Physical Pharmacy

DIGESTER : PHYSICAL PHARMACY DIGESTER
PHYSICAL PHARMACY
DIGESTER -176
GAS LAWS
S.no. NAME OF LAW EQUATION USED COMMENTS

P1 P2
1. Gay-Lussac Law  # Volume constants
T1 T2
P1 P2
2. Boyle's Law  # Temp. constant
V1 V2
V1 V2
3. Charle's Law  # Pressure constant
T1 T2
V1 V2
4. Avagadro's Law  
n1 n2
# a, b  constants,
 an2 
5. Vander waal's equation  P+ 2   V  nb   nRT a
 V   internal pressure/mole
 v2
DIGESTER -177
PARTICLE SIZE DISTRIBUTION
S. NO. DIAMETER DESCRIPTION

1. Surface diameter, ds It is the diameter of a sphere having the same
surface area as that of asymmetric particle
2. Volume diameter, dv It is the diameter of a sphere having the same
volume as that of asymmetric particle
3. Projected diameter, dp It is the diameter of a sphere having the same area
of the same area of the asymmetric particle as
observed under a microscope
4. Stoke's diameter, dst It is the diameter of an equivalent sphere
undergoing sedimentation the same rate as the
asymmetric particle.
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89
DIGESTER GPAT DISCUSSION CENTER : MAKES STUDY EASY
DIGESTER -178
PARTICLE SIZE DETERMINATION
S.NO. METHOD SIZE RANGE INSTRUMENT FEATURES

1 Microscopy 0.2-100 m Optical microscope  Feret, Martin and
projected diameter is
0.001 - 0.1 m Transmission
measured
Electron Microscope
(TEM)  It can detect presence
of agglomerates &
0.01-1000 m Scanning Electron
particles of more than
Microscope (SEM)
one component
01-1000 m Light microscope  Diameter is two
dimensions :- length
and breadth, thickness
is not estimated
2 Sieving 50-1500 m Mechanical shaker Standard sieves are used
calibrated by National
Bureau of Standards.
3 Sedimentation 1-200 m Anderson pipette Stoke’s diameter is
(Gravity measured
sedimentation
based)
4 Conductivity 0.5-500 m Coulter counter or Equivalent volume
Royco/HIAC diameter is measured
DIGESTER -179
FACTORS AFFECTING FLOW ABILITY
S. No. FACTORS EFFECTS ON FLOW ABILITY

1. Particle size and Mixing of coarse and fine particles, fills the void space so
distribution reduces interparticle cohesive force and increases flow.
2. Particle shape & Spherical shape particles gives maximum flow rate and
surface irregular shape of particle causes bridging in hopper and
decreases flow.
3. Density Higher density, better flow rate.
4. Porosity Less porosity, better flow rate.
5. Hygroscopicity ↑ Hygroscopicity, ↑ adhesion and cohesion forces, low rate.
6. Electrostatic ↑ In the charge, lowability.
charge

90
DIGESTER -180
SURFACE AND INTERFACIAL TENSION
S.NO. INTERFACIAL TENSION (I.T.) SURFACE TENSION (S.T.)

1. Force per unit length acting at interface Force per unit length acting at surface
at right angle. at right angle
2. Interface is boundary between two phase Surface is boundary between two phases,
(liquid or solid) where one of the two phase is gas or
vapour.
3. Indicates strength of adhesive force Indicates strength of cohesive force.
(force between different particles) (Force between common particles)
4. Unit :- N/m or dyne/cm Unit :- N/m or dyne/cm
Solid-gas
S S
S G interface
Solid-Solid Solid-liquid
interface interface
DIGESTER -181
EXPRESSION OF SURFACE TENSION
S.NO. IN TERMS OF EQUATION USED ABBREVIATIONS

F   Surface or Interfacial tension
1. Force per unit length =
2L F  Force applied
L  Length of bar
2. Energy per unit area W W  Work needed to displace
=
increases A bar
A  Increase in area
3. Pressure difference across
curved surface
P =  ( 1r + 1r )
1 2
r1 r2  Radii of Curvature
P  Pressure difference
DIGESTER -182
SURFACE TENSION & INTERFACIAL TENSION OF SOME SUBSTANCES AT 20OC
S.NO. SUBSTANCE S.T. (dyne/cm) I.T. AGAINST H2O

1. Water 72.8 -
2. Mercury 476 428
3. Olive oil 35.8 22.9

91
DIGESTER -183
MEASUREMENT OF SURFACE TENSION & INTERFACIAL TENSION
USED FOR
S.NO. METHODS USED EQUATION USED
MEASUREMENT OF
Capillary Rise Method For surface tension 1 rphg
1. =
2
(Young laplace equation)
2. Drop weight method For S.T. and I.T. w weight of one drop
=
2r
3. Drop count method For S.T. and I.T. mg m  mass of 1 drop
=
2rn n  no. of drop
4. Wilhelmy’s plate For S.T. and I.T. WL-W
=
method 2(L+T)
WL Reading (prior)
W  weight of plate
L,T  Length, thickness
5. Ring detachment or For S.T. and I.T. P
Du Nouy Tensiometer =
2 (r1 + r2)
Dial Reading  
=
2  Ring circumference
  Correction factor
DIGESTER -184
DIFFERENCE BETWEEN PHYSICAL & CHEMICAL ADSORPTION
S.NO PHYSICAL ADSORPTION CHEMICAL ADSORPTION

1. Vander waal forces are involved Chemical bonds are involved
2. Weak, Reversible Seldom reversible
3. Multilayer Monolayer
4. Absorbate free to move Not free to move
DIGESTER -185
ELECTROKINETIC PHENOMENON
Electrophoresis Movement of charged dispersed phase through a liquid

Zero potentials medium upon applying potential difference.
(V/E  4n  / ) 9  104 volt
Electro-osmosis Movement of liquid relative to a fixed solid under
influence of field.

92
Streaming Potential Potential difference is set-up when liquid flow through a

fixed solid. It is opposite process of electro-osmosis.
Sedimentation Potential Potential difference is set-up when movement of
suspended particle takes place in liquid medium. It is
opposite process of electrophoresis.
DIGESTER -186
TYPES OF TIME DEPENDENT FLOW SYSTEM
THIXOTROPY NEGATIVE/ANTITHIXOTROPY
Gel  Sol  Gel Sol  Gel  Sol
Shear thickening system
Heat Brownian movement
Eg :- Low solid content [1-10%] flocculating
Brings molecules close by zig-zag movement
system
Shear thinning system Magnesia magma at equilibrium it form
solution
After deformation  Breaking of Bonds Rate of shear, (G)
Viscosity decreases A B C D
Thixotropic  stability of suspension

ointment, emulsion
i.e. - on sedimentation ses, particle
remains suspended
Shearing stress, (F)
Viscosity increases, so, downward curve
more towards right
DIGESTER -187
TYPES OF NON-NEWTONIAN FLOW SYSTEM
S.No. PLASTIC FLOW PSEUDOPLASTIC FLOW DILATANT FLOW

1 Curves do not pass through Curve begins at the origin It also originate from
origin origin
2 Lines extrapolates to axis, No part of curve is linear No yield value
leads to format ion of linear so, no yield value
curve called yield value.
3 Flocculated suspension Mainly natural & synthetic Curve exhibit dilatant flow
 ses yield value gum exhibit Pseudoplastic
flow.

93
4 Slope = Mobility
Rate of Shear 
G
G
f = yield value
Shearing stress  F F
5 Equn  Equn  Equn 
F-f F = ’G
N
FN = ’G
U=
G
U = Plastic viscosity N = 1 (Newtonian flow) N<1 = degree of dilatency
f = Yield value [N/m2] N > 1 (Non-newtonian flow) ses
G = Rate of shear [S] N=1 = Newtonian flow
F = Shear stress [N/m 2]
N>1 = Non-newtonian
6 Known as Bingham bodies SHEAR THINNING SHEAR THICKENING
SYSTEM SYSTEM
7 It doesn’t flow until shearing H2O
Stress
H2O H2O Rate of
stress is extended as yield H2O H2O ing
Closed Open
value H2O
Shear
Polymer at rest Polymer under packed packed
random arrangement flow. alignment particle particle
water is bound on Long axis
water is released Minimum Maximum
void volume void volume
Low High
consistency consistency
8 Viscosity is linearly Viscosity of pseudoplastic Viscosity of dilatant
increase with increase substance decrease with substance increases with
in rate of shear increase rate of shear increase in stress
9 Eg : Flocculated particles in Eg : Liquid dispersion of Eg:
concentrated suspension natural and synthetics gums  Suspension containing high
(tragacanth, Sodium alginate, concentration of solids,
 Suspension of starch in water,
Methyl cellulose, Sodium  Inorganic pigments in water,
carboxy methyl cellulose) kaolin in water, zinc oxide in
water
DIGESTER -188
TYPE OF FLOW
TYPE OF FLOW EXAMPLE

Newtonian Water, Glycerin, Benzene, Alcohol, Syrup solution, Very
dilute colloid solution
Plastic (Bingham body) Suspension of ZnO2 in mineral oil point, Printing inks and
Firm jellies Flocculated suspension (1.10% solid content)
Pseudoplastic Natural and synthetic gums, Polymers such as MC, CMC,
Tragacanth, Sodium alginate, gelatin
Dilatant De Flocculated suspension (more than 50% solid content)
e.g. Concentrated titanium dioxide suspension

94
DIGESTER -189
DETERMINATION OF RHEOLOGICAL PROPERTIES
S.N VISCOMETER NAME PRINCIPLE EXAMPLE

1. CAPILLARY Ostwald Measuring time required Eg :- Liquid paraffin,
VISCOMETER viscometer for liquid to pass between dextran injection,
two marks of a Capillary methyl cellulose
solution
1 1t1
2 = 2t2
Poiseuille’s law :-
r tP
4
=
8LV
2. ROTATIONAL [a] Cup and Bob Torque is directly Cuvette type 
VISCOMETER proportionaly to Cup is rotated
viscosity
Eg :- MacMichael
Z Viscometer
Searle type -
Cup is stationary
and bob is rotating
Eg :- Rotavisco
viscometer and
stormer instrument
They Show Plug
flow
[b] Cone and Rate of shear is constant Eg :- Ferrantishirety
plate throughout the entire viscometer
sample being shared No Plug flow
[c] Brookefield Eg :- use for
viscometer suspension
[T spindle]
3. FALLING SPHERE Hoppler T ime required for
VISCOMETER viscometer sedimentation depends
on viscosity

95
DIGESTER -190
CLASSIFICATION OF DISPERSED SYSTEM BASED ON PARTICLE SIZES
S. MOLECULAR COLLOIDAL COARSE

No. DISPERSION DISPERSION DISPERSION
1. Less than 1nm particle From 1nm to 0.5 m size 10-1000 m size
size
2. Invisible in electron Not resolved by ordinary Visible under microscope
microscope microscope but in electron
microscope
3. Pass through ultrafilter Do not pass through Do not pass through
and semipermeable semipermeable membrane normal filter paper & does
membrane pass through filter paper not dialyze through
semipermeable membrane
4. Undergo rapid diffusion Diffuse very slowly Do not diffuse
5. Eg :- Oxygen molecule, Eg :- Colloidal silver Eg :- Grains of sand, Most
ordinary ions, glucose solution, natural and pharmaceutical emulsion,
synthetic polymers, Cheese suspension of red blood
Butter, Cream etc. cells etc
DIGESTER -191
CLASSIFICATION OF DISPERSED SYSTEM BASED ON STATE OF MATTER
S. DISPERSION DISPERSED COLLOID COLLOID

No. MEDIUM PHASE TYPE TYPE
1. Solid Solid Solid Sol Pearls, Opals
Liquid Solid Emulsion Cheese, Butter
Gas Solid Foam Pumice, Marshmaflow
2. Liquid Solid Solid gel Jelly, Paint
Liquid Emulsion Milk, Mayonnaise
Gas Foam Whipped Creams, Shaving
Cream
3. Gas Solid Solid aerosol, Smoke, Dust
Liquid Liquid aerosol Clouds, Mist, Fog

96
DIGESTER -192
TYPES OF COLLOIDAL DISPERSION
LYOPHILIC LYOPHOBIC ASSOCIATION

COLLOIDS COLLOIDS COLLOIDS
Mostly organic molecules Largely inorganic particles Aggregation of surface active
agents
Lyo means solvent phillic Lyo means solvent phobic = Known as amphiphilic
means loving hating colloids
i.e. Solvent loving colloids i.e. Solvent hating colloids
Interaction are stronger in Little interaction Aggregates are solvated
both phase, solvent sheath
around particle
Less charged but solvated Highly charged Charged micelles but solvated
Prepared readily from sol Special methods are Radily from when
required concentration is equal to CMC
Thermodynamically stable. Thermodynamically unstable. Thermodynamically stable
So easy to operate So difficult to prepare
Viscosity of dispersion Viscosity of medium doesn’t Viscosity increases with
medium increase with increase with addition of increase in concentration of
addition of dispersed phase dispersed phase amphiphilics
Stable in presence of Unstable in presence of CMC is reduced by addition
electrolyte electrolyte of electrolyte
Salting out of high Stable at high concentration Salting out at high
concentration of electrolyte concentration of electrolyte
Reversible in nature Irreversible Reversible
Highly solvated Low solvation Solvated by polar and
non-polar groups
Rubber, Polystyrene Gold, Silver, Sulphur in water Surfactant
DIGESTER -193
GOLD NUMBERS OF LYOPHILIC COLLOIDS
LYOPHILIC COLLOID GOLD NUMBER

Gelatin 0.005 - 0.01
Egg albumin 0.08 - 0.10
Gum arabic 0.10 - 0.15
Potato starch 25
Tragacanth 2
Sodium oleate 1-5

97
DIGESTER -194
PROPERTIES OF COLLOIDS
OPTICAL KINETIC THERMALLY ELECTRICAL

INDUCED
1. Tyndall effect/faraday 1. Brownian movement  Zeta potential
-tyndall  Robert brown proposed (Electrokinetic)
 Narrow beam of light this theory  Nernst potential
pass through a dispersion  Particles do not sediment (Electrothermodynamic)
path of light becomes in colloidal dispersion
illuminated and observed because of their smaller size Zeta potential =
at right angles. difference in potential
2. Diffusion
st difference between surface
Expressed by Fick’s 1 law
2. Ultramicroscope of tightly bound layer
RT (shear plane) and

 Appear as bright spot 3 4N
D=
against dark background 6  r0 N 3mV electroneutral region may be
+ or - or zero
Used to determine molecular
3. Electron microscopy
weight of polymer Nernst Potential =
 Size, shape and structure M = Molecular weight  Potential at the interface
of colloids V = Partial specific volume (solid surface) or actual
4. Light scattering 0= Viscosity of solvent surface
R = Molar gas constant
 Used for determine  Difference in potential
T = Absolute temperature
weight of colloids difference and
r = radius of spherical particle
 Shape and size of electroneutral region
N = Avogadro’s number
particles
 Described in terms of 3. Osmotic Pressure
 Electrophoresis
Turbidity []  Calculate molecular weight
 Also determine the no. C  Electro-osmosis
of molecules of surface P=
MRT
active agent where -  Sedimentation potential
Turbidity = fractional P - Osmotic pressure
de creas e i n i nten si ty C - Concentration in gram  Electrical double layer
du e t o s c a tt e r i n g a s solute per litre solvent
incident light pass through M - Molecular weight
1 cm of solution R - Gas constant
Expressed by T - Temperature in kelvin
I = IO Exp
-l 4. Sedimentation
I0 = Intensity of incident  Used to determine
light molecular weight
I = Intensity by transmitted  Applying by stoke’s law
light lower limit = 0.5 m
l = Length of sample  Expressed as
 = turbidity RTS
M=
D(1-v0)
 Molecular weight of 5. Viscosity
colloids expressed
 Spherical colloidal particles
low viscosity
 Linear colloids more viscous

98
DIGESTER -195
PREPARATION OF COLLOIDS
LYOPHILIC LYOPHOBIC
Easy to form because of DISPERSION METHOD CONDENSATION METHOD
high affinity for dispersion
medium by pacing colloidal  Colloid mill  By addition of non-solvent
material in contact with Coarsed particle sheared 
 nucleation growth
between static cone and 
proper solvent. 
rotating cone. Molecules
in solution
Nucleus
subcolloidal
Colloidal
particles
 Peptization particles
Breaking up to aggregates eg :- 2H2S + SO2  3S + 2H2O

into particles of colloidal
size by low concentration Colloidal Sulphur
of electrolyte 
solvent  growth
alcohol 

 Electrical dispersion Solids in Molecules of Colloidal
Electric are is produced sulphur sulphur in
solution
particles
b/w two electrode under
cold water.  Chemical method
 Ultrasonic reduction :
Reaction Dispersion
Size reduction of coarse
particle to colloidal size by Reduction : Gold, Silver,
passage of ultrasonic Platinum
waves, produce high Oxidation : Sulfur
frequency socillators
Hydrolysis : Ferric oxide
Double : Arsenic
decomposition oxide

 Reaction
+ 

Reactant Reactant Colloidal
A in B in particles
solution solution
DIGESTER -196
CLASSFICATION OF COMPLEXES
1. METAL ION COMPLEXES (A) Inorganic types [ Co(NH3)6 ]

+3
(B) Chelates EDTA

(C) Olefin type
(D) Aromatic type (i) Pi bond compound
(ii) Sigma bond compound
(iii) Sandwich compound

99
2. ORGANIC MOLECULAR (A) Quinhydrone type Quinhydrone of salicylic acid

COMPLEXES (B) Picric acid type Butesin picrate
(C) Drug and Caffeine Caffeine complexes
complexes
(D) Polymer type Polymer complexes
3. NO-BOND COMPLEXES OR (A) Clathrate
INCLUSION COMPOUNDS
(B) Channel lattice type
(C) Layer type
(D) Monomolecular
(E) Macromolecular
DIGESTER -197
TERMINOLOGY IN KINETICS & DRUG STABILITY
S. NO. TERMS DESCRIPTION

1. Rate of reaction It is defined as velocity with which a reactant undergoes
chemical change.
2. Order of It is sum of powers of the concentration of a reactant or
reaction reactant influences the rate of chemical reaction.
3. Unimolecular Only one type of molecules undergoes a change to yield the
product
Br2→ 2Br
4. Bimolecular Two types of molecules are stoichiometrically involved in
reaction
H2+ I2→ 2HI
5. Half life It is the time required for concentration of the reactant to
reduce to half of its initial concentration
6. Shelf Life It is defined as time required for concentration of the reactant
to reduce to 90% of its initial concentration. it is expressed as
= t90
DIGESTER -198
METHODS OF DETERMINING ORDER OF REACTION
SUBSTITUTION GRAPHICAL METHOD HALF-LIFE METHOD

METHOD
Collect the data on the It is more reliable because Calculate the average k
time course of changes deviation from the best fit value using data for, 0, 1, 2
in concentration of line can be easily observed order as given in
reactant substitution or graphic
method

100
DIGESTER -199
ORDER OF REACTION
ZERO ORDER FIRST ORDER SECOND ORDER

Ra t e o f r e a c t i o n i s Rate of reaction is directly Rate of reaction is
i n dep en den t o n t he proportional to first power proportional to second
concentration of reacting of concentration of a single power of concentration of a
species reactant single reactant
(Rate equation) (Rate equation) (Rate equation)
A0 - At 2.303 log a 1 x
K= K= a-x K= a-x
t t at
A0 = Original concentration a = initial concentration Initial concentration of A and
At = Concentration after t x = decrease in concentration B are not equal.
time t = time ab
2.303 log b(a-x)
Kt = a(b-x)
a-b
Half Life Half Life Half Life
A0 0.693
t1/2 = t1/2 = t1/2 = 1/ak
2K K
Shelf Life Shelf Life
0.1 A0 2.303 Co
t90 = t90 = log
K K 0.9 Co
or
t90 = 0.1052/K
Graph Graph Graph
Log concentration
concentration
Concentration
Slope =
-K x
Slope = -K 2.303 Slope = K
a(a - x)
Time Time  Time Time

Concentration v/s time concentration Log concentration
v/s time v/s time
Unit Unit Unit

K = moles/ liter/second K = sec
-1 -1
K = litre.mole .sec
-1

101

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DIGESTER : PHYSICAL PHARMACY DIGESTER

S.no. NAME OF LAW EQUATION USED COMMENTS

PARTICLE SIZE DISTRIBUTION

S. NO. DIAMETER DESCRIPTION

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S.NO. METHOD SIZE RANGE INSTRUMENT FEATURES

FACTORS AFFECTING FLOW ABILITY

S. No. FACTORS EFFECTS ON FLOW ABILITY

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S.NO. INTERFACIAL TENSION (I.T.) SURFACE TENSION (S.T.)

S.NO. IN TERMS OF EQUATION USED ABBREVIATIONS

S.NO. SUBSTANCE S.T. (dyne/cm) I.T. AGAINST H2O

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S.NO PHYSICAL ADSORPTION CHEMICAL ADSORPTION

Electrophoresis Movement of charged dispersed phase through a liquid

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Streaming Potential Potential difference is set-up when liquid flow through a

Thixotropic  stability of suspension

S.No. PLASTIC FLOW PSEUDOPLASTIC FLOW DILATANT FLOW

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TYPE OF FLOW EXAMPLE

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S.N VISCOMETER NAME PRINCIPLE EXAMPLE

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S. MOLECULAR COLLOIDAL COARSE

S. DISPERSION DISPERSED COLLOID COLLOID

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LYOPHILIC LYOPHOBIC ASSOCIATION

LYOPHILIC COLLOID GOLD NUMBER

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OPTICAL KINETIC THERMALLY ELECTRICAL

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Breaking up to aggregates eg :- 2H2S + SO2  3S + 2H2O

1. METAL ION COMPLEXES (A) Inorganic types [ Co(NH3)6 ]

(B) Chelates EDTA

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2. ORGANIC MOLECULAR (A) Quinhydrone type Quinhydrone of salicylic acid

S. NO. TERMS DESCRIPTION

SUBSTITUTION GRAPHICAL METHOD HALF-LIFE METHOD

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ZERO ORDER FIRST ORDER SECOND ORDER

Time Time  Time Time

Unit Unit Unit

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