP – PHARMACY DEPARTMENT
PHYSICAL PHARMACY (LABORATORY)
Exercise 10: Particle Size Determination
Lecturer: Patrick Ian Ortega
PARTICLE SIZE
 Term which is mostly used to denote the dimensions of solid
particles
 Physical properties of active pharmaceutical ingredients and
excipients largely depend on their particle size which are used
to formulate pharmaceutical dosage form
 That is because particle size and shape have profound impacts
on each and every manufacturing step including mixing,
granulation, drying, milling, blending, coating, encapsulation
and compression
 Particle size or grain size refers to the diameter of a grain of
granular material
Gravel – 2-75mm
Sand – 0.05-2mm
Silt – 0.002-0.05mm
Clay – <0.002mm
Particle Size Distribution
 A measurement that defines the number of particles present
according to their size
 Spherical: diameter
 Irregular: vertical and horizontal projections (length and width)
Influence of Particle Size
 Dissolution
 Small particles dissolve more rapidly than large
ones (directly proportional), which is important not
only in determining the behavior of the drug in vivo
but also in various manufacturing processes
 There are tablets that we want to dissolve rapidly
and there are some that we want to dissolve longer
 enteric-coated, extended-release
 Stability of dispersions
 Refers to their long-term integrity and ability to
remain in the state they were initially formulated
 Tablet: how long will it remain as a tablet; how long
will it take for it to disperse inside the body
Suspension
 Flow properties of powders
 The flow properties of powders are strongly
dependent on particle size and, in particular, particle
shape
 Since most powders are moved from one place to
another by flowing, control of flow behavior is
highly important
 Generally, coarse, roughly spherical particles flow
much more easily than small or elongated particles
 Suspension: small particle size  free-flowing,
dispersed; big particle size  settle at the bottom,
aggregates, sedimented
EFFECT OF PARTICLE SHAPE
 Particle shape influences such properties as:
 Flowability of powders
 Packing
 Interaction with fluids
 Covering power of pigments – such as colorants for
aesthetic appeal
 The variation between diameters increases as the particles
diverge more from the spherical shape
 Different results from different techniques can be compared by
applying shape factors and shape coefficients
EXPERIMENT
METHODS TO DETERMINE PARTICLE SIZE
OPTICAL MICROSCOPY
 0.2-100um (micrometer); most simple
 In this method, small sample size is mounted on the stage of the
microscope and the particle size is measured using the
micrometer attached to it
 The image of a particle seen in a microscope is 2D (two-
dimensional) and from this image an estimate of particle size
must be made
 Manual analysis of microscope slides is tedious and error prone;
semi-automatic and automatic systems have been developed
which speed up analyses and reduce the tedium of manual
methods
 A least 300-500 particles must be counted in order to obtain a
good size distribution analysis of data
Advantages
 Inexpensive
 Each particle individually examined
 Detect aggregates
 Permanent record (photograph)
 Small sample size required
Disadvantage
 Time-consuming
Procedure
1. Spray the aerosol in a clean, dry microscope slide
2. Examine the slide under a microscope equipped with calibrated
ocular micrometer
3. Focus on the particles and note the size of the great majority of
individual particles
4. Record the size of individual particles until you measured not
less than 200 particle size of the aerosol powder
5. Calculate the average particle size of the powder of the particles
2 3
Renhart M. Salas, fRPh 1|Pa ge
 AUF CAMP – PHARMACY DEPARTMENT
PHYSICAL PHARMACY (LABORATORY)
Exercise 10: Particle Size Determination
Lecturer: Patrick Ian Ortega

4 Other
3 4
SIEVE METHOD
SEDIMENTATION TECHNIQUE
 5um-3mm
 Performed using a nest or stack of sieves where each lower  Particle size distribution is determined using the Andreasen
sieve has a smaller aperture size than that of the sieve above it pipette

Sieves

Sieves
 The woven sieve is the oldest design, and it is normally made
by weaving fine metal wire into a square pattern, then soldering
the edges securely into a flattish cylindrical container
 Woven-wire sieves were originally designated by a mesh
number, referred to the number of wires per inch, which is the
same as the number of square apertures per square inch

Advantages
 Easy to perform  tap only
 Wide size range
 Inexpensive

Disadvantages
 Problems in reproducibility  some powders are stuck and/or
will block the apertures
 Wear/damage in cleaning  cannot be brushed nor wetted
 Irregular/agglomerated particles
 Rod-like particles  “pahaba” will pass through vertically
 Labor intensive
 Particle aggregation

Procedure
1. Weigh about 25g of citric acid powder
2. Let the citric acid powder pass through a series of sieves
arranged in such a manner that the sieve with smaller number
should be on top
3. Shake the sieve (tap method)
4. Weigh the amount of powder remaining on the sieves and in the
receiving pan
5. Calculate the average particle size of the substance used
 % retained = (weight retained / initial weight) x 100

1 2

Renhart M. Salas, fRPh 2|Pa ge

 AUF CAMP – PHARMACY DEPARTMENT
PHYSICAL PHARMACY (LABORATORY)
Exercise 11: Viscosity of Different Liquids
Lecturer: Patrick Ian Ortega

VISCOSITY  Suitable only for Newtonian systems

 U-tube with two bulbs (left – sample; right – testing area)
 Property of liquids that is directly related to the resistance to
flow Upper mark indicating where sample is moved to by
 It is a measure of how easily a liquid can flow suction
 Resistance in the flow of a liquid
 Internal friction between two layers of liquids which resist the Lower mark representing original position which
flow of a liquid sample returns to when suction force is released

Capillary tube which tests samples’ viscosity by

reducing the diameter of tube which oil flows in

Oil is drawn into tube to start mark by suction

Tube is submerged into constant temperature bath
Start Mark (seconds)  Stop Mark

Stoke’s Law Time is measured in seconds as fluid flows from the start to
stop marks (efflux time)
 Proponent: Sir George Gabriel Stokes
 F = 6πanv  mathematically equates viscosity
Advantages
Factors Affecting Viscosity  Small, portable  Measure precise viscosities
1. Size of molecules – high particle size solutions show high  Inexpensive  Easy to use
viscosity (directly proportional)
2. Shape of the molecules – spherical molecules show low Disadvantages
viscosity; non-spherical and/or irregular-shaped molecules  Difficult to clean  because of its shape
have high viscosity  Basic models can only be used for translucent fluids (water, oil)
3. Intermolecular forces – large intermolecular forces have  No single tube is suitable for all viscosities  if used with oil,
greater viscosity (directly proportional) then it should be used only for oil; if non-Newtonian fluid is
4. Temperature – high temperature shows low viscosity measured, then it cannot be used anymore
(inversely proportional)
FALLING SPHERE VISCOMETER
TYPES OF FLUID (VISCOSITY BEHAVIOR)

Newtonian Fluids
 Fluid with a constant viscosity at a fixed temperature with no
effect by pressure  fluid is not compressible
 Named after Sir Isaac Newton – also discovered the laws of
gravity and invented calculus
 Described flow behavior of fluids with a simple
linear relationship between shear stress and shear
rate  Newton’s Law of Viscosity
 Examples: water, alcohol, chloroform, gasoline, mineral oil
 In this method, the metal or glass ball rolls down in a vertical
Non-Newtonian Fluids glass tube which is filled with the sample solution
 When shear (pressure) is applied, the viscosity of the fluid  Suitable only for Newtonian systems
changes  enough force applied, viscosity changes
 Principle: Stoke’s Law that states “when a body falls in viscous
 Examples: suspensions, emulsions media, it experiences a resistance which oppose the motion of
 Classes a fluid”
 Plastic – paints, ointments
 Pseudoplastic – ketchup, quicksand Advantage
 Shear thinning – gets thinner when force  High shear devices  can be used for viscous substances
is applied
 Dilatant – sand on the beach Disadvantages
 Shear thickening – gets thicker when
 Maintenance intensive  glass ball may be lost or broken
force is applied
 Parts intensive  parts are expensive
TYPES OF VISCOMETERS
CUP BOB VISCOMETER
There are mainly four types of viscometers mainly employed for the
determination of viscosity.  Consist of two coaxial cylinders of different diameters
 Suitable for Newtonian and non-Newtonian systems
CAPILLARY VISCOMETER
Types
 Based on the principle of the measurement of the time taken for  Searle type viscometer
the liquid to flow between two marks  Stormer viscometer, Brookfield viscometer
 The bub (like hand mixer) is rotated while the cup is
 Commonly known as Ostwald viscometers  named after
held stationary
Wilhelm Ostwald

Renhart M. Salas, fRPh 1|Pa ge

 AUF CAMP – PHARMACY DEPARTMENT
PHYSICAL PHARMACY (LABORATORY)
Exercise 11: Viscosity of Different Liquids
Lecturer: Patrick Ian Ortega

 Couette type viscometer

 MacMichael viscometer
 The cup is rotated and the viscous drag on the bob
produced by the liquid results in a torque which is
proportional to the viscosity of the liquid
 Platform (cup), where the beaker/container is rested,
is the one that spins
1 2 4

B. Effect of Temperature on Viscosity

1. Prepare 3 graduated cylinders
2. Fill cylinders 1, 2, and 3 with 20mL of tap water, water
previously cooled inside the refrigerator for 15 minutes, and
water previously heated to about 60℃ for 15 minutes
3. Perform the procedure in letter A in the three samples
4. Repeat the same procedure using mineral oil as the sample

CONE AND PLATE VISCOMETER

 The cone is driven by variable speed motor and the sample

solution is sheared in the narrow gap between the stationary
plate and the rotating cone. The sample solution is placed at the
center of the plate.
 A cone plate is precise torque meter which driven at discrete
rotational speed.
 The torque measuring system which consist of a calibrated 1 2
beryllium copper spring connecting the driven mechanism to
the rotating cone.
 Sense of resistance to rotation caused by presence of sample
fluid between the cone and the stationary flat plate.

Advantages
 Can measure viscosities of opaque, non-Newtonian fluids
 Cannot be used for Newtonian fluids because they
may flow out on the side of the plate
 Speed of the rotating part easily adjusted
 Linked to computers for semi-automated measurements

Disadvantages
 Expensive  high accuracy
 Large and not portable – for manufacturing

EXPERIMENT

A. Viscosity of Various Dosage Forms

1. Fill a graduated cylinder with 20mL of the sample solution
(water)
2. Drop six pebbles one at a time into the solution
3. Using stopwatch, record the time it takes for each pebble to
reach the bottom
4. Repeat the same procedure using emulsion, suspension, and
syrup as the samples
 Left – suspension (pink, light red)
 Center – solution (clear deep red)
 Right – emulsion (amber)

Renhart M. Salas, fRPh 2|Pa ge

 AUF CAMP – PHARMACY DEPARTMENT
PHYSICAL PHARMACY (LABORATORY)
Exercise 12: Rheology
Lecturer: Patrick Ian Ortega
RHEOLOGY
 “rheo” – to flow, stream; “logy” – study of
 Science/physics that concerns with the flow of liquids
 Study of the flow of materials that behave in an interesting or
unusual manner
 Normal: water, oil
 Unusual: mayonnaise, chocolate, peanut butter
 Study of what happens when you squish stuff  there is an
element of pressure or force that comes into play
Importance in Pharmacy
 Formulation of medicinals and cosmetics (creams, lotions,
pastes)
 Formulation of emulsions, suspensions, and suppositories
 Passage of a liquid to a syringe (IM, IV, intraosseous,
intraocular)
 Mixing and flow of materials during packaging and use
 Achieved whether by pouring from a bottle or
passage to a container or even passage through a
syringe needle
Newton’s Law
 The higher the viscosity of a liquid, the greater is the force per
unit area (shearing stress) required to produce a certain rate of
shear
 Shear – movement of material relative to a parallel layer
 Shear stress – force required for a substance to flow
 Shear rate – difference in velocity between two planes of liquid
separated by distance
Difference Between Normal Stress and Shear Stress
 Normal stress – if the force is applied from the top
 Shear stress – force applied is from the side
TYPES OF FLOW
NEWTONIAN FLOW
 Fluid whose shear stress versus shear rate curve is linear and
passes through the origin
 Viscosity is linearly dependent on the shear rate (viscosity is
constant no matter how much the shear rate is)
 Viscosity will only change with change in temperature but not
pressure; shear rate is constant in terms of velocity
 Examples: water, chloroform, alcohol, gasoline, honey
NON-NEWTONIAN FLOW
 Defined as one for which the relation between shear stress and
shear rate is not linear
 When the shear rate is varied, the shear stress is not varied in
the same proportion
 When shear is applied, the viscosity of the fluid changes
 Can be seen in liquids and in solid heterogenous dispersions
such as emulsions, suspensions, colloids and ointments
 Classes: plastic, pseudoplastic, dilatant
Plastic
 Also known as Bingham bodies
 The plastic flow curve does not pass through the origin and it
intersects the shearing stress axis at a particular point referred
to as yield value
 A Bingham body does not begin to flow until a shearing stress,
corresponding to the yield value, is exceeded
 Examples: toothpaste, mayonnaise, chocolate, pastes (tomato
paste, chili paste)
 A certain shear stress has to be applied in order to let the sample
flow  the applied force has to be higher than the structural
force
Pseudoplastic
 Known as “shear thinning”
 Viscosity decreases as the shear rate increases (not shear stress)
 Increased shear rate, increased shear stress
 The curve for a pseudoplastic material begins at the origin (or
at least approaches it at low rates of shear)
 In contrast to Bingham bodies, there is no yield value
 Examples: blood, milk, and quicksand (common and naturally
occurring), latex paint, ketchup
Dilatant
 Known as “shear thickening”
 Viscosity increases with the rate of shear strain
 Such systems actually increase in volume when sheared and
hence termed “dilatant”
 When stress is removed, it returns to its original state of fluidity
 Examples: wet sand, Oobleck (mixture of cornstarch and water)
Renhart M. Salas, fRPh 1|Pa ge
 AUF CAMP – PHARMACY DEPARTMENT
PHYSICAL PHARMACY (LABORATORY)
Exercise 12: Rheology
Lecturer: Patrick Ian Ortega

 What Kind of Liquid Lets You Run Across Its Surface | Street Science
Oobleck pool
 13-ton cement mixer, 9-ton Oobleck NON-NEWTONIAN TIME-DEPENDENT BEHAVIOR
 25-foot long pool THIXOTROPY

The pressure of the foot striking the surface causes the liquid to thicken  It is the decrease in viscosity as a function of time upon
enough to support the runner, but the substance will not stay solid for long. shearing, then recovery of original viscosity as a function of
Once the runner stops lifting his or her feet, force stops being transferred time without shearing
to the Oobleck and when the particles of cornstarch are no longer squeezed  As the shear stress persists for longer time, the less viscous the
together by force, water fills in the gaps between the particles and the fluid becomes
Oobleck returns to a more liquid state. It seems the only way not to get  A decrease in apparent viscosity with time under constant shear
stuck or fall through the leg is to continue to apply force to the particles. rate or shear stress, followed by a gradual recovery when the
shear rate or stress is removed
For the bicycle, you need to build up enough speed first. To go faster, you  It happens with pseudoplastic materials (shear thinning)
need to pedal the bike hard which creates enough downward force to make
the liquid behave like a solid. Entering from a standstill with far less RHEOPEXY
pedaling in speed will change things and there will be no downward force
to harden the Oobleck and the bike sinks and gets stuck.  An increase in apparent viscosity with time under constant
shear rate or shear stress, followed by a gradual recovery when
 Shear Thickening vs Shear Thinning the stress or shear rate is removed
For normal Newtonian fluids, the viscosity stays the same no matter how  As the shear stress persists for longer time, the more viscous the
much shear stress is applied. Non-Newtonian fluids, on the other hand, do fluid becomes at a constant shear rate
not behave the same way. While there are several varieties of non-
 Also known as anti-thixotropy or negative thixotropy
Newtonian fluids, we will focus on shear thinning and shear thickening
fluids.
 Brookfield Viscometer, How To Take A Viscosity Reading
Start by filling your beaker with the sample material. Air bubbles in your
For shear thinning fluids, the apparent viscosity decreases with increasing
sample can cause high readings. Tilting the beaker as you pour your sample
shear rate. The harder the fluid is sheared, the less viscous it becomes.
will help limit air bubbles. To prevent air bubbles from being trapped
Tomato ketchup, for instance, stays almost solid in the bottom of a plastic
underneath your spindle, tilt the spindle at a 45° angle as you dip it into
bottle until it is squeezed, at which point it squirts out easily. To
your sample.
demonstrate this in a more dramatic way, we see that by simply placing a
golf ball on top of the ketchup that settles and remain stationary. However,
With the motor off, attach the spindle by gently lifting up the coupling nut
when the ball is dropped and needs to catch up at greater speed, it passes
on the viscometer with one hand and screwing the spindle on with the other.
through easily. As the rate of shear rate increases, the apparent viscosity
Lifting the coupling nut protects the suspension system inside the
decreases and the ball moves with less resistance.
instrument by raising the pivot point off the jewel bearing. As you attach
the spindle, keep in mind that it has a left-handed thread. Turn the gear
For shear thickening fluids, the apparent viscosity increases with
knob to move the instrument up and down until the fluid is level with the
increasing shear rate. The harder the fluid is sheared, the more viscous it
spindle’s immersion groove.
becomes. An example of this is a mixture of cornstarch and water, which
turns from being fluid-like to near solid when shear is applied. As you can
Now that you have attached the spindle, a spindle entry code must be
see, it behaves very differently. When the ball is gently placed on top of
entered. You will find the codes for all spindles in an appendix in your
the surface of the mixture, it slowly but surely sinks. However, by applying
manual. To enter the spindle entry code, push the “Select Spindle” button,
more shear and an attempt to remove it, the solid-like qualities of the
scroll using the up/down arrows to the correct spindle code. and push the
substance are demonstrated. We see that if the ball is dropped and impacts
“Select Spindle” button again to lock in the code. To set the speed, scroll
the mixture with a high initial velocity and greater shear force, its apparent
using the up/down arrows to the speed of choice and press the “Set Speed”
viscosity is much higher.
button. Press the “Motor On” button to rotate the spindle. If you need to
take readings at multiple speeds, repeat the same process. It is not necessary
to turn the motor off to change speeds.

Renhart M. Salas, fRPh 2|Pa ge

 AUF CAMP – PHARMACY DEPARTMENT
PHYSICAL PHARMACY (LABORATORY)
Exercise 13: Sedimentation Rate
Lecturer: Patrick Ian Ortega

SEDIMENTATION SEDIMENTATION VOLUME

 This is a phenomenon which occurs in dispersed system where  A ratio of the ultimate volume of sediment to the original
the dispersed particles settle to the bottom of the container volume of sediment before settling
 This occurs because the particles are too large to remain  Gives a qualitative account of flocculation
permanently suspended in the vehicle
 Velocity of sedimentation expressed by Stokes Equation F = Vu/Vo where
 Stokes – developed an equation which relates the rate of
sedimentation to the physical properties of the suspension  Vu – ultimate volume or final volume
 Vo – initial volume or original volume
V = d2(p1 -p2)g / 18no where
 When F=1  Vu=Vo
 V – sedimentation (Stokes unit: poise)  The system is in flocculated equilibrium and show
 d – diameter no clear supernatant on standing
 p1, p2 – density of suspension or fluid
 g – gravity  When F<1  Vu<Vo
 n0 – viscosity  Flocculation or sedimentation

Limitation of the Stokes Equation  When F>1  Vu>Vo

Stokes Equation only applies to  Sediment volume is greater than the original volume
1. Spherical particles in a very dilute suspension (0.5-2g/100mL)  Loose and fluffy sediment
2. Particles which freely settle without collision
3. Particles with no physical and chemical attraction

SUSPENSIONS

 A suspension is a heterogenous (mixture) system containing

dispersed solids of such size that they settle  has particles
which are somehow big that, in the long run, settle at the bottom
 The rate of sedimentation or settling for a suspended phase
depends on several factors which are under the control of the
formulator or pharmacist  we can counter sedimentation

FACTORS AFFECTING SEDIMENTATION

PROCEDURE
1. Particle size diameter
 Sedimentation velocity (how fast the particles settle
1. Prepare four 25mL graduated cylinders and label A, B, C, and
at the bottom) is directly proportional to the square
D, respectively.
of diameter of particle
2. Pour 25mL of each of the samples in the labeled cylinders.
 Bigger particle, the faster it will settle at the bottom
 Cefalexin, Amoxicillin, Antacid, Paracetamol
3. Set aside the cylinders without moving and touching for 30
2. Density difference between dispersed phase and dispersion
minutes.
medium
4. Observe.
 Generally, particle density is greater than dispersion
medium, but in certain cases particle density is less
than dispersed phase, so suspended particle floats
and is difficult to distribute uniformly in the vehicle
 If density of the dispersed phase and dispersion
medium are equal, the rate of settling becomes zero
 Milo analogy: hot and cold water  density of water
changes with temperature

3. Viscosity of dispersion medium

 Sedimentation velocity is inversely proportional to 15 minutes 30 minutes
viscosity  malapot, slower settling of particles Cefalexin – some settling Cefalexin – similar amount of settling
 Increase viscosity of medium, decreases settling, so Amoxicillin – settling Amoxicillin – more flocculation
the particles achieve good dispersion system but Antacid – no settling Antacid – no settling
greater increase in viscosity gives rise to problems Paracetamol – no settling Paracetamol – no settling
like pouring, syringeability (IV, IM) and
redispersibility of suspension COMPUTATION

Degree of Flocculation Sedimentation Volume

 F = Vf/Vi, where
 F = sedimentation volume
 Vf = final volume of sediments
 Vi = original volume of suspension
 F = Vu/Vo
Cake Flock / floccules

Renhart M. Salas, fRPh 1|Pa ge

 AUF CAMP – PHARMACY DEPARTMENT
PHYSICAL PHARMACY (LABORATORY)
Exercise 13: Sedimentation Rate
Lecturer: Patrick Ian Ortega

Problem
The original volume of an amoxicillin suspension was measured to be
60mL, and the final volume of the sediments is 5mL, what would be the
sedimentation volume of the sample?

F = Vf/Vi
F = 5mL / 60mL
F = 0.0833 mL  there is flocculation since F<1

Renhart M. Salas, fRPh 2|Pa ge