Physical Pharmacy

Buffers and Buffering Agents

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 What is buffer solution, define the following:
Buffer solutions are solutions of compounds or mixtures of compounds which resist
changes in their pH upon addition of small quantities of an acid or alkali.

Composition:
Most buffers solutions usually consist of a mixture of a weak acid and one of its salts
or a weak base and one of its salts.

Buffer Action:
It is the ability of buffer solutions to resist pH change upon addition of an acid or a
base.

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Example 1:
NaCl solution in water → its pH 7 on addition of 1 ml 1N HCl solution (acid) to
1 liter of NaCl solution → pH from 7 well become about 3.
Example 2:
On addition of 1 ml of 1N NaOH solution (alkali) to 1 liter of NaCl solution →
raises pH from 7 to about 11.
From Example 1, 2: Sodium Chloride NaCl is not a buffer
Example 3:
Mixture of weak acid (acetic acid) and its salt (sodium acetate); here acetic acid is
very slightly dissociated in solution but sodium acetate being a salt is completely
dissociated.

The mixture thus consists of CH3COOH molecules as well as CH3COO- + Na+ ions.
◊ If a strong acid is added to the mixture → H+ ions supplied by the acid are
immediately taken up by CH3COO- ions → slightly dissociated CH3COOH

H+ + CH3COO- → CH3COOH (slightly dissociated)

The H+ ions are neutralized by acetate ions → very little change in the pH of the
mixture.
◊ On the other hand; if a strong base is added, the OH- ions
supplied by the base are neutralized by acetic acid present in
the mixture → very little change in pH of solution.

OH- + CH3COOH → CH3COO- + H2O

What the mixture of a weak base and its salt will behave?
Example: mixture of ammonium hydroxide and largely dissociated salt
ammonium chloride. Here the mixture contains the undissociated NH4OH as
well as NH4+ + Cl- ions
If a strong acid is added to the mixture → H+ supplied by the acid is neutralized
by the
base NH4OH
H+ + NH4OH → H2O + NH4+
On the other hand, if a strong base is added, the OH- ions are neutralized by NH4+
forming very slightly dissociated NH4OH
OH-+ NH4+ → NH4OH (very slightly dissociated)
From the previous two concepts, there is very little change in the pH
Buffer equation:
Buffer equation is an expression developed by considering the effect of a salt on the
ionization of a weak acid or a weak base when the salt and the acid or base has a
common ion.

Buffer equation for a weak acid and its salt (common ion effect):
On adding sodium acetate with acetic acid solutions, there is a common ion between
then:
CH3COOH on dissociation → CH3COO- + H+ --------→ (1)
CH3COONa on dissociation → CH3COO- + Na+ --------→ (2)

The presence of common ion (equation 1,2) increases the concentration of CH3COO- in
equation (3) (numerator (‫البسط‬
To make the dissociation constant [H+] in the numerator will be decreased → resulting
in [CH3COOH] in the denominator . ‫المقام‬as follows :
H+ + CH3COO- → CH3COOH
pH of the buffer solution is obtained by rearranging the equation "3" as follows :

- Where CH3COOH --------→ slightly dissociated acid

CH3COOH --------→ from the dissociated salt
Expressing equation (5) logarithmically as follows:
log [H+] = log ka + log [ acid ] – log [ salt ] multiplying both sides by – 1
- log ( H+) = -log ka - log ( acid ) + log ( salt )

Equation (6) is known as the buffer equation for a weak acid and its salt.
This equation is useful for preparation of buffered pharmaceutical solutions.
[acid]

[salt]
Where pKw = 14 (ionic product of water)
 Factors Affecting pH of buffer Solutions
(1) Temperature:
Change in temperature → changes Buffer pH with Buffers consisting of a base and its salt show greater
changes with temperature.
↑ in temperature → ↓ the pH of a buffer solution containing boric acid and sodium borate
On the other hand, ↑ in temperature → ↑ the pH of a buffer solution containing acetic acid and sodium
acetate.

(2) Dilution effect:

Dilution with water in moderate quantities small effect on the pH of the buffer
Dilution of acidic buffer → ↑ in pH
Dilution of basic buffer → ↓ in pH

(3) Salts effect:

When a salt is added to an acidic buffer solution → ↓ pH
When a salt is added to a basic buffer → ↑ its pH
Buffer capacity:
It is a measure of the magnitude of the resistance of solution to the change in pH on
adding an acid or base

Other derivatives:
Buffer capacity = buffer index = buffer efficiency = buffer coefficient = buffer
value.

Other definition for buffer capacity:

It is the ratio of the increment of strong base or acid to the small change in pH
brought by this addition.

B = buffer capacity
ΔB = the small increment in gm equivalent / liter of strong base
or acid added to the buffer.
Δ pH = pH change.
Van Slyke’s Equation for Buffer Capacity

The buffer capacity calculated from the previous equation is only approximate. It gives the
average buffer capacity over the increment of base added. Van Slyke developed a more
exact equation,

Where C is the total buffer concentration (i.e., the sum

of the molar concentration of the acid and the salt).
Maximum Buffer Capacity:
An equation expressing the maximum buffer capacity may be derived from the buffer
capacity formula of Van Slyke. The maximum buffer capacity occurs where pH = pKa, or,
in pKa equivalent terms, where [H3O+] = Ka.
Substituting [H3O] for Ka in both numerator and denominator of equation gives

In which C is the total buffer concentration.

( )2
 Biological Buffers
Blood: pH of blood is maintained at 7.4 by the component of plasma and erythrocytes.
The plasma contains:
1- Carbonic acid/carbonate
2- Phosphoric acid / sodium phosphate
Erythrocytes (RBSs) contains
1- Oxyhaemoglobin/haemoglobin
2- Phosphoric acid / potassium phosphate
The pH range of blood is 7 → 7.8 (above or below this range → life in danger)

Lachrymal fluid or tears: pH is about 7.4 ( range 7 → 7.8)

Urine: is about 6 (range 4.5 → 7.8) when the pH of urine is altered above or below
this range kidney is diseased.
 Pharmaceutical Buffers
In pharmaceutical industry we adjust the pH of the product for maximum stability or
maintain the pH of the product within the optimum physiological range.
1- Buffers in tablet formulation:
Buffers employed in tablet or capsule formulations containing acidic drugs to reduce
gastric irritation or antacid drugs such as sodium bicarbonate, sodium citrate or
magnesium carbonate.

2- Buffers in ophthalmic preparations:

Buffers are used here to maintain the pH of the product within the pH range of
lachrymal fluids. The lachrymal fluid has good buffering capacity where the solutions
within 3.5 – 10.5 can usually be tolerated Outside this range → eye irritation and
increase lacrimation.
The most commonly used buffers in ophthalmic preparations include borate,
phosphate and carbonate buffers.
3- Buffers in parental preparations:

In parentral, the consideration of pH is very important, where high pH (above 9) →

tissue necrosis while highly acidic pH (below 3) extreme pain in site of injection.
The ideal pH for parental is 7.4 similar to the blood. There must be compromised
between the blood pH and the solubility and stability of the product.
The most widely used buffers in parental are acetate, phosphate, citrate and glutamate
buffers.

4- Buffers in creams and Ointments:

Topical preparations on storage usually ender go change in pH, this affect the stability
of the drugs therefore, buffers must be induced in this formulations. The most widely
used buffers here are citrate and phosphate.
 Physical Pharmacy

SURFACE ACTIVETY

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 Interface: is the boundary between two phases.

Surface: is the boundary between 2 phases one of them is vacuum (air).

The properties of the molecules forming the surface or interface → different from
those in the bulk of each phase
Liquid interfaces involve the association of a liquid phase with a gaseous or another
liquid phase.
Solid interfaces deal with systems containing solid/gas and solid/liquid interfaces.

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Surface and Interfacial Tension
In a liquid drop suspended in air:

1- Molecules in the bulk of the liquid are surrounded in all

directions by other molecules → they have an equal attraction.

2- Molecules at the surface → develop attractive cohesive forces with other liquid
molecules that are situated below and adjacent to them.

3- The net effect is that the molecules at the surface of the liquid experience an inward
force towards the bulk.

Such a force pulls the molecules of the interface together and as a result, contraction
of the surface takes place → the surface behaves as stretched elastic membrane.

Liquid droplets → tend to assume a spherical shape since a sphere has the smallest
surface area per unit volume.
In order to ↑ the area of the surface → it is necessary to do work to bring molecules
from the bulk into the surface against the inward attractive forces.

Surface energy or Surface free energy: the work required to increase the area by 1
cm .
2

Surface Tension: the force (in dyne) acting along the surface of a liquid at right
angles to any line 1 cm in length to counterbalance the net inward pull.

Surface tension can be expressed as:

W is the work done or surface free energy

expressed in ergs,
𝜸 is the surface tension in dynes/cm and
ΔA is the increase in area in cm2.
By means of a three-sided wire frame across which a movable bar is placed.
A soap film is formed over the area ABCD and can be stretched by applying a force F
(such as a hanging mass) to the movable bar (of length L), which acts against the
surface tension of the soap film.
When the mass is removed → the film will contract owing to its surface tension.
The surface tension of the solution forming the film is then a function of the force that
must be applied to break the film and of the length of the movable bar in contact with
the film.
𝜸 = Fb / 2 L
In which Fb is the force required to break the film and L is the length of the movable
bar.

Example: If the length of the bar L is 5 cm and the mass required for break the film is
0.5 gm. What is the surface tension of the soap solution?
Note: The downward force is equal to the mass multiplied by the acceleration due to
gravity.
Solution: 𝜸 = (0.5 gm x 981 cm/sec2)/(2x5) cm = 49 dynes/cm
Interfacial Tension
The force per unit length existing at the interface between 2 immiscible liquids Unit =
dyne/cm
The interfacial tensions are usually less than the surface tensions → because the
adhesive forces between 2 liquid phases forming an interface are greater than when a
liquid and a gas phase exist together.
If two liquids are completely miscible → no interfacial tension exists.

Factors affecting surface tension

1- Nature of the liquid.
2- Temperature: 𝛾 of most liquids ↓ with temperature ↑
3- Solutes: certain molecules and ions when dispersed in the liquid move to the
interface → their concentration in surface layer exceeds their concentration in the bulk
of the liquid.
On the other hand non electrolytes as sucrose and ethanol → not strongly hydrated in
solution and can be found at the interface as well as in the bulk of a solution →
weaken the water-water interactions and cause a small decrease in the surface tension
 Measurement of Surface and interfacial Tension
1- Capillary rise method

Due to the force of adhesion → the liquid is said to wet

When a capillary tube is placed between the liquid the capillary wall, spreading
in a liquid contained in a molecules and the capillary
beaker→ the liquid rises up the wall is greater than the over it, and under the effect
tube to a certain distance. cohesion between the liquid of its surface tension rising
molecules in the tube.

The liquid continues to rise in the tube due to the

surface tension →until the upward movement is just
balanced by the downward force of gravity due to
the weight of the liquid.
1- Capillary rise method

Example: A sample of chloroform rose to a height of 3.67 cm at 20°C in a

capillary tube having an inside radius of 0.01 cm. What is the surface tension of
chloroform at this temperature? The density of chloroform is 1.476 g/cm3.

Solution:
𝜸 = 1/2 r h d g
𝜸 = 1/2 x 0.01 cm x 3.67 cm x 1.476 g/cm3 x 981 cm/sec2
= 26.6 [Link]/sec2 cm = 26.6 dynes/cm.
2- Drop weight and drop count method:

If a liquid is allowed to → finally detaches from

fall slowly through a the tip when the weight of
capillary tube → the the drop equals the total
liquid first forms a drop at surface tension at the
the tip of the tube which border of the tip →
increase in size

𝐰=𝟐𝛑𝐫𝜸

w= weight of one drop of liquid

r= radius of the capillary
𝜸 = surface tension of the liquid
Using a drop pipette (stalagmometer)
2- Drop weight and drop count method:

A- Drop weight method

Stalagmometer consists of a glass tube with a bulb. It has two

marks A and B one above the bulb and the other below it. There
is a capillary at its lower tip.
Process: clamp the stalagmometer vertically in the determined liquid. Suck up to the
mark A. allow the liquid to drop down. Collect 20 or 30 drops in a tarred vessel. The
weight of one drop is determined (w).
The surface tension is given by the equation
𝜸 = 𝐰/𝟐 𝛑 𝐫
We can determine the relative surface tension of a liquid, related to water.
2- Drop weight and drop count method:

B - Drop count method

Process: as previous method fill the liquid into the stalagmometer to be between A and
B marks, the number of drops formed between A, B are counted and apply the
Equation:

𝜸 = 𝑽 𝒅 𝒈 /𝟐 𝝅 𝒓 𝒏

V d = volume x density = mass of one drop

n = number of drops g = gravitational force
For determination of relative surface tension of a liquid to water

Where:
d1=density of liquid d2= density of water=1
n1=number of liquid drops n2=number of water drops
3- Du Nouy ring method

Du Nouy Tensiometer is widely used for measuring surface and interfacial tensions.

Principle: depends on the fact that the force necessary to detach a platinum-iridium ring
immersed at the surface or interface is proportional to the surface or interfacial tension.

The force required to detach the ring in this manner is provided by a torsion wire and is recorded
in dynes on a calibrated dial.

The surface tension is given by the formula:

The correction factor: is important to account for certain variables such as:
1- Radius of the ring,
2- Radius of the wire used to form the ring
3- Volume of the liquid raised out of the surface by the ring.
Spreading Coefficient

When a substance such as oleic acid is placed on the surface of water, it will spread as
a film → if the force of adhesion between the oleic acid molecules and the water
molecules is greater than the cohesive force between the oleic acid molecules
themselves.
The film obtained is a duplex film, which is a sufficiently thick (100 Å or more)
opposed to a monomolecular film → surface (boundary between oleic acid and air)
and interface (boundary between water and oleic acid) are independent of one another.

The work of adhesion (the energy required to break the attraction between the unlike
molecule → oleic acid and water) → W = 𝜸. ΔA
If we consider a hypothetical cylinder (cross-sectional area of 1 cm2) of a sub layer
liquid S (water) overlaid with a similar section of the spreading liquid L (oleic acid).
The work required to separate the two sections of liquid each with a cross-sectional area of 1
cm2 is therefore, numerically
= Surface tension x Unit area change (unity)
The work of adhesion → Wa = 𝜸 L + 𝜸 S - 𝜸 LS
 The work of cohesion

(the energy required to separate the molecules of the spreading liquid)

→ so that it can flow over the sub layer is obtained by the same way.
Obviously, no interfacial tension exists between the like molecules of the liquid,
and when the hypothetical 1 cm2 cylinder is divided into 2 new surfaces each with
a surface tension of 𝜸L.
The work of cohesion → Wc = 2 𝜸L

The term (Wa - Wc) is known is the spreading coefficient (S); if positive, the oil will
spread over water surface:
S = Wa - Wc = (𝜸L + 𝜸S - 𝜸LS) - 2 𝜸L → S = 𝜸S – (𝜸L + 𝜸LS)
In which
𝜸S is the surface tension of the sub layer liquid
𝜸L is the surface tension of the spreading liquid
𝜸LS is the interfacial tension between them.
With reference to the spreading of oil on a water surface, spreading occurs if the work
of adhesion (attraction force between oil and water) is greater than the work of
cohesion (attraction force between oil molecules).
1- If the 𝜸S surface tension of the sub layer is greater than the sum of the surface
tension of the spreading layer and the interfacial tension between the two layers →
+ve S → spreading will occur.
2- If (𝜸L + 𝜸LS) is greater than 𝜸S → the substance
forms globules or floating lens and fails to spread
over the surface an example is mineral oil on
water.

Example: If the surface tension of water 𝜸S is 72.8

dynes/cm at 20°C, the surface tension of benzene 𝜸L is 28.9 and the interfacial tension
between benzene and water 𝜸LS is 35.0 what is the initial spreading coefficient?
Following equilibration, 𝜸S is 62.2 dynes/cm and 𝜸L Is 28.8 What is the final
spreading coefficient?
Solution:
S = 72.8 - (28.9 + 35.0) = 8.9 dynes/cm
S = 62.2 - (28.8 + 35.9) = - 1.6 dynes/cm
It is important to know that the molecular structure of oil has a great effect on its
spreading behavior on water.
- Oil spreads over water because it contains polar group such as -COOH or -OH.
- As the carbon chain of an acid (e.g. oleic acid) ↑ →the ratio of polar/non polar
character ↓ → spreading coefficient on water ↓

Importance of Interfacial phenomena in pharmacy and medicine

Important in studying factors that affect adsorption of drugs onto solid adjuncts in
dosage forms, penetration of molecules through biologic membranes, emulsion
formation, stability and the dispersion of insoluble particles in liquid media to form
suspensions etc....
 Surface Active Agents (SAA) = Surfactants

1- They are molecules and ions that are adsorbed at interfaces → ↓ surface tension of
the solvent.
2- They are also known as amphiphiles → molecules or ions have certain affinity for
both polar and nonpolar solvents.
3- They may be hydrophilic (water-loving), lipophilic (oil-loving) or well balanced
between these two extremes → depending on the number and nature of the polar and
nonpolar groups present in their molecules.
4- In an aqueous dispersion of SAA → the polar groups are able to associate with
water molecules.
5- The non-polar portion is rejected (because the adhesive force with water molecules
is small in comparison to the cohesive force between the adjacent water molecules) →
amphiphile molecule is adsorbed at the interface.
Chemical or Structural Classification of SAA
 Hydrophile - Lipophile Classification
The higher the HLB of an agent, the more
hydrophilic it is.
Spans are lipophilic and have low HLB values
of 1.8 to 8.6.
Tweens are hydrophilic and have HLB values of
9.6to 16.7.
The HLB of a number of polyhydric alcohol
fatty acid esters, such as glyceryl mono stearate
may be estimated by using the formula:
HLB = 20 [1- S/A]
In which S is the saponification number of the
ester and A is the acid number of the fatty acid.
The HLB of polyoxyethylene sorbitan
monolurate (tween 20), where S = 45.5 and A =
276 is: HLB = 20[1- 45.5/276] = 16.7
For the materials with it is not possible to obtain good saponification numbers
e.g.
bees wax and lanolin derivative
The following formula is used: HLB = [E + P]/5
Where E is the percent per weight of oxyethylene chains and P is the percent by
weight of polyhydric alcohol groups (e.g. glycerol, sorbitol).
5- For substances containing only oxyethylene groups
The following formula is used: HLB = E/5
Where E is the percent per weight of ethylene oxide
 Applications of Surface-Active Agents
I. Solubilization by micelle formation
At low concentration of SAA → the molecules migrate at the interface between water
and air so that the hydrophilic portion is directed towards water and the hydrophobic
portion is directed towards air.
Further addition of the surfactant leads to the saturation of the surface and molecules
are forced to the bulk of the solution.

After saturation of the bulk and at a specific concentration

known as the critical
micelle concentration (CMC) → SAA molecules aggregate to
form micelles of
spherical shapes so that the hydrophilic portions of the
molecules are directed outward
(facing water) and the hydrophobic portions are
directed inward.
At constant temperature and specific concentration for the same SAA, all micelles
contain the same number of molecules.
1- Number of SAA monomer in micelle is 25 – 100 molecules.
2- The diameter of micelles range from 30 - 80 A° (Submicroscopic)
3- Micelles are not permanent aggregates → each molecule finds itself randomly
alternating between the single and the aggregate state
4- Micelles are formed so that polar groups are in contact with water and the
hydrophobic groups are out of contact with water forming the core.
5- Water insoluble compounds can be
solubilized in the hydrophobic core of the micelles forming a molecular dispersion in
a submicroscopic aggregates leading to solution.
Examples of drugs that are solubilized by this way are:
Vitamins (A, D, E & K) – Hormonal steroids - Alkaloidal drugs - Glycosides
6- Water insoluble drugs are better absorbed orally or parenterally from surfactant
solubilized solutions than from oil solutions.
II- Antibacterial Activity
a. SAA may increase the activity of antibacterial compounds → SAA ↓ the interfacial
tension between the liquid phase containing the drug and the cell wall of the organism
→ ↑ penetration through the cell membrane.
For example the penetration of hexylresorcinol into the pinworm ascaris is increased
by the presence of a low concentration of SAA.
b. Some SAA have antimicrobial activity.
Quaternary ammonium compounds → adsorbed on the cell surface → ↑ the
permeability of the lipid cell membrane leading → loss of essential materials from the
cell → cell death.
Ill- Foam Formation & Antifoam Effect
a. Foaming agents are surfactants which facilitate the formation of air globules
inside
water film and stabilize them.
They are important for tooth paste and fire extinguishing products.
b. Antifoaming agents are important for most pharmaceutical liquid preparations
containing SAA for wetting or flocculating effect.
Antifoam SAA have low HLB (1 - 3) → destroy air pockets.
IV- Wetting Effect
Some SAA has the ability to ↓ the solid/liquid interfacial tension and ↓ the contact
angle between the solid surface and the wetting liquid → liquids can spread on the
solid and wet its surface.
They decrease the contact angle by adsorbing at the interface between the solid and
liquid facilitating the spreading of the liquid over the solid.
V- Emulsifying Agents
Based on the HLB value they can either emulsify water droplets in oil phase, or
emulsify oil drops in a water phase leading to the formation of W/O or O/W
emulsions.
VI- Detergents
These are surfactants used to remove the dirt. The process of detergency is complex.
It includes many of the action of surfactants:
1- Initial wetting of the dirt and of the surface to be cleared.
2- Suspension of dirt materials.
3- Emulsification or solubilization of the dirt.
 Adsorption at Solid Interfaces
Adsorption: is the accumulation of a substance over the surface of another substance.
Adsorbent: the substance which accumulates the other substances over its surface.
Usually finely divided porous solid
Adsorbate: the substance being adsorbed
Absorption is the penetration of a substance through another substance.
Applications of adsorption phenomena at a solid interface:
I. Adsorption of gases on solid surfaces
1- The removal of toxic gases using gas masks.
2- Adsorption of objectionable odors from rooms and foods.
3- Measurement of powder particle size through measuring the surface area per fixed
volume.
II. Adsorption from liquids on solid surfaces:
1- De colorization of liquids.
2- Antidotes in oral intoxication by oral administration of charcoal for adsorption and
removal of toxins e. g. atropine and strychnine.
3- Fixation of volatile oils on the surface of a solid of large surface area for permanent
smell.
4- Liquid chromatography where mixtures of materials are separated by an eluting
liquid, from the surface of an adsorbent based on their affinity to the surface.
5- Wetting and detergency.
 The Solid/Gas Interface

The degree of adsorption of a gas on a solid surface depends on:

1. Chemical nature of adsorbent and adsorbate.
2. The surface area of the adsorbent (particle size and porosity).
3. The temperature (adsorption is exothermic process).
4. The partial pressure of the adsorbed gas or the concentration of
solute in solution
Application of Adsorption in Pharmacy and Allied Fields
I. Decolorizing agents: e.g removal of colour from solutions by activated charcoal.
2. Desiccants and Drying Agents: e.g., removal of water from organic solvents by passing on alumina or silica gel.
3. Adsorption Chromatography: This separation technique depends on the difference in affinity of an adsorbent for
various solutes.
4. Ion Exchange.
5. Medicinal Adsorbent: e.g., kaolin, charcoal and attapulgite are used as gastro
intestinal adsorbents.
6. Adsorption of Gases on Solids.
7. Surface Area Determination.
Adsorbent Materials
Kaolin: Native hydrated aluminum silicate (heavy and light).
Attiapulgite: Hydrated Mg, Al silicate, activated.
Bentonite: Native colloidal hydrated aluminum silicate usually containing some Mg and iron.
Charcoal: Prepared from vegetable matter.
Animal Charcoal: Prepared from crude animal charcoal (obtained by heating bones)
Diatomite: Pure silicon dioxide obtained from siliceous deposites.
Purified Talc: Purified native magnesium silicate
Veegum: A brand of colloidal aluminum magnesium silicate.
Alumina: Prepared by dehydration of alumina trihyrdate and it is a mixture of alumina and a small percentage of
alumina monohydrate
Silica: Obtained from purified ground quartz sand.
Rheology:
Understanding the
Flow of Matter
Rheology is the study of how materials deform and flow under stress. It
encompasses liquids, solids, and everything in between.
Defining Rheology: The Study
of Flow and Deformation
Rheology is the branch of physics, which deals with
deformation, and flow of matter, It is important in many fields.
It explores how substances respond to applied forces, leading
to deformation or flow.

Flow Deformation
The continuous movement of The change in shape of a
a material under applied material in response to applied
stress. forces.
The Importance of
Rheological Properties To the pharmacist, rheology is
important in the flow of
Rheological properties influence the behavior of materials in various emulsions through colloid mills
applications, from manufacturing and processing to product and pumps, working of
performance and safety. ointments on slabs or roller
mills, trituration of suspensions
1 Product Design 2 Manufacturing in mortar and pestle, and
Processes mechanical properties of glass
Rheology guides the
formulation and Understanding rheology or plastic containers and of
optimization of products enables efficient processing rubber closures.
like paints, cosmetics, and of materials in industries
food. like plastics,
pharmaceuticals, and
petroleum.
Shear Stress and Shear Rate
Shear stress is the force per unit area acting parallel to the flow, while
shear rate represents the rate of deformation.

1 Shear Stress
The force that causes a fluid to flow.

2 Shear Rate
The rate at which a fluid is deformed.

3 Viscosity
The relationship between shear stress and shear rate.
Measuring Rheological Characteristics
Specialized instruments called rheometers are used to measure the rheological properties of materials.

Rotational Rheometers Capillary Rheometers

Measure viscosity by applying a controlled torque to a Determine viscosity by measuring the flow rate of a material
rotating spindle immersed in the sample. through a capillary tube under a known pressure.
 Viscosity and its Measurement

Viscosity is a measure of a fluid's resistance to flow. It represents the

internal friction within a fluid.

- Units of Absolute Viscosity The units of viscosity is the poise (p), A

more convenient unit for most work is the centipoise (cp).
I cp being equal to 0.01 poise.
- Fluidity (), a term sometimes used, and is defined as the
reciprocal of viscosity:
=1/ Ƞ
- Kinematic viscosity is the absolute viscosity divided by the density
of the liquid. Kinematic viscosity = Ƞ/ρ

The units of kinematic viscosity are stoke (s) and centistoke (cs).
1-Newtonian Behavior
Newton was the first to study the flow properties of liquids in a quantitative
way. He recognized that the higher the viscosity of a liquid, the greater the
force per unit area (shearing stress) required to produce a certain rate of
shear. Hence, the rate of shear should be directly proportional to the shearing
stress
Ƞ = F/G (1)
where F = F'/A (shear stress) and G = dv/dr (shear rate).
Where Ƞ is the coefficient of viscosity, usually referred to simply as viscosity.
Newtonian Behavior
Newtonian fluids exhibit a constant viscosity, independent of shear rate.
Their behavior is linear, meaning shear stress is directly proportional to
shear rate.

1 Examples
Water, air, and many simple
liquids.
2- Non-Newtonian Systems

The pharmacist probably deals more frequently with non-Newtonian material than with
simple liquids, and he should therefore have suitable methods for the study of these complex
substances.
Non-Newtonian bodies are those substances, which fail to follow Newton‘s low; liquid and
solid heterogeneous dispersions such as colloidal solutions, emulsions, liquid suspensions,
ointments and similar products comprise this class.
Non-Newtonian Fluids and Their Behavior
Non-Newtonian fluids exhibit a complex relationship between shear stress and shear rate, deviating from the linear behavior
of Newtonian fluids.

Plastic flow Pseudo plastic flow (Shear-Thinning) Dilatant flow

.
Plastic Flow
In the coming figure the curve is representative of a body, which exhibits plastic flow such
materials are known as Bingham bodies.
The plastic flow curve does not pass through the origin, but rather intersects the shearing
stress axis (or will if the straight part of the curve is extrapolated to the axis) at a
particular point referred to as yield value (f).
A Bingham body does not begin to flow until a shearing stress corresponding to the yield
value, is exceeded, at stresses below the yield value the substance acts as an elastic
material. Plastic materials are sometimes called Bingham bodies or semisolids.

The slope of the rheogram in the figure is g termed mobility, analogous to

fluidity in Newtonian systems, and its reciprocal is known as the plastic
viscosity (U).
The equation describing plastic flow is:
U = (F-f)/G (2)
Where f is the yield value or intercept on the shear stress axis in dynes cm-2.
F and G are as previously defined
Plastic flow is associated with the presence of flocculated particles in
concentrated suspensions.
As a result, a continuous structure is set up throughout the system The yield
value is present because of the contacts between adjacent particles (brought
about by Van der WaaI’s forces), which must be broken down before flow can
occur. Consequently, the yield value is an indication of the force of flocculation;
the more flocculated the suspension, the higher will be the yield value
Frictional forces between moving particles can also contribute to the yield value.
Once the yield value has been exceeded, any further increase in shearing stress
(i.e., F-f) brings about a directly proportional increase in G (the rate of shear) In
effect; a plastic system resembles a Newtonian system at shear stresses above
the yield value.
Pseudoplastic Flow
A large number of pharmaceutical products including natural and
synthetic gums e.g. liquid dispersions of tragacanth, sodium alginate,
methylcellulose, and sodium carboxymethylcellulose, exhibit
pseudoplastic flow.
As a general rule, pseudoplastic flow is exhibited by polymers in solution,
in contrast to plastic systems, which are composed of flocculated particles
in suspension as seen in coming figure, the consistency curve for a
pseudoplastic material begins at the origin (or at least approaches it at
low rates of shear)
- Consequently, in contrast to Bingham bodies, there is no yield value.
Since, however, no part of the curve is linear; one cannot express the
viscosity of a pseudoplastic material by any single value. The viscosity of a
pseudoplastic substance decreases with increasing rate of shear.
-An apparent viscosity may be obtained at any rate of shear from the
slope of the tangent to the curve at the specified point. However, the
most satisfactory representation for a pseudoplastic material at the
present time is probably a graphical plot of the entire consistency curves.
The curved rheogram for pseudoplastic materials results from a shearing action on
the long chain molecules of materials such as linear polymers. As the shearing
stress is increased, the normally-disarranged molecules begin to align their long
axes in the direction of flow. This orientation reduces the internal resistance of the
material and allows a greater rate of shear at each successive shearing stress. In
addition, some of the solvent associated with the molecules may be released,
resulting in an effective lowering of the concentration and size of dispersed
molecules.
An equilibrium exists between the shear induced changes and random coiling tendency caused by
Brownian motion which entraps water inside the coils. The rate of entanglement and randomization by
Brownian motion is constant, while the rate of disentanglement and alignment increases with
increasing shear. Therefore the viscosity diminishes as the shear increased.
- Obviously, objective comparisons between different pseudoplastic systems are difficult than with
either Newtonian or plastic systems. Thus, a Newtonian system is completely described by Ƞ, the
viscosity. A system exhibiting plastic flow is adequately described by the yield value and the plastic
viscosity. Accordingly, several approaches have been used to obtain meaningful parameters which will
allow different pseudoplastic materials to be compared. The exponential formula has been used most
frequently.
F N = Ƞ' G (3)
The exponent N rises as the flow becomes increasingly non-Newtonian.
When N = 1, equation (3) reduces to equation (1) and the flow is Newtonian. The term Ƞ' is a viscosity
coefficient.
Following rearrangement, equation (3) may be written in the logarithmic form:
log G = N log F - log Ƞ' (4)
This is an equation for a straight line. Many pseudoplastic systems fit this equation when log G is
plotted as a function of log F.