PHYSICAL

PROPERTIES AND
MOLECULAR
CONSTITUTION

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Physical properties of a substance are defined as those properties which could be studied and
determined without causing any chemical change in it. For examples, Refractive index, Surface
tension, Viscosity and Dipole moment etc.
Physical properties may be classified as:
(1) Additive Property:
It is the property which depends upon the nature and number of atoms present in a molecule of
a compound, such that its magnitude is equal to the sum of the corresponding properties of the
constituent atoms. For example, the Molecular mass of a substance is equal to the sum of the
atomic masses of the constituent atoms.
(2) Constitutive Property:
It is the property which depends entirely upon the ode of arrangement of atoms in the molecule,
but independent of their number. For example, Optical activity of a molecule.
(3) Additive-Constitutive Property:
It is an additive property which also depends upon the manner in which the atoms are bonded to
each other. For example, Molecular refraction and Parachor are additive-constitutive properties.
Molar refraction:
The molar refraction of a compound is the sum of the refraction of the atoms and the array of
functional groups making up the compound. Because the arrangement of atoms in each group
are different, the refractive index of two molecules will also be different. That is, the individual
groups in two different molecules contribute different amounts to the overall refraction of the
molecules.
O CH3-CH CH-CH2-OH

C2H5-C-CH3

8H 8 x 1.100 8.800 8H 8 x 1.100 8.800

3C(single) 3 x 2.418 7.254 2C(single) 2 x 2.418 4.836
1C(double) 1 x 1.733 1.733 2C(double) 2 x 1.733 3.466
1O (C=O) 1 x 2.211 2.211 1O (OH) 1 x 1.525 1.525
Total 19.998 = 20.0 Total 18.627 = 18.7
The two compounds have the same number and type of atoms, their molar refractions are
different. The molar refractions of the atoms are additive, but the carbon and oxygen atoms are
constitutive in refraction. Refraction of a single-bonded carbon does not add equally to that of a
double-bonded carbon, and a carbonyl oxygen (C=O) is not the same as a hydroxyl oxygen;
therefore the two compounds exhibit additive-constitutive properties and have different molar
refractions.
Parachor:
Mocleod in 1923 pointed out that

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 𝛾1/4
=𝐶
𝐷−𝑑
Where: γ = surface tension of liquid.
D = density of liquid. C = constant
d = density of vapors of a liquid at experimental temperature.
Multiplying both side by M (molecular mass) we have
𝛾 1/4
𝑀 = 𝑀𝐶 = [𝑃]
𝐷−𝑑
“d” is negligible as compare to “D” therefore
𝛾 1/4
𝑀 = [𝑃]
𝐷
𝑀
= molar volume
𝐷
[P] = molar volume x 𝛾1/4
Parachor [P] may be defined as “the product of molar volume of a liquid and its surface tension
raised to the power ¼”
If γ = 1 at a particular temperature thens
[P] = molar volume

Parachor of Paraffins:
Paraffins Molecular formula Parachor Difference Parachor of CH2
Ethane C2H6 110.5
40.3 40.3
Propane C3H8 150.8
119.3 39.8
Hexane C6H14 270.1
39.2 39.2
Heptane C7H16 309.3
35.7 35.7
Octane C8H18 345.0
79.2 39.6
Decane C10H22 424.2 Average 39

Atomic Parachor: It is the contribution of each atom present in the molecule. C10H22 has
parachor value 424.2.
C10H22 = 10(CH2) + 2H
3
 = 10(39) + 2 atomic parachor of hydrogen
424.2 = 390 + 2 atomic parachor of hydrogen
Atomic parachor of hydrogen = (424.2-390)/2 = 17.1

Parachor of CH2 = 39
Atomic parachor of carbon = 39-2H
= 39- 2(17.1)
= 39.0-34.2 = 4.8
Similarly atomic parachor of oxygen in ether, nitrogen in amine and halogen in alkyl halide
can be determined.

Structural Parachor: It is the contributions of the various bonds and rings present in the
molecule. Parachor is an additive-constitutive property.
For example the parachor of C2H4 should be = (2 x 4.8) + (4 x 17.1) = 78.0 but it was found
99.5. Hence double bond should make a contribution of 21.5. Similarly triple bond has been
making a contribution of 46.6.

Atomic & Structural Parachor:

C 4.8
H 17.1
O 20.0
Cl 54.3
Br 68.0
I 90.9
C=O 44.4
-OH 30.2
-COOH 73.7
-NO2 73.8
C-C (single bond) 0.0
C=C (double bond) 23.2
C≡C (triple bond) 46.6
Ring (3-membered) 16.7
Ring (4-membered) 11.6
Ring (5-membered) 8.5

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 Ring (6-membered) 6.1

Application of parachor in structure elucidation:

The observed value of parachor of Quinone (C6H4O2) is 236.8. Determine the structure of
Quinone.
For C6H4O2 two structures are possible (I) and (II)
O
O O

O (II)
(I)

4H 4 x 17.1 68.4 4H 4 x 17.1 68.4

6C 6 x 4.8 28.8 6C 6 x 4.8 28.8
3C(C=C) 3 x 23.2 69.6 4C(C=C) 4 x 23.2 92.8
2O 2 x 20.0 40.0 2O 2 x 20.0 40.0
2ring 2 x 6.1 12.2 1ring 1 x 6.1 6.1
(6-membered) (6-membered)
Total 219.0 Total 236.1
Observed value is close to structure (II). The structure of Quinone is (II).
DIPOLE MOMENT
Definition: It is the product of the magnitude of the separated charge and the distance of
separation between the charges.

q1(+) q2(-)
Dipole moment (μ) = q x r
Unit of dipole moment: 1Debye = 1D = 3.33 x 10-30 c. m (coulomb. meter) (S.I. unit)

Indication: It is indicated by an arrow having a symbol ( ) positive sign at positive

pole and head of the arrow towards the negative end. Dipole moment has both magnitude and
+
direction and therefore it is a “vector” quantity. For example, H Cl

Bond dipole & Molecular dipole:

Dipole moment is actually measure the polarity of a “bond” and a “molecule”. The polarity of
bond is created due to electronegativity difference between the two dis-similar atoms like HCl.
Di-atomic molecules have no dipole moment (Cl2).The greater the electronegativity difference,

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 the more polar the bond and greater is the “bond dipole moment”. The polarity of a molecule
depends upon the geometry of the molecule. The net “dipole moment of the molecule” is the
vector sum of all the individual bond dipole moments.

 B
A 
2 C

𝜇 (𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒) = √(𝜇1)2 + (𝜇2)2 + 2𝜇1𝜇2𝐶𝑜𝑠𝜃

Dipole moment of symmetrical polyatomic molecules:
These are not polar because they have not net molecular dipole [μ (molecule) = 0] and bond
dipole moments present in the molecule cancel out each other are in same direction. For
example dipole moment of CO2 molecule is zero, μ(c=o) bond (is the difference of E.N of O
and C) = 3.5-2.5 =1.0. Dipole moment of CO2 = μ(c=o)-μ(c=o) =1.0-1.0 = 0.

F H
B C
O C O H H
F F
H
(CO2) (BF3) (CH4)

Dipole moment of unsymmetrical molecules:

They always have net value of dipole moment, thus molecules are “polar” in nature. The bond
dipoles of the molecule are not in same direction. μ(CH3Cl) = 1.86D and μ(CH3OH) = 1.68D.

H Cl
108o
1.53D
CH3 O C
H H
1.3D 0.86D
H
According to Law of parallelogram

𝜇 (𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒) = √(0.3 + 0.86)2 + (1.53)2 + (2 × 1.16 × 1.53)𝐶𝑜𝑠 108

= √1.35 + 2.34 + 5.38 (−0.309)

= √2.03
= 1.68D

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Dipole moment of lone pair of electron containing molecules:

:
:
P
N N O H 900 H
H H

:
F F H H H
1070 104.50
H F
(NH3) (NF3) (H2O) (PH3)
Both NH3 and NF3 have pyramidal shape with one lone pair of electron on nitrogen atom. The dipole
between N-atom and lone pair of electron is in the direction of the lone pair of electron in both the
cases. Resultant moment of 3N-H bonds adds up to the bond moment of lone pair of electron,
whereas that of 3N-F bonds of NF3 counter the bond moment of lone pair of electron and has less
dipole moment (μ = 0.24D) than NH3 (μ = 1.46D).
In water there are two lone pairs of electron which reduces the bond angle up to 104.5ᵒ as LP-LP
repulsion is greater than BP-LP repulsion. The bond dipole moment of N-H is less than O-H (oxygen
is more electronegative than nitrogen) therefore overall dipole moment of H2O (μ = 1.84D) is greater
than NH3.
Regarding PH3 (μ = 0.58D) the bond angle is 90ᵒ shows that it does not undergo hybridization and
therefore has very less dipole moment.
Ionic bond has E.N. difference ˃ 1.7, Polar covalent ˃ 0.5 and < 1.7. Covalent < 0.5.
Dipole moment of hetero-cyclic compounds:
:

:
:

O O S S N N
H H
:

:
:

(I) (II) (III) (IV) (V) (VI)

(0.70D) (1.73D) (0.51D) (1.90D) (1.81D) (1.58D)
:

Z Z Z
(Z = O, S and N)

Structure, Furan (I) and Thiophene (III) both have two lone pairs of electron. One of them is involve
in resonance and other is located in sp2 hybridized orbital. The lone pair of electron involves in
resonance tends to polarize the bond from O→C or from S→C but lone pair of electron present in

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sp2 orbital opposite in direction of the ring system counter the effect of the lone pair of electron
involve in resonance and keep the dipole moment C→O or C→S with μ = 0.70D and μ = 0.51D
respectively. In structure, Tetrahydrofuran (II) and Tetrahydrothiophene (IV) when lone pair of
electron is not involve in resonance both the lone pairs of electron reinforce the dipole moment of
the molecule in same direction with μ = 1.73D and μ = 1.90D respectively.
In structure, Pyrrole (V) the lone pair of electron involves in resonance tends to polarize the bond
from N→C and there is no any other lone pair of electron to counter its effect therefore inversion in
dipole moment is observed. In structure, Tetrahydropyrrole (VI) resonance does not occur therefore
bond dipole moment is C→N and it is μ = 1.58D.
Dipole moment of aromatic compounds:
:

:
NH2 : OH : OCH3 CH3

(I) (II) (III) (IV) (V)

( = ) (1.52D) (1.45D) (1.20D) (0.40D)
(Benzene with electron donating group substitution)

Benzene has zero dipole moment due to symmetrical in nature. Benzene with electron donating
groups has dipole moment towards the ring system.
NO2 CN CO2CH3 Cl Cl

(VI) (VII) (VIII) (IX) (X)

(3.94D) (3.90D) (1.91D) (1.56D) (2.2D)
(Benzene with electron withdrawing group substitution)

Benzene with electron withdrawing groups has dipole moment opposite the ring system. Presence
of resonance in chloro-benzene (IX) makes C-Cl bond shorter than chloro-cyclohexane (X) therefore
its dipole moment is less.

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 (Azulene) (Resonsnce contributor of Azulene)

The most stable contributor of Azulene has negative charge in the 5-membered ring and positive
charge in the 7-membered ring. This separation of positive and negative charge give rise to molecular
dipole moment 1.08D.
Dipole moment gives idea about the geometrical shape of the molecule:
Formula Geometry Dipole moment Examples
AX2 Linear μ≠0 H-F, H-Cl
Linear μ=0 CO2, CS2
Bend or V-shaped μ≠0 H2O, H2S, NO2
AX3 Triangular planar μ=0 BF3
Pyramidal μ≠0 NH3, PCl3
AX4 Tetrahedral μ=0 CH4, CCl4
Square planar μ=0 XeF4
AX5 Triangular μ=0 PCl5
bipyramidal
Square pyramidal μ≠0 BrCl5
AX6 Octahedral μ=0 SF6
Distorted octahedral μ=0 XeF6
AX7 Pentagonal μ=0 IF7
bipyramidal

Dipole moment gives idea about the isomers:

(1) Dipole moment of isomers of dichlorobenzene decreases with increasing angle θ.
Cl Cl Cl

Cl

600 1800
1200
Cl
(o-isomer) (m-isomer) (p-isomer)
(2.54D) (1.72D) Cl ( = )
The resultant (molecular dipole moment) of o-isomer is 2.45D, m-isomer is 1.72D and of p-
isomer is zero because at 180ᵒ the bond dipole moments are opposite and cancel out each other.

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(2) Cis-2-butene has dipole moment 0.4D because methyl groups are an the same side and have
some resultant value, in trans-isomer methyl groups are opposite and cancel out bond dipole of
each other and the isomer has zero dipole moment.
H H H CH3

C C C C

H3C CH3 H3C H

(cis-2-butene) (trans-2-butene)
( = 0.4D) ( = 0)
Dipole moment gives idea about the ionic character of the molecule:
Dipole moment of HCl is 1.11D and distance between atoms is 127pm. 1onic % of HCl can be
calculated as:
For 100% ionic character μ = q x r
= (1.60 x 10-19 C) (127 x 10-12 m) (1D/ 3.336 x 10-30 C. m)
= 6.09D
Ionic% of HCl = 1.11/6.09 x 100 = 18.2%

Dipole moment gives idea about the solubility of the substance:

It is a measure of polarity of the substance, therefore it gives idea about solubility of a substance in
polar or non-polar solvent (like dissolve like). For example sucrose (2.35D, means polar)) is soluble
in water (polar solvent) but I2 (μ = 0, means non-polar)) is not soluble in water (polar solvent) but
soluble in CCl4 (non-polar).

Dipole moment helps to explain activity of drug molecules:

(1) DDT has three isomers its p-isomer has dipole moment 1.10D ( other isomers have 1.55D,
1.90D) due to having less dipole moment it is less polar and can penetrate easily into insect’s
cell (cell wall is composed of lipid) and shows greater toxic effect as compare to other isomers.
(2) Morphine (3.39D) is an analgesic drug due to having –OH groups it is polar and water soluble.
Its acetyl derivative, Heroin (3.13D) is less polar and highly lipid soluble therefore it can cross
BBB and can produce CNS disorders.

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 Cl Cl Cl
Cl C Cl Cl C Cl Cl C Cl

C C C
Cl
H H H
Cl

Cl Cl Cl Cl
(DDT p-isomer) (DDT m-isomer) (DDT o-isomer)
(1.10D) (1.55D) (1.90D)

HO H3CCO

O O

N CH3 N CH3

HO H3CCO

(Morphine) (Heroin)
O
(3.39D) (3.13D)

DIELECTRIC CONSTANT

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When a dielectric, insulating material is placed between the plates of a capacitor, cause the electric
field inside the capacitor to be reduced for the same amount of charge on the plates. This is because
the molecules of the dielectric material get polarized in the field, and they align themselves in a way
that set up another field inside the dielectric, opposite to the field from the capacitor plates.
The dielectric constant is the ratio of the electric field without the dielectric (E°) to the electric
field with the dielectric (E).
Electric field (E) = V/d ------------ (1)
Dielectric constant (Ɛ) = E°/ E
Dielectric constant can also be defined on the basis of “capacitance”. The capacitance (C), in
Faraday, is equal to the quantity of electric charge (Q) in coulombs stored on the plates divided by
potential difference (V) in volts between the plates.
Capacitance (C) = Q /V ------------- (2)
Comparing the equations (1) and (2) we know electric field (E) is directly proportional to V (d is
distance between the plates is constant) and capacitance (C) is inversely proportional to V (Q is
constant for same charge on the plates in both the cases). Electric field (E) and capacitance (C) are
inversely proportional to each other.
The dielectric constant is the ratio of the capacitance with the dielectric (C) to the capacitance
without the dielectric (C°).
Dielectric constant (Ɛ) = C/C°

d d d
- + - _ _ + - + - +
+ + _ +
- + - _ _ _ + -
+ + + +
Q(-) - Q(+) Q(-) - Q(+) Q(-) - Q(+)
+ _ + + +
+ _ +
_
+ -
- - -
+ _ + +
- - + _ +
_
+ - +
+ + - +
- - + _ +
_
+ _ -
+ + +

V V V

(I) (II) (III)

(I) E= electric field without dielectric
(II) Alignment of dielectric molecules
(III) Surface charges on dielectric reduce the electric field i.e E

Dielectric constant has no unit because it is a ratio and dielectric constant of vacuum is 1. C° (vacuum
capacitance) is used as a reference to compare capacitance of the other substances.
Dielectric constant is a measure of the ability of molecules (solvent) to resist charge separation.
If the ratio of the capacitance are close, its means there is greater resistance to charge separation and
as the ratio increases the molecule has ability to separate charge.
If water (polar solvent) (dielectric constant = 78.5) is placed, the capacitance is increased because
water molecules can orientate itself so that its (-) end lies nearest the (+) plate and its (+) end lies
nearest the (-) plate. This alignment provides ease with which electrons can flow between the plates
and additional charge can be placed on the plates per unit applied voltage.

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Pentane (dielectric constant = 1.84) is not a polar molecule and therefore its electronic structure
would not be able for a large charge separation.
1-Pentanol (dielectric constant = 13.9) has –OH group and has ability to undergo charge separation
and has greater dielectric constant than Pentane.

Dielectric constant of the solvent and solubility of the compounds:

Water is a universal solvent for ionic compounds or salts: When a salt is dissolved in a solvent, the
force of attraction between its ions is governed largely by the dielectric constant of the medium in
which it is dissolved and the distance between the ions. The force of attraction between two ions can
be calculated by using formula:
𝑄1 𝑄2
𝐹= 2
𝑟 Ɛ

Where Q1 and Q2 are the charges on the ions and “r” is the distance of separation and “Ɛ” is the
dielectric constant of the medium. The dielectric constant of water is about 80 means in water the
force of attraction between the ions would be 80 times less than in vacuum (Ɛ of vacuum is 1). Water
is the best solvent for ionic compounds due to its high dielectric constant.
NaCl dissolves in water at 1g in 2.8ml in glycerol which has half the dielectric constant of water 1g
dissolves in 10ml. NaCl is almost in soluble in ethanol (dielectric constant = 30) due to its low
dielectric constant.

Dielectric constant (Ɛ) Solvent (s) Soluble solutes

80 Water Inorganic and organic salts
50 Glycols Sugars, Tannins
30 Methanol / Ethanol Castor oil, waxes
20 Aldehydes, ketones, Volatile oils, weak electrolytes (Barbiturates,
higher alcohols, ethers alkaloids, phenols)
and esters
5 Hexane, benzene, Fixed oil, fats, petrolatum, paraffin and
CCl4, ethyl ether hydrocarbons.

Dielectric constant in Pharmaceutical preparations:

If we know the dielectric constant of our drug we can prepare a solvent system with the appropriate
dielectric constant to dissolve that drug.
The significance of co-solvency is that it is very useful to prepare a solution of the neutral (unionized)
form of an ionize-able drug like weak acids and weak bases, because neutral form is more absorbed
form of a drug. If absorption from solution form is concern we can maximize the absorption by
dissolving the neutral form of drug using co-solvency. For example Phenobarbital (Ɛ = 35) which is
weakly acidic drug that is poorly soluble in the neutral (unionized) form. To prepare oral solution

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(containing only neutral form) we can use a co-solvent system water, alcohol or glycerol in proper
proportion to have a dielectric constant about 35.
Ɛ (mixture) = 92% propylene glycol (Ɛ = 32) + 8% water (Ɛ = 80)
= (0.92 x 32) + (0.08 x 80)
= (29.44) + (6.40)
= 35.8
REFRACTIVE INDEX

Refraction: Bending of light ray when it passes from one medium to another medium (of different
densities) is known as refraction. When it passes from lighter medium (air) to denser medium (water)
it bends towards the normal and when it passes from denser medium (water) to lighter medium (air)
it bends away from normal. Light has different velocities in mediums of different densities therefore
when it enters from one medium to another change in velocity of light takes place and bending of
light is observed.

(incident ray)
(normal) (normal)
(air) (refrected ray) (air)
(water) (water)

(refrected ray)

(incident ray)
(ray bends toward normal) (ray bends away from normal)
When light enters a denser substance, the advancing waves interact with the atoms in the substance
at the interface and throughout the thickness of the substance. These interactions modify the light
waves by absorbing energy, resulting in the waves being closer together by reducing the speed and
shortening the wave length and bend of light is observed.

Refractive index: It is measure of the bending of a ray of light when it passing from one medium
to another. If “i” is the angle of incidence (angle between incoming ray and the normal) of a ray in
vacuum (or air) and “r” is the angle of refraction (angle between the ray in medium and the normal)
the refractive index (n) is defined as the ratio of sine of angle of incidence to the sine of angle of
refraction.
Refractive index (n) = sin i /sin r ------------- (1) (Snell’s law)

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 (incident ray)
(normal)
i
(vacuum or air)
(water)
r
(refrected ray)

(Snell's law)
Snell’s law can also be represented as:
𝑛1 𝑠𝑖𝑛𝜃1 = 𝑛2 𝜃2 ------------------ (2)
θ1 = angle of incidence, n1 = refractive index of medium of incidence.
θ2 = angle of refraction, n2 = refractive index of medium of refraction.
Refractive index (n) can also be defined as ratio of velocity of light of a given wave length in
vacuum (or air) (c) to its velocity in a substance (v).
Refractive index (n) = c / v ------------------ (3)
The velocity of light in vacuum is maximum therefore value of refractive index is greater than 1.
Use of air as a reference produces a difference in refractive index (n) of only 0.03% from that in a
vacuum and is more commonly used.
By combining equations (1) and (3) we have:

𝑠𝑖𝑛 𝑠𝑖𝑛 𝑖 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑜𝑓 𝑙𝑖𝑔ℎ𝑡 𝑖𝑛 𝑣𝑎𝑐𝑢𝑢𝑚 (𝑜𝑟 𝑎𝑖𝑟) 𝑐1

𝑛= = =
𝑠𝑖𝑛 𝑠𝑖𝑛 𝑟 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑜𝑓 𝑙𝑖𝑔ℎ𝑡 𝑖𝑛 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑐2

When refractive index is being determined by using vacuum (or air) as a reference the refractive
index is known as absolute refractive index ( for vacuum or air n =1) and when any other medium
is used as reference the refractive index is known as relative refractive index.
Refractive index is a ratio therefore it has no unit.
Factors effecting refractive index:
The refractive index varies with the wavelength of light and the temperature because both alter the
energy of interaction. These values are identified when a refractive index is reported; for example,
𝑛𝐷20 signifies the refractive index using the D-line emission of sodium, at 589 nm, at a temperature
of 20°C.
Significance of refractive index:
It is a characteristic property of liquid, can be used to identify a substance, to measure its purity, and
to determine the concentration of one substance dissolved in another. Refractometers can be used
for studying pharmaceutical compounds that do not undergo extensive UV-Vis absorption due to
their electronic structure.

Specific refraction or Specific refractivity:

Lorenz and Lorenz (1880), on the basis of electromagnetic theory of light derived the following
relation for the refractive power of a substance.

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 𝑛2 − 1 1
𝑅= ( )
𝑛2 + 2 𝑑

Where: R = Specific refraction, n = refractive index, and d = density

Molar (Molecular) refraction or Molecular Refractivity (Rm):

The product of molecular weight (M) and specific refractivity (R) is known as Molar refraction (Rm).
𝑛2 −1 𝑀
𝑅𝑚 = 𝑛2 +2 ( 𝑑 )

Value of molar refraction is characteristic of a substance, it is independent of the physical state of

the molecule and temperature. Since the value of refractive index (n) is dimensionless, from the
equation it is evident that Rm α M/d and M/d is molar volume, therefore Rm is expressed in cm3/mole.
Rm is proportional to molar volume, therefore Rm like Parachor is also an additive-constitutive
property and can be used to determine structure of molecule by comparing with experimental value
of the compound.
For example it can be used to distinguish between keto and enol tautomers. Experimental Rm of
C3H6O is 16.974 cm3/mole, compound is acetone (CH3-CO-CH3) or allyl alcohol (CH2=C(OH)-
CH3)?
3C = 3 x 2.42 = 7.26 3C = 3 x 2.42 = 7.26
6H = 6 x 1.10 = 6.60 6H = 6 x 1.10 = 6.60
1C=C =1 x 1.73 = 1.73 1(C=O) = 1 x 2.21 = 2.21
1(O-H)=1 x 1.53 = 1.53 _____________________
____________________ CH3-CO-CH = 16.07 cm3/mole
CH2=C(OH)-CH3 = 17.12 cm3/mole .Experimental value is close to value of Allyl alcohol.

Critical angle and total internal reflection:

When a ray of light AO passes from an optically denser medium to a rarer medium, at the interface,
it is partly reflected back into the same medium along OB and partly refracted into the rarer medium
along OC.
With increasing angle of incidence (i) the angle of refraction (r) also increases and at a certain stage
r becomes 90°. Now the refracted ray OC is bent so much away from the normal and it grazes the
surface of separation of two media. The angle of incidence in denser medium at that point is known
as critical angle (c) of the denser medium.
If i is increased further, the refraction is not possible and the incident ray is totally reflected into the
same medium itself. It is known as total internal reflection.
For total internal reflection two things are necessary: (1) Light must travel from a denser medium to
a rarer medium (2) The angle of incidence inside the denser medium must be greater than critical
angle (i ˃ c).

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 C

r
r = 900
rarer O rarer O rarer O
denser denser denser
ic
i i=c A B
A B
A B
(critical angle) (total internal reflection)
If rarer medium = air, denser medium = water, na and nw are refractive indices of air and water.
𝑛𝑤 𝑆𝑖𝑛 𝑖 = 𝑛𝑎 𝑆𝑖𝑛 𝑟 ------------------------- (According to equation 2)
𝑛𝑤 𝑆𝑖𝑛 𝑐 = 𝑛𝑎 𝑆𝑖𝑛 90°
𝑛𝑤 𝑆𝑖𝑛 𝑐 = 1 (na =1 and Sin 90°= 1)
1 1 1
Critical angle of water (c) = 𝑆𝑖𝑛 𝑛 = 𝑆𝑖𝑛 (𝑛 )
𝑤 𝑤

Medium Refractive index Critical angle

Water 1.33 48.75°
Diamond 2.42 24.41°

Abbe’s refractometer:
In the Abbe’s refractometer the liquid sample is sandwiched into a thin layer between an illuminating
prism and a refracting prism. The refracting prism is made of a glass with high refractive index (e.g.
1.75) and the refractometer is designed to be used with samples having a refractive index smaller
than that of the refracting prism. A light source (sodium D line at 589nm) is projected through the
illuminating prism, the bottom surface of which is ground, so each point on this surface can be
thought of as generating light rays traveling in all directions. Light traveling from point A to point
B will have the largest angle of incidence (θi) and hence the largest possible angle of refraction (θr)
for that sample. All other rays of light entering the refracting prism will have smaller θr and hence
lie to the left of point C. Additional optics (detector) associated with refracting prism are used to
show a light region to the left and dark region to the right. Different samples will produce different
angle of refraction and this will be reflected in a change in the position of borderline between light
and dark region. This position of borderline can be used to determine the refractive index of a sample.
In Abbe’s refractometer view in the telescope through eye piece appears to be divided into light and
dark bands, and correct position of borderline can be obtained by placing the point of cross hair of
the telescope at the borderline and refractive index of the sample can be determined directly on an
engraved scale.

17
 (illuminating prism)
A
(sample) i (light)
B
(dark)
(refractng prism)
r C
(light) (dark) (position of cross hair)

If white light is used in simple Abbe’s refractometer a set of “compensating prisms” is used in the
optical path after the refracting prism to correct the dispersion of the sample in such a way that they
reproduce the refractive index that would be obtained with monochromatic light of 589 nm, the
sodium D line.
Since density of liquid decreases with increasing temperature, the refractive index normally
decreases with increasing temperature (0.0005 for every 1°C increase in temperature). Many
refractometers are equipped with a thermometer and prisms are enclosed in water jacket to maintain
a given temperature.

Advantages of Abbe’s refractometer:

(1) The instrument is easy to handle.
(2) Only few drops of liquid are required.
(3) Refractive index can be measured directly.
(4) Temperature can be maintained.
(5) The refractive index range is from 1.3-1.7 with an accuracy of ± 0.0002 units

OPTICAL ROTATION

Un-polarized and Polarized light:

Light is an electromagnetic wave, and the electric field of this wave oscillates perpendicularly to the
direction of propagation. Light is called un-polarized if the direction of this electric field fluctuates
randomly in time e.g. sunlight. If direction of the electric field is well defined, it is called polarized
light e.g. laser.
Passing un-polarized light through a polarizing prism (Nicol prism) sorts the randomly distributed
vibrations of electric radiation so that only those vibrations occurring in a single plane are passed to
give plane polarized light.

(randomly oriented light) (polarizer) (plane-polarized light)

Classification of polarized light:
Depending on how the electric field is oriented, polarization may be of 3 types:
(1) Linear polarization: The electric field of light is confined to a single plane along the direction of
propagation.
18
(2) Circular polarization: The electric field of light consists of two linear components that are
perpendicular to each other, equal in amplitude but have a phase difference of Π/2. The resulting
electric field rotates in a circle around the direction of propagation and, depending on the rotation
direction, is called left or right-hand circularly polarized light (Curl the fingers of both hands
around in loose fist, holding the thumbs steady. The thumbs indicating the direction of
propagation toward your nose, and the curling of the fingers shows how the light vectors are
spiraling into two separate vectors).
(3) Elliptical polarization: Two linear components with different amplitudes and/or a phase
difference that is not Π/2.
Optical rotation:
The angle by which the linear plane polarized light is rotated by the compound when it passes
through it is known as optical rotation of that compound.
Optical activity:
The ability of a substance to rotate the plane polarized light is known as optical activity and the
substance is known as optically active substance. The substance which cannot rotate the plane
polarized light is known as optically inactive substance. When the plane of light is rotated by the
sample in a clockwise manner, the sample is known as dextrorotatory and for counterclockwise
direction is known as levorotatory. A dextrorotatory substance , which rotates the beam of light to
the right, produces an angle of rotation (α), that is defined as positive (+), whereas the levorotatory
substance , which rotates the beam of light to the left, produces an angle of rotation (α), that is
defined as negative (-).
Specific rotation:
It is standard measurement of optical rotation for a substance. It is intrinsic property for a particular
substance at constant temperature. It is characteristic for a pure, optically active substance and can
be used to identify the compound.
It is represented as:
𝛼𝑣
[∝]𝑡𝜆 =
𝑙𝑔

∝ = specific rotation (in degree)

t = temperature (°C) (optical rotation, depends on density and density depends on temperature)
𝜆= wavelength ( D line of sodium) (by changing 𝜆 value of specific rotation can be changed)
𝛼 = observed optical rotation (in degree)
𝜐= milliliter (ml)
l = length in dm
g = number of grams of optically active substance.

The subscript D on [α] indicates that the measurement of specific rotation is made at a wavelength,
λ, of 589nm for sodium light. When the concentration is not specified, the concentration is often
assumed to be 1g per milliliter of solvent. [α] should be reported at specific temperature and
concentration including solvent.
Drug [α]D Temperature (°C) Solvent

19
 Ampicillin +283 20 Water
Quinidine +230 15 Chloroform
Nicotine -162 20 Pure liquid

How optical rotation takes place?

● The velocity of plane polarized light can become slower or faster as it passes through a sample.
This change in velocity results in refraction of the polarized light in a particular direction for an
optically active substance.
● It can be considered as the interaction of a plane-polarized radiation with electrons in a molecule
to produce electronic polarization. This interaction rotates the direction of vibration of the radiation
by altering the electric field.
● Fresnel’s theory of optical rotation:
*The beam of plane polarized light on entering a substance along the optic axis is divided into two
circularly polarized vibrations, one right handed (R) and other left handed (L).
* In an optically in active substance the two circularly polarized vibrations reached at point Q
(along the path of plane polarized incidence light) by traveling with the same angular velocity
and the resultant vector of these velocities remain along the optical axis, and no rotation is
observed.
(resultant vector)

L R

(opic axis)

(no optical rotation)

* In an optically active substance these two circularly polarized vibrations move with different
velocities. In dextrorotatory substance right-handed (clockwise) motion travels faster and in
levorotatory substance left-handed (counterclockwise) motion travels faster. Circularly polarized
vibration R arrives at Q first, and as the wave travels on, the displacement turns through an angle
θ before the circularly polarized vibration L reached at point Q. The resultant vector of two
velocities (R and L) has an angle θ with respect to optic axis as optical rotation.

20
 L (resultant vector)
 R
Q

(opic axis)

(optical rotation,)
Polarimeter:
A polarimeter is a scientific instrument used to measure the angle of rotation caused by passing
polarized light through an optically active substance.
Construction & Working of Two-field (half shade) Polarimeter:
It consists of two Nicol prisms N1 (polarizer) and N2 (analyzer). Behind N1, there is a Nicol prism
N3 which covers half the field of view. G is the glass tube which contains optically active solution.
Light from a monochromatic source (sodium D line, 589nm) is incident on the polarizer (N1). The
light transmitted by polarizer (N1) in plane-polarized light. The polarized beam then pass through
N3 and then through the glass tube (G). The light emerging from the solution will be incident on
analyzer (N2).The light is observed through a telescope (T). The analyzing Nicol (N2) can be rotated
about the axis of the tube and the rotation can be measured with the help of a graduated circular scale
(S).

.
(source of light) ( N1 ) ( N3 ) (G) ( N2 ) (S) (T)
Two field (half-shade):
N1 and N3 have their planes of vibration inclined at small angle. Suppose the plane of vibration of
N1 is along AB and that of N3 is along CD. The angle between two planes is θ. When the analyzer
(N2) is rotated such that the plane of vibration of N2 in along AB, the left half will be brighter than
the right half (I). If the analyzer (N2) has its plane of vibration along CD, the right half will be
brighter than left half (II). When the plane of vibration of the analyzer (N2) is along YY' (bisector of
angle AOC), the field of view is equally illuminated (III). Therefor by rotating the position for equal
brightness can be obtained to determine optical rotation. (See diagram below)

Three field system:

The defect in two field system is that if the eye is off the axis, even for the position of equal brightness
of the field of view, one side appears brighter than the other. Just behind N1 there are two prism N3
and N4. The planes of vibration of N3 and N4 are parallel to each other and make a small angle with
plane of vibration of N1. For a particular position of analyzer (N2) the field has three parts. The
central position is illuminated by light, which has passed through N1 and N2 while the other two
positions, which are equally bright, are illuminated by light passing through N1, N2 and one of the
prisms N3 and N4.

21
Applications of optical rotation or optical activity in pharmacy:
(1) Enantiomers are mirror image to each, have same physical and chemical properties, but have
only difference in optical activity. By optical activity they can be identified (having either R
or S configuration). Their actual configuration should be known, because sometime
enantiomers have different pharmacological activity e.g. S-Thalidomide is sedative but R-
Thalidomide is teratogen.
O O

H H
N N
O O
S R
NH NH
O O O
O

(S-Thalidomide) (R-Thalidomide)
(2) It can be used to determine the % purity of an optically active compound. Specific rotation
of pure S-Ibuprofen is 54.5°. A sample of S-Ibuprofen has specific rotation 53.2°. Determine
% purity of the sample.

[∝](𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑) 53.2
% 𝑝𝑢𝑟𝑖𝑡𝑦 = [∝](𝑎𝑐𝑡𝑢𝑎𝑙)
𝑥 100 = 54.5 𝑥 100 = 97.6%

(3) It is used in pharmaceutical industries to determine purity and concentration of the substances
includes: Alkaloids (cocaine, codeine, and nicotine), Amino acids (glutamic acid), Organic
compounds (camphor) and vitamins (ascorbic acid).

(4) To check presence of sugar and albumin in urine.

(5) To determine sugar in sugar syrups and sugar-free sweetener (isomalt).

(6) To check purity and identification of optically active essential oils and essences like lemon
oil, orange oil, lavender oil and spearmint oil.

SURFACE & INTERFACIAL TENSION

Interfacial tension:

22
At the interface of two phases (A and B) due to difference in cohesive (between A-A or B-B) and
adhesive (between A-B) forces of the molecule a tension is developed, which is known as interfacial
tension.
Phase Interfacial tension Example
Gas-gas - No interface because they are miscible.
Gas-liquid γLV Water exposed to air
Gas-solid γSV Sodium chloride exposed to air
Liquid-liquid γLL Water and benzene (immiscible liquids) or emulsion
Liquid-solid γLS Paracetamol in water or suspension
Solid-solid γSS Powder particles of A and B in contact
The term surface tension is reserved for γLV and γSV tensions and interfacial tension is most often
used for γLL tension. The interfacial tensions are less than surface tensions because the adhesive
forces between two liquid phases forming an interface are greater than when a liquid and a gas phase
exist together.
Surface tension:
Molecules in the bulk liquid are surrounded in all directions by other molecules for which they have
an equal attraction (cohesive forces to neighboring molecules). Molecules at the surface (at the
liquid-air interface) have only attractive cohesive forces with other liquid molecules that are situated
below and adjacent to them (missing cohesive forces to neighboring molecules). They can develop
adhesive forces of attraction with the molecules constituting the other phase, but in this case other
phase is air therefore, this adhesive force of attraction is very small. The molecules at the surface of
the liquid experience an inward force toward the bulk. Such a force pulls the molecules of the
interface together and, as a result, contracts the surface, resulting in surface tension.

(missing cohesive forces

to beighboring molecules)

air
water

(cohesive forces to
neighboring
molecules)

(cohesive forces to neighboring Surface tension

molecules)

Definition-1: (in term of force/length)

23
Surface tension is the force per unit length that must be applied parallel to the surface so as to
counterbalance the net inward pull.

A soap film is formed over the rectangular frame (ABCD), composed of three unmovable sides (AB,
BC and CD) and a fourth movable side (AD). The surface tension will pull the movable side (AD)
to the left; the force (F) required to hold the movable side is proportional to the length (L) of the
movable side (AD) and parallel to the moveable side (AD). The ratio of F/L will remain constant for
all other shapes s(other than rectangular). Therefore surface tension (γ) =1/2(F/L). The reason for ½
is that the film has two liquid-gas interfaces (one above and one below the plane of paper), the total
length of contact is in fact equal to twice the length of movable side (AD). The surface tension has
the units of dynes/cm in cgs system and of N/m in the SI system.

B A

L F

C D

Definition-2: (in term of energy/area)

To move a molecule from the inner layers to the surface, work (W) needs to be done against the
force of surface tension. Each molecule near the surface of liquid possesses a certain excess of
potential energy as compared to the molecules in the bulk of the liquid. The higher the surface of the
liquid, the more molecules have this excessive potential energy. Therefore, if the surface of the liquid
increases, the energy of the liquid also increases. Greater the work is done, the higher the surface of
the liquid and greater will be the surface energy. Surface tension (γ) of a liquid is the ratio of the
change in surface energy to the change in surface area of the liquid. Surface energy is defined as the
work per unit area done by the force that creates the new surface.
As we know 𝛾 × 2𝐿 = 𝐹------------(1)
Multiplied both side by distance “d” we have
𝛾 × 2𝐿 × 𝑑 = 𝑑 × 𝐹----------------(2) ( see left figure)
2𝐿 × 𝑑 = ∆𝐴 and 𝑑 × 𝐹 = 𝑊, therefore equation (2) can be written as:
𝛾 × ∆𝐴 = 𝑊
𝑊
𝛾=
∆𝐴

Where “W” is the work done, or increased surface energy (ergs), γ is the surface tension (dynes/cm)

24
and ∆A is increase in area (cm2). The surface tension has the unit of ergs/cm2 in cgs system and J/m2
in the SI system.

Each molecule of the liquid has a tendency to move inside the liquid from the surface (due to surface
tension) therefore liquid takes form with minimal surface and minimal surface energy, therefore a
free droplet of liquid naturally assumes a spherical shape, which has a minimum surface
area/volume.

Determination of surface tension:

Capillary rise method:

When a capillary tube with an inside radius (r) immersed in a liquid that wets its surface, due to
surface tension of the liquid, liquid begins to rise in the capillary tube up to height (h), where two
forces, surface tension of liquid along the circumference of the tube (upward) and weight of liquid
inside the capillary tube (downward) are balanced. This method can determine surface tension only.

Surface tension of liquid is divided into two components γsinθ (horizontal) and γcosθ (vertical).For
upward force only vertical component is useful and total upward force along the circumference of
the tube = 2Πrγcosθ. Total downward force = weight of liquid in capillary tube = mass of liquid x
gravity = (volume of liquid in tube) x (density of liquid) x (gravity) = (Πr2h) (d) (g) = Πr2hdg.

Upward force = downward force

2Πrγcosθ = Πr2hdg (for most of the liquids cosθ =1)

γ=hrdg/2
=cm.cm.(g/cm3).(981cm/sec2)
= g/sec2 = dynes/cm (dyne = g.cm/sec2)

Q. A sample of chloroform rose to a height of 3.67cm at 20°C in a capillary tube of inside radius of
0.01cm. Density of chloroform is 1.476g/cm3. Calculate surface tension of the sample.

γ = (3.67cm x 0.01cm x 1.467g/cm3 x 981cm/sec2)/2 = 26.6g/sec2 = 26.6 dynes/cm

Drop count method (stalagmometer):

25
This method can determine surface tension only. In this method same stalagmometer is used to count
number of drops of water and liquid (nW and nL respectively) by flowing them between specified
volume (V) between marks A & B. The drop forms at the tip of the stalagmometer is supported by
two forces. Surface tension (upward) and weight of the drop (downward). When these two forces
are balanced, drop breaks down, therefore at the breaking point:

Surface tension = Weight of drop

2Πrγ = m.g

For water 2ΠrγW = mw.g

For liquid 2ΠrγL = mL.g

2𝜋𝑟𝛾𝐿 𝑚𝐿 . 𝑔
=
2𝜋𝑟𝛾𝑊 𝑚𝑊 . 𝑔
𝛾𝐿 𝑚𝐿
𝛾𝑊
= 𝑚𝑊
----------(1) (mL
and mW are masses of single drop of liquid and water
respectively).
𝑉
𝑚𝐿 𝑛𝐿
𝑥 𝑑𝐿 𝑑𝐿 𝑥 𝑛𝑊 𝑑𝐿 𝑥 𝑛𝑊
𝑚𝑊
= 𝑉 = 𝑑𝑊 𝑥 𝑛𝐿
= 𝑛𝐿
---------- (2) (dw =1)
𝑛𝑊
𝑥 𝑑𝑊

By placing value of mL /mW from equation (2) into equation

(1) we have:
𝛾𝐿 𝑑𝐿 𝑥 𝑛𝑊
=
𝛾𝑊 𝑛𝐿
𝑑𝐿 𝑥 𝑛𝑊
𝛾𝐿 = 𝑥 𝛾𝑊
𝑛𝐿
𝑑𝐿 𝑥 𝑛𝑊 (𝑑𝑦𝑛𝑒
𝛾𝐿 = 𝑥 72.8
𝑛𝐿 𝑐𝑚)

dL= density of liquid (g/cm3), nW and nL are number of drops of water and liquid respectively, γL=
surface tension of liquid (dynes/cm).

nL < nw means drops of liquid are bigger in size (have greater mass) than water. Greater the mass of
the drops, more the surface tension of the liquid than water.

nL ˃ nw means drops of liquid are smaller in size (have less mass) than water. Less the mass of the
drops, less the surface tension of the liquid than water.

Ring detachment method (DuNouy tensiometer):

26
The principle of the instrument is that the force necessary to detach a platinum-iridium ring
immersed at the surface is proportional to the surface tension of the liquid. The force required to
detach the ring is provided by a torsion wire is recorded in dynes on a calibrated dial. One end of the
torsion wire is fixed while other is attached to a knob carrying a pointer. The pointer moves on a
fixed previously calibrated scale. The liquid whose surface tension is to be determined in placed in
a watch glass so that platinum-ring just touches its surface. The knob of the torsion wire is slowly
turned till the ring just detach from the surface. The reading shown by the pointer on the scale gives
force (F) directly in dynes. By using value of force (F) in formula, surface tension or interfacial
tension of the liquid can be determined.

According to definition of surface tension we know

𝐹
𝛾 = 2𝐿 (Where L = length of movable side)-------- (1)

By replacing length (L) with circumference of platinum-ring (2Πr) we have

𝐹 𝐹
𝛾 = 2(2𝜋𝑟) = 4𝜋𝑟---------- (2) (“F” in dynes from tensiometer, “r” is the radius of the platinum ring).

Maximum bubble pressure method:

This method can be used to determine surface or interfacial tension of the liquid. It is most commonly
used to measure the dynamic surface tension of systems containing surfactants because it does not
require contact angle measurement. In this method air pressure (which can be measured by taking
hm from manometer) is applied slowly through a capillary tube which is introduced up to the depth
(ha) into the liquid whose surface tension is to be determined.

By applying air pressure at the end of the capillary bubble grows and when it becomes hemispherical,
the radius of capillary and bubble are identical and maximum bubble pressure is observed on
manometer. With increasing radius of the bubble the bubble pressure is going to reduce slowly. The
maximum bubble pressure (Pb) equals that of the opposing hydrostatic pressure (Ph) and the surface
tension (γ) at the circumference of the capillary.

27
Pb = Ph + Surface tension at the circumference of the capillary
𝜋𝑟2 ℎ𝑚 𝑑𝑚 𝑔 = 𝜋𝑟2 ℎ𝑎 𝑑𝑎 𝑔 + 2𝜋𝑟𝛾

2𝜋𝑟𝛾 = 𝜋𝑟 2 ℎ𝑚 𝑑𝑚 𝑔 − 𝜋𝑟 2 ℎ𝑎 𝑑𝑎 𝑔
2𝜋𝑟𝛾 = 𝜋𝑟 2 𝑔(ℎ𝑚 𝑑𝑚 − ℎ𝑎 𝑑𝑎 )
𝜋𝑟 2 𝑔(ℎ𝑚 𝑑𝑚 − ℎ𝑎 𝑑𝑎 )
𝛾=
2𝜋𝑟
1
𝛾= 𝑟𝑔(ℎ𝑚 𝑑𝑚 − ℎ𝑎 𝑑𝑎 )
2

Where r = radius of capillary (cm), g (981cm/sce2), hm = height of mercury (cm), dm = density of

mercury (g/cm3), ha = depth of capillary in liquid (cm), da = density of liquid g/cm3).
𝑐𝑚 𝑔
= 𝑐𝑚 (𝑆𝑐𝑒 2) (𝑐𝑚2 )

𝑔 𝑔.𝑐𝑚 1
= 𝑆𝑒𝑐 2 = ( 𝑆𝑒𝑐 2 ) 𝑐𝑚 = 𝑑𝑦𝑛𝑒𝑠/𝑐𝑚

air
Pb

hm
ha
r
S.T S.T
(bubble)
(Liquid) Ph
(hemispherical drop) (spherical drop)
(Pb= maximum bubble (with increasing
(manometer)
pressure when radius radius of bubble,
of tube and bubble are bubble pressure
same) decreases)

Factors affecting surface tension of liquids:

Inter-molecular attraction:

28
Greater the inter-molecular attraction more the surface tension of the liquid at given temperature.
Polar liquids (water) have greater surface tension as compare to non-polar liquids (benzene), because
they have greater inter molecular attraction (hydrogen-bonding) between their molecules.

S.No. Liquid Nature/interaction Surface tension (dynes/cm) at 20°C

1 Water Polar / hydrogen bonding 72.75

2 Benzene non-polar 28.90

Structure of the molecule:

Along with interaction, structure of the molecule also affects the surface tension at given
temperature. Structure with less surface area (spherical) (tert-butyl alcohol) has less surface tension
than molecule with more surface area (chain) (n-butyl alcohol) because with decreasing surface area
of the molecule the interaction between the molecules decreases.

S.No. Compound Structure / shape Surface tension (dynes/cm) at 25°C

1 n-butyl alcohol CH3-CH2-CH2-CH2-OH /chain 24.93

2 tert-butyl alcohol (CH3)3C-OH / spherical 20.70

Temperature:

With increasing temperature inter-molecular forces between the molecules of liquid decreases,
therefore surface tension of the liquid also decreases. Eotvos-Ramsay & Shield gave a linear
relationship between surface tension and temperature. This relationship based on the fact that at
temperature 6°C below the critical temperature, the surface tension of liquid becomes zero.
2
𝑀 3
𝛾 ( ) = 𝐾 (𝑡𝑐 − 𝑡 − 6)
𝑑

γ = surface tension = dynes/cm

M = Molecular mass of the liquid (g/mole)

d = Density of liquid (g/cm3)

K = Eotvos constant = 1.436 x 10-7 dynes.cm/°C.mole2/3 .For associated liquid it has some low value

tc = Critical temperature (°C) ( temperature at which or above liquid totally changes to vapors phase
and cannot be liquefied). Critical temperature of water is 374°C.

t = Temperature at which surface tension is determined (°C).

29
 Liquid Surface tension of water (dynes/cm) at different temperatures

20°C 40°C 60°C 80°C

Water 72.758 68.577 64.395 60.214

Impurities:

The presence of impurities either on liquid surface or dissolved in it, considerably affect the surface
tension, depending on degree of contamination. A highly soluble substance like sodium chloride
when dissolved in water, increases the surface tension of water. But the sparingly soluble substances
like phenol when dissolved in water, decreases the surface tension of water.

Surfactants:

They reduce the surface tension of liquid (water). Surfactants (surface acting agents) have two
distinct regions in their chemical structure, one of which is hydrophilic (water loving) and other of
which is hydrophobic (water hating).When surfactants are dissolved in water they orientate at the
surface so that the hydrophobic regions are removed from the aqueous environment. When surfactant
molecules are adsorbed at the surface of the liquid (water) they replaced some of the water molecules
from the surface of the liquid and since force of attraction between surfactant molecules and water
molecules is less than force of attraction between the water molecules therefore inward force (surface
tension) is reduced.

Applications of surface tension:

(1) Pure liquids have their specific surface tension at particular temperature and presence of
impurities changes the surface tension of liquids, therefore it can be used to check the
%purity of the liquids.
(2) Parachor ([P] = molar volume x 𝛾 1/4) which is determined by surface tension of liquid, can
be used in structure elucidation of the isomers (as explained above).
(3) Hot water and addition of surfactant in water decreases the surface tension of water and
increases its penetration to improve cleaning and washing property.

30
(4) Antiseptics (Dettol) have low surface tension to spread out easily on the surface of wound as
compare to water.
(5) In toothpaste surfactant is used to reduce surface tension of the paste to spread out easily
between the teeth.
(6) In liver disorder surfactants from bile come into blood and reduce the surface tension of
urine. It can be used for diagnostic purpose.
(7) Alveoli are lined with a thin layer of fluid called surfactant which is a mixture of
phospholipids that reduce the surface tension and increase lung compliance. Large alveoli
require minimal pressure to keep them open; while small alveoli require more pressure (Law
of Laplace). Small alveoli are ideal for increasing surface area but without surfactant they
collapse and lung compliance decreases.
(8) Coating of tablet can improve product appearance, mask taste and odor or control the rate of
drug release. If the surface tension of coating material is too high, the wetting process will
be hindered. In addition if surface tension is too low the leveling process will be influenced.
Therefore, it is important to control the surface tension of the coating solution for a
presentable product.
(9) The rate limiting step in tablet disintegration is the penetration of the dissolution media
through the pores of the tablet. Liquid penetration into tablet pores is related to pore structure
and capillary tubes on the tablet surface. Washburn equation can be used to analyze liquid
penetration:
𝑟𝛾𝑐𝑜𝑠𝜃𝑡
𝜐2 =
2𝜂
Where v = volume of liquid penetrated in time (t), γ = surface tension, θ = contact angle, η =
viscosity and r = capillary radius. The equation indicates that surface tension is the driving
force for liquid penetration into solid dosage form.

(10)The average volume of a human tear is 7μl. The conjunctival sac is capable of holding 20-
30μl without overflowing. The average drop size of a commercial topical medication is 39μl.
This excess amount can be reduce by reducing the size of the drop. According to Tate’s law
(W = m.g =2Πrγ). This equation shows that by reducing the surface tension (by adding
surface active agents) the size of weight of the drop can be reduced.

(11)In general, surface tension of clean and dry human skin is 27-28 dynes/cm. For ant substrate
to adhere to the surface of the skin, its surface energy must be equal or less than that of the
human skin. It is taken into consideration to design skin adhesive used in bandage, wound
healing and transdermal systems.

(12) In suspension measuring of surface tension is a good approach to predict the flocculation
and investigate re-dispersion time of suspension and helpful to achieve a suitable and stable
formulation product.

VISCOSITY

31
Introduction / Definition:

A liquid may be considered to be consisting of molecular layers arranged one over other. Viscosity
is the measure of the internal friction between the layers of a liquid. This friction becomes apparent
when a layer of liquid is made to move in relation to another layer. The greater the friction, the
greater the amount of force required to produce this movement (called shear).

Two parallel layers of a liquid of equal area (A) are separated by a distance dx and are moving in
the same direction at different velocities v1 and v2 and dv = v2-v1.

The velocity gradient (dv/dx), is a measure of the change in speed at which the intermediate layers
move with respect to one another. It describes the shearing the liquid experiences and is called shear
rate.

The term F/A indicates the force per unit area required to produce the shearing action and is known
as shear stress.

Mathematically coefficient of viscosity or simply viscosity is the ratio of shear stress to share rate
𝐹
𝑠ℎ𝑒𝑎𝑟 𝑠𝑡𝑟𝑒𝑠𝑠 𝐹 𝑑𝑥
𝑉𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 (𝜂) = = 𝐴 = ( )
𝑠ℎ𝑒𝑎𝑟 𝑟𝑎𝑡𝑒 𝑑𝑣 𝐴 𝑑𝑣
𝑑𝑥

The viscosity is the force per unit area required to maintain the difference in speed between the two
layers of a liquid.

dv

A
V2
F
A
V1
dx

Units of viscosity:

𝐹 𝑑𝑥 𝑓𝑜𝑟𝑐𝑒 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑁 𝑚 𝑁. 𝑠𝑒𝑐 𝑁

𝑉𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 (𝜂) = ( )= ( ) = 2( 𝑚 ) = 2
= ( 2 ) 𝑠𝑒𝑐 = 𝑃𝑎. 𝑠𝑒𝑐
𝐴 𝑑𝑣 𝑎𝑟𝑒𝑎 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑚 𝑚 𝑚
𝑠𝑒𝑐
1 1 1 1 1 1
= (𝐾𝑔 2
) 𝑠𝑒𝑐 𝑠𝑒𝑐 = 𝐾𝑔 = 1000𝑔
𝑚 𝑠𝑒𝑐 𝑚 𝑠𝑒𝑐 100𝑐𝑚 𝑠𝑒𝑐
𝑔
= 10 ( ) 10𝑝𝑜𝑖𝑠𝑒
𝑐𝑚. 𝑠𝑒𝑐
32
 𝑔. 𝑐𝑚
𝐹 𝑑𝑥 𝑓𝑜𝑟𝑐𝑒 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑑𝑦𝑛𝑒𝑠 𝑐𝑚 𝑑𝑦𝑛𝑒 𝑠𝑒𝑐 ( 𝑠𝑒𝑐 2 ) 𝑠𝑒𝑐
𝑉𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 (𝜂) = ( ) = ( )= ( )= =
𝐴 𝑑𝑣 𝑎𝑟𝑒𝑎 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑐𝑚2 𝑐𝑚 𝑐𝑚2 𝑐𝑚2
𝑠𝑒𝑐
𝑔
= = 𝑝𝑜𝑖𝑠𝑒
𝑐𝑚. 𝑠𝑒𝑐
In SI unit of viscosity is N.sec.m-2 = Pa. sec = 10 (g.cm-1.sec-1) = 10poise
In cgs unit of viscosity is dyne.sec.cm-2 = g.cm-1.sec-1 = poise
The fundamental unit of viscosity measurement is poise (p) and more convenient unit for work are
centipoise (1cp = 10-2 p) and millipoise (1mp = 10-3p).
Liquid Viscosity (cp) at 20°C
Castor oil 1000
Olive oil 100
Ethyl alcohol 1.19
Water 1.0019
Chloroform 0.563

Kinematic viscosity:
Absolute viscosity divided by the density of the liquid at specific temperature is known as kinematic
viscosity.
𝜂
𝐾𝑖𝑛𝑒𝑚𝑎𝑡𝑖𝑐 𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 =
𝑑
Units of kinematic viscosity are stoke (s) and the centistoke (cs) and 1cs = 1mm2/sec.
Fluidity (ø): It is defined as reciprocal of viscosity (ø) = 1/η
Newtonian & Non-Newtonian liquids:
Newton’s law of flow or viscosity: It can be defined in the following three different ways:

(1) Shear stress (S.S) is directly proportional to shear rate (S.R).

S.S α S.R
S.S = η S.R
η = S.S/S.R (η = viscosity of liquid)
(2)Graphically there is a linear relationship in between shear stress and shear rate (below left figure).
(3)Viscosity of the liquid remains constant at any shear rate at constant temperature (below right
figure).
Shear rate (1/sec) 30 50 60 80
Shear stress (Pa) 20 30 40 50

33
 Viscosity (Pa.sec) 0.66 0.60 0.66 0.63

80 0.8

X X X X
60 0.6
X
shear stress viscosity
(Pa) 40 X (Pasec) 0.4
X

20 X 0.2

20 40 60 80 20 40 60 80
shear rate (1/sec) shear rate (1/sec)

Newtonian liquids:
The liquids which in their flow obey Newton’s law are called Newtonian liquids. These liquids have
linear relationship between shear stress and shear rate and their viscosity remain constant, no matter
the shear (shear rate) applied at particular temperature. Examples are water, mineral oil, gasoline
and alcohol.
Non-Newtonian liquids:
The liquids which in their flow do not obey Newton’s law are called Non-Newtonian liquids. They
have no linear relationship between shear stress and shear rate and viscosity of the liquids changes
with the shear (shear rate) applied at particular temperature.
The behavior of non-Newtonian liquids can be described in the following ways:
(1) Dilatant:
The viscosity of the liquid increases with increasing shear rate (shear thickening behavior) e.g.
corn-starch suspension.
(2) Pseudoplasic
The viscosity of the liquid decreases with increasing shear rate (shear thinning behavior) e.g.
blood.
(3) Rheopectic:
The viscosity of the liquid increases with increasing shear rate but it is time dependent e.g.
gypsum paste.
(4) Thixotropic:
The viscosity of the liquid decreases with increasing shear rate but it is time dependent e.g. glue.
Shear rate (1/sec) 30 50 65 70
Dilatant Shear stress (Pa) 5 10 - 20

34
 Viscosity (Pa.sec) 0.16 0.20 - 0.28
Pseudoplastic Shear stress (Pa) 40 60 75 -
Viscosity (Pa.sec) 1.33 1.20 1.15 -
1.33 X
1.20 Pseud X
80 oplas
1.15 tic(vi X
75 X sc osity
decre
1.10 sing)
c
60 st i X 1.05
o pla
d X 1.00
eu
shear stress Ps viscosity 0.30 X X X
(Pa) 40 X X (Pa.sec) Newtonian (viscosity constant)
n X
nia 0.25
e wto X g)
N si n
0.20 X rea
20 X tan
t X y inc
D ila X o sit
0.15 ( vis
X ant
10 la t
5 X 0.10 Di

20 40 60 65 80 20 40 60 65 80
shear rate (1/sec) shear rate (1/sec)

Determination of viscosity by different types of viscometers:

Capillary viscometer (Ostwald’s viscometer):
The viscosity of a liquid can be determined by using Poiseuille’s equation:
𝑝𝜋𝑟 4 𝑡
𝜂= ------------- (1)
8𝑣𝑙

Where volume of the liquid (v) flowing through a capillary of radius (r) and length (l) in time (t) at
applied pressure (d).
Experimentally p, r, l and v are difficult to measure, therefore it is difficult to measure absolute
viscosity of the liquid by the equation (1) but with some modification in the equation (1) the new
equation (2) can be used to determine Relative viscosity of Newtonian liquids with respect to water
by Ostwald’s viscometer.
Modification in equation (1) to equation (2).
In equation (1), Π, r, v and l are constant and only p and t are variables.
𝜋𝑟 4
= 𝑘, Putting this value of k in equation (1) we have:
8𝑣𝑙

𝜂 = 𝑝𝑡𝑘, since pressure (p) is directly proportional to density (d) of liquid, therefore it can be
replaced by density (d), we have:
𝜂 = 𝑑𝑡𝑘, For water 𝜂𝑤 = 𝑑𝑤 𝑡𝑤 𝑘 and for liquid 𝜂𝑙 = 𝑑𝑙 𝑡𝑙 𝑘, taking ratio of them we have:
𝜂𝑙 𝑑𝑙 𝑡𝑙
=
𝜂𝑤 𝑑𝑤 𝑡𝑤

35
 𝑑𝑙 𝑡𝑙
𝜂𝑙 = 𝑥 𝜂𝑤
𝑑𝑤 𝑡𝑤
𝑑𝑙 𝑡𝑙
𝜂𝑙 = ------------------ (2)
𝑡𝑤

𝑔
𝑑𝑙 = 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 ( ) , 𝑑𝑤 (𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟) = 1, 𝜂𝑤 = 𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 (1𝑐𝑝)
𝑐𝑚3
𝜂𝑙 = 𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑(𝑐𝑝), 𝑡𝑤 𝑎𝑛𝑑 𝑡𝑙 𝑎𝑟𝑒 𝑡𝑖𝑚𝑒 𝑜𝑓 𝑓𝑙𝑜𝑤 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑎𝑛𝑑 𝑙𝑖𝑞𝑢𝑖𝑑 (𝑠𝑒𝑐).

Construction and working of Ostwald’s viscometer:

It consists of U-shaped glass tube having two bulbs. The left hand arm is essentially a capillary tube
with two marks A and B above and below the bulb. The right hand arm is wide (pipette) and has a
bulb at the base.
● First of all density of liquid (dl) is determined by R.D bottle.
● A definite volume of liquid is introduced with the help of pipette into the right arm.
● The liquid is sucked through the left arm slightly above the mark A.
● The liquid is adjusted at mark A and time of flow (tl) (in seconds) is noted between mark A and B.
● Same procedure is repeated with water and time of flow of water (tw) (in seconds) is noted.
● By using values of dl, tl and tw in equation (2) the viscosity of liquid (ηl) is determined.

(liquid sucked) (liquid introduced)

A
A Fd

tl or tw Fb Fb
rte
wa

(ball)
ter

B
wa

(glass tube)
B

W
(water jacket)
Rolling ball viscometers (Falling sphere viscometer):
When a body (sphere) falls in a liquid due to gravity, it accelerates until the weight of the body
(sphere) is equivalent to drag force (Fd) and buoyancy (Fb) and the velocity of the body (sphere)

36
at this point is known as terminal velocity. We may determine viscosity of the liquid by
determining the terminal velocity of the body in that liquid.
Weight of the sphere (W) that acts vertically downward:
4
𝑊 = 3 𝜋𝑟 3 𝑑𝑏 𝑔

(Where r = radius of sphere, db = density of sphere and g = acceleration due to gravity)

Upward force of the liquid due to buoyancy (force exerted by a liquid that opposes the weight
of a partially or fully immersed subject) (Fb):
4
𝐹𝑏 = 3 𝜋𝑟 3 𝑑𝑙 𝑔 (Where dl = density of liquid)
Drag force (viscosity of liquid) acting upward (Fd):
𝐹𝑑 = 6𝜋𝜂𝑟𝑣 (Where η = viscosity, v = terminal velocity)
At terminal velocity (v) upward forces (Fb and Fd) are downward force (W) are balanced therefore:
𝐹𝑏 + 𝐹𝑑 = 𝑊
𝐹𝑑 = 𝑊 − 𝐹𝑏
4 4
6𝜋𝜂𝑟𝑣 = 𝜋𝑟 3 𝑑𝑏 𝑔 - 3 𝜋𝑟 3 𝑑𝑙 𝑔
3
4 3
6𝜋𝜂𝑟𝑣 = 𝜋𝑟 𝑔(𝑑𝑏 − 𝑑𝑙 )
3
4 4 2
𝜋𝑟 3 𝑔(𝑑𝑏 −𝑑𝑙 ) 𝑟 𝑔(𝑑𝑏 −𝑑𝑙 ) 2 1
𝜂= 3
= 3
= 9 𝑟 2 𝑔 (𝑑𝑏 − 𝑑𝑙 ) (𝑣)--------- (1)
6𝜋𝑟𝑣 6𝑣

Terminal velocity (v) can be calculated by measuring the timing (in seconds) of the fall of the
sphere and distance between the markings in glass tube (v = distance/time or v = l/t).
By placing value of v in equation (1) we have:
2 𝑡
𝜂 = 9 𝑟 2 𝑔 (𝑑𝑏 − 𝑑𝑙 ) (𝑙 )s
2 1
𝜂 = 9 𝑟 2 𝑔 ( 𝑙 ) (𝑑𝑏 − 𝑑𝑙 )𝑡
2 1
𝜂 = 𝐵 (𝑑𝑏 − 𝑑𝑙 )𝑡 Where B = 9 𝑟 2 𝑔 ( 𝑙 ) = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑 𝑏𝑦 𝑚𝑎𝑛𝑢𝑓𝑎𝑐𝑡𝑢𝑟𝑒𝑟.
(Where B = constant, db = density of sphere (g/cm3), dl = density of liquid (g/cm3) and t = time
interval in seconds for the sphere to fall between the two points).
Construction and working of Falling sphere viscometer:
It can determine dynamic viscosity of Newtonian liquids only. A glass or steel ball rolls down an
almost vertical glass tube containing the test liquid at a known constant temperature. The rate at
which a ball of a particular density (db) and radius (r) falls is an inverse function of the viscosity
of the sample.
The sample (of density dl) and ball are placed in the inner glass tube and allowed to reach
temperature equilibrium with the water in the surrounding constant-temperature jacket. The tube
and jacket are then inverted, which effectively places the ball at the top of the inner glass tube. The
time for the ball to fall between two marks (A and B) is accurately measured and repeated several
times. The viscosity of a Newtonian liquid can be determined by using above formula.

37
Q. A ball of density 8.0g/cm3 travels 1.0m distance in 10 seconds. If radius of ball is 0.5cm and
density of liquid is1.2g/cm3 calculate the dynamic viscosity of the liquid. (g = 9.8m/sce2)
η = dynamic viscosity of liquid
r = 0.5 cm db = 8.0g/cm3
g = 9.8m/sec = 980cm/sec dl = 1.2g/cm3
2 2

l = 1m = 100cm t = 10sec
2 1 2 1 𝑐𝑚 1 𝑔
𝜂 = 9 𝑟 2 𝑔 ( 𝑙 ) (𝑑𝑏 − 𝑑𝑙 )𝑡 = (0.52 )(980) ( ) (8.0 − 1.2)10 (𝑐𝑚2 ) (𝑠𝑒𝑐2) (𝑐𝑚) (𝑐𝑚3) (𝑠𝑒𝑐)
9 100
= 37 g.cm-1.sec-1 = 37 poise = 3.7 Pa.sec.

Rotational viscometers:
(1) Cup and Bob viscometer:
In cup-and-bob viscometers, sample is sheared in the space between the outer walls of a bob and
the inner wall of a cup into which a bob fits. In Couette type of viscometers, the cup is rotated and
bob remains stationary whereas in Searle type of viscometers (as show in figure), bob is rotated
and cup remains stationary. The torque resulting from the viscous drag of the system under
examination is proportional to the viscosity of the sample and is measured by a spring or sensor in
the device to the bob. It can measure dynamic viscosity of both Newtonian and non- Newtonian
liquids.
The liquid sample is placed in the space between the cup and the bob and allow to reach
temperature equilibrium. With the help of revolution counter and time, numbers of revolution per
minute (rpm) (N) are calculated.
𝑇
𝑠ℎ𝑒𝑎𝑟 𝑠𝑡𝑟𝑒𝑠𝑠 (𝑑𝑦𝑛𝑒𝑠/𝑐𝑚2 ) =
2𝜋𝑅𝑏2 ℎ

2𝛺𝑅𝑐2 𝑅𝑏2
𝑠ℎ𝑒𝑎𝑟 𝑟𝑎𝑡𝑒 (𝑠𝑒𝑐 −1 ) =
𝑅𝑏2 (𝑅𝑐2 − 𝑅𝑏2 )
𝑇
𝑠ℎ𝑒𝑎𝑟 𝑠𝑡𝑟𝑒𝑠𝑠 2𝜋𝑅2 𝑏ℎ 𝑇 𝑅𝑏2 (𝑅𝑐2 −𝑅𝑏2 ) 𝑇 𝑅𝑐2 −𝑅𝑏2 𝑇 1 1
𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 (𝜂) = 2𝛺𝑅2 2 = × = ( )= ( − 𝑅2)
𝑠ℎ𝑒𝑎𝑟 𝑟𝑎𝑡𝑒 𝑐 𝑅𝑏 2𝜋𝑅𝑏2 ℎ 2𝛺𝑅𝑐2 𝑅𝑏2 4𝛺𝜋ℎ 𝑅𝑐2 𝑅𝑏2 4𝛺𝜋ℎ 𝑅𝑏2 𝑐
𝑅𝑏 (𝑅𝑐 −𝑅2
2 2
𝑏)

T = torque acting on surface of bob (dyne.cm) (instrument reading).

2𝜋
Ω = angular velocity of bob (radians/sec) = 60 × 𝑁 (where N = numbers of rpm)
h = the depth to which bob is immersed in the liquid (cm).
Rb = radius of bob (cm).
Rc = radius of cup (cm).
η = viscosity of liquid (dynes.sec/cm2 or poise).

By using above equation viscosity of liquid in dynes.sec /cm2 or poise can be determined.

38
(2) Cone-plate viscometer:
A cone and plate viscometer consists of a flat plate and an inverted cone, whose apex just
contacts the plate. The liquid whose viscosity is to be determined is placed in the gap between
cone (of radius R) and plate. The cone is rotated at a known angular velocity (Ω), and the
torque (T) required to turn the cone is measured. An expression which relates viscosity of the
liquid in terms of Ω, T and the angle (Ψₒ or θ) between the cone and the plate (for commercial
instruments Ψₒ = θ =1°) can be written as:
𝑇
𝑠ℎ𝑒𝑎𝑟 𝑠𝑡𝑟𝑒𝑠𝑠(𝑑𝑦𝑛𝑒𝑠/𝑐𝑚2 ) =
2 3
3 𝜋𝑅
𝛺
𝑠ℎ𝑒𝑎𝑟 𝑟𝑎𝑡𝑒 (𝑠𝑒𝑐 −1 ) =
𝑠𝑖𝑛𝜃
𝑇
2 3
𝑠ℎ𝑒𝑎𝑟 𝑠𝑡𝑟𝑒𝑠𝑠 3
𝜋𝑅 3 𝑇(𝑠𝑖𝑛𝜃) 3 𝑇𝜓𝜊
𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 (𝑝𝑜𝑖𝑠𝑒) = = 𝛺 =2 𝑜𝑟
𝑠ℎ𝑒𝑎𝑟 𝑟𝑎𝑡𝑒 𝜋𝛺𝑅 3 2 𝜋𝛺𝑅 3
𝑠𝑖𝑛𝜃
3 𝑇𝜓𝜊 3 𝑇(𝑠𝑖𝑛𝜃)
𝜂 = 2 𝜋𝛺𝑅3 𝑜𝑟 --------- (1)
2 𝜋𝛺𝑅 3

3 𝜓𝜊 3 (𝑠𝑖𝑛𝜃)
𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡(𝐶) = 2 𝜋𝑅3 𝑜𝑟 By placing value of constant (C) in equation (1) we have:
2 𝜋𝑅 3

𝑇
𝜂 = 𝐶𝛺

Where η = viscosity of liquid (dynes. sec/cm2 or poise), T = measured torque (dyne.cm) and
Ω = applied angular velocity (radian /sec), C = constant supplied by manufacturer.

The advantage of cone-plate viscometer over cup-bob viscometer besides measuring dynamic
viscosity of both Newtonian and non- Newtonian liquids is that in cone-plate viscometer the
rate of shear is constant throughout the entire sample therefore it can be used also for the
materials showing plastic flow, and only 0.1-0.2 ml sample is required.

39
(3) High-Pressure-High-temperature viscometer (HPHT-viscometer):
With this rotational viscometer the absolute/dynamic viscosity (5-100,000 cP) of shear rate
dependent (Newtonian) fluids as well as shear rate independent (non-Newtonian) fluids can be
measured under pressure of 21750 psi and temperature up to 200°C.

Vibrational viscometers:
It can measure viscosity of Newtonian liquids and commonly used in industries to measure
viscosity of liquid in tank or pipe during manufacturing processing. Vibrational viscometers use a
powered vibrating rod or plate to measure the viscosity. Different liquids are more or less resistant
to vibrations depending on how viscous they are. Therefore, by measuring the dampening of the
vibration, or by measuring how quickly the vibration of the viscometer degrades, viscosity can be
determined.
A vibrational viscometer consists of a plate (of mass m and area A) is attached to the end of a
spring and allowed to oscillate (vibrate) in a liquid. If τn is the natural period of undamped
oscillation, that is, with the system oscillation in air, and τd is the damped period with the plate
immersed in the liquid. By observing τn and τd, viscosity of the liquid can be determined.
1
2 2 )2
4𝜋𝑚(𝜏𝑑 −𝜏𝑎
Shear stress (dynes.cm) = damping force on the plate = Fd = ×𝑣
𝜏𝑑 𝜏𝑛
Shear rate (cm3/sec) = 2Av
1
4𝜋𝑚(𝜏2 −𝜏
𝑑 𝑎
2 )2
1
𝑠ℎ𝑒𝑎𝑟 𝑠𝑡𝑟𝑒𝑠𝑠 ×𝑣 2
2𝜋𝑚(𝜏𝑑 2 )2
−𝜏𝑎 𝑑𝑦𝑛𝑒𝑠.𝑐𝑚 𝑑𝑦𝑛𝑒𝑠.𝑠𝑒𝑐
𝜏𝑑 𝜏𝑛
Viscosity (η) = = = = 𝑐𝑚3
= = poise
𝑠ℎ𝑒𝑎𝑟 𝑟𝑎𝑡𝑒 2𝐴𝑣 𝐴𝜏𝑑 𝜏𝑛 𝑐𝑚2
𝑠𝑒𝑐
1
2 2 )2
2𝜋𝑚(𝜏𝑑 −𝜏𝑎
Viscosity of liquid (η) (poise) = 𝐴𝜏𝑑 𝜏𝑛

Factors affecting viscosity of liquids:

Inter molecular attraction:
Liquids with inter molecular attraction (hydrogen bonding or H.B) resist more to flow and have
greater viscosities as compare to liquids which have no inter molecular attractions. Therefore
ethylene glycol, propanol, ethanol, water and methanol which have inter molecular attraction
(H.B) have greater viscosity than acetone and dimethyl ether which do not have inter molecular
attraction (H.B).

40
 Liquid Structure Molecular interaction Viscosity(cP) at 25°C
Ethyleneglycol HOCH2-CH2-OH 6 HB 61.1
1-Propanol CH3-CH2-CH2-OH 3 HB & LDF ˃˃ HB 1.96
Ethanol CH3-CH2-OH 3HB & LDF ˃ HB 1.07
Water H-O-H 4 HB 0.91
Methanol CH3-OH 3 HB & LDF < HB 0.54
Acetone CH3-CO-CH3 Dipole-dipole (more) & 0.31
LDF
Diethyl ether C2H5-O-C2H5 Dipole-dipole (less) & 0.22
LDF

Among the above H.B containing liquids, ethylene-glycol has maximum viscosity, because it has
two OH groups and can form 6 hydrogen bonds (it can donate 2H and accept 4H). This enhanced
clinginess is responsible for its higher viscosity. Water can in principle form four hydrogen bonds
(it can donate 2H and accept 2H), therefore its viscosity is less than ethylene-glycol. Methanol has
one OH and can form 3 hydrogen bonds (it can donate1H and accept 2H), so it has a little less
hydrogen bonding than water, and CH3 (methyl) has LDF < HB. Its viscosity is lower than water.
Like methanol, 1-propanol and ethanol have one OH group but they have more viscosity than
water. 1-propanol and ethanol have 3HB as well as London dispersion forces in their hydrocarbon
chain which resist to flow and they have greater viscosity than water. London dispersion forces
(LDF) arise due to closeness of the molecules and unsymmetrical distribution of electrons to create
temporally dipole-dipole interaction and it increases with increasing hydrocarbon chain, therefore
1-propanol is more viscous than ethanol.
Acetone and Diethyl ether both have no hydrogen bonding at all, although they have dipole-dipole
interaction & LDF which hold the molecules together. The dipole-dipole interaction of acetone is
relatively more than ether therefore it has greater viscosity than ether.

41
 H H

:
O:

: :
R :O R O

H H
H

:
:
O:

:
H H O:

:
H O: H O CH2CH3 O H :O H

:
O: H

:
H
R R H
H
H H

:O
R O: :O R

:
H

:
:
One molecule of ethylene-glycol is bonded with 6H.B with other molecules (R = HO-CH2CH2-) oneH2O is bonded with 4HB with other molecules

H H H H H H
: :

: :
: :
O O O

O −

H H H C2H5 − C2H5
+

: :
O

:
:

:
O: H3C CH3
O: H O: O: H O: H O:
O −
:

H3C H3C-H2C H3C-H2C-H2C

+ +
H H H

H H H + H 3C O CH3

H3C CH3
:O :O :O
:
:

H H H
Acetone has more dipole-dipole +LDF &
(CH3OH has 3HB+ LDF  HB) (C2H5-OH has 3HB + LDF ) (C3H7-OH has 3HB + LDF  )
ether has less dipol-dipole + LDF
Molecular mass the molecules:
When other factors are common molecular mass of the molecule is also a factor affects viscosity.
By increasing molecular mass force of friction increases and resists to flow, therefore with
increasing molecular mass viscosity increases.
Hydrocarbon Formula Molecular mass Viscosity (cP) at 20°C
n-Pentane C5H12 72 0.240
n-Hexane C6H14 86 0.326
n-Heptane C7H16 100 0.409
n-Octane C8H18 114 0.542
n-Nonane C9H20 128 0.711

Shape of molecules:
Spherical shape molecule (Neo-pentyl alcohol) results decrease in surface area and weaker in
dispersion forces and cylindrical shape molecule (n-pentanol) results increase in surface area and
stronger in dispersion forces. Therefore Spherical molecules have less viscosity than cylindrical
molecules.
Molecule Structure Shape Viscosity (cP) at 20°C
Neo-pentyl alcohol (CH3)3C-CH2-OH spherical 2.5

42
 n-Pentyl alcohol CH3(CH2)3CH2-OH cylindrical 4.5

Temperature:
Viscosity depends strongly on temperature. In liquid it usually decreases with increasing
temperature, whereas in gases it increases with increasing temperature.

Viscosity in gases arises from molecules traversing layers of flow and transferring momentum
between layers. This transfer of momentum is considered as a frictional force between layers of
flow. Since the momentum transfer is caused by free motion of gas molecules between collisions,
increasing thermal agitation of the molecules results in a large viscosity. Hence, gaseous viscosity
increases with temperature.

In liquids, viscous forces are caused by molecules exerting attractive forces on each other across
layers of flow. Increasing temperature results in a decrease in viscosity because a large temperature
means molecules have greater thermal energy and more easily able to overcome the attractive
forces binding them together. Hence, in liquids, viscosity decreases and fluidity (reciprocal of
viscosity) increases with temperature.
The temperature dependence of viscosity of liquids usually follows the Arrhenius equation:
𝐸𝑎
𝜂 = 𝐴℮𝑅𝑇
Use the following model to predict viscosity (cP) of water at 30°C.
T (°C) 0 20 40 100
η (cP) 1.54 1.07 0.75 0.25
By using the known viscosities of water at various temperatures, and developing functions that
model this relationship in program such as Microsoft Excel or on graphics calculator, the
approximate viscosity (cP) of water at any temperature can be found by substituting value of
temperature into the relevant formula.
𝜂 = 1.5396 ℮−0.018 ×𝑇(℃)
𝜂 = 1.5396 ℮−0.018 ×30
𝜂 = 1.5396 ℮−0.54
𝜂 = 0.8972 𝑐𝑃

Viscosity of water at different temperatures

2 1.54
Viscosity(Pc)

1.5 1.07
1 0.75

0.5 0.25

0
0 20 40 100
T (°C)

43
The modified form of Arrhenius equation is as follow:
𝐸𝑎 1
𝑙𝑛𝜂 = 𝑙𝑛𝐴 +
𝑅 𝑇
The equation is commonly used to calculate viscosity of a liquid at any temperature if in a model
viscosities of a liquid at different temperatures are known. From a linear regression of lnη ( in cP
or Pa.sec) verses 1/T( in 1/K) the values of lnA and Ea/R can be calculated easily because intercept
at y-axis = lnA and slope = Ea/R. With the help of Microsoft Excel given data is transformed to
calculate lnA and Ea/R and then viscosity of a liquid can be determined at any temperature.
In the given model calculate viscosity (cP) of liquid (olive oil) at 28°C.
T (°C) 20 30 40 50 60 70 80
η (cP) 81.9 53.0 36.3 25.9 19.3 14.9 11.8

Data is transformed into Microsoft Excel and viscosity of olive oil at 28°C was found 57.43cP.
lnη (cP) (y- slope = intercept at y-axis = lnη= lnA+ (Ea/R η(cP)
η(cP) axis) T(°C) T(K) 1/T (1/K) (x-axis) Ea/R lnA )(1/T) calculated
3334.0548
81.9 4.405498991 20 293 0.003412969 96 -7.026077599 4.352949348 77.7
3334.0548
53 3.970291914 30 303 0.00330033 96 -7.02608 3.977401505 53.3
3334.0548
36.3 3.591817741 40 313 0.003194888 96 -7.02608 3.625852575 37.5
3334.0548
25.9 3.254242969 50 323 0.003095975 96 -7.02608 3.296071381 27
3334.0548
19.3 2.960105096 60 333 0.003003003 96 -7.02608 2.986096865 19.8
3334.0548
14.9 2.701361213 70 343 0.002915452 96 -7.02608 2.694196665 14
3334.0548
11.8 2.468099531 80 353 0.002832861 96 -7.02608 2.41883472 11.23
3334.0548
28 301 0.003322259 96 -7.02608 4.050514339 57.427
It has also been found that there is 1.5% -2% decrease in viscosity occurs for every increase in one
degree of temperature of the liquid.

Applications of viscosity in pharmacy:

(1) The viscosity of cough syrup should be preferably as high as possible but it should still be
drinkable in order to smoothly flow past the digestive tract. To evaluate the flow behavior of
cough syrup two parameters are obtained (i) Consistency index K: This parameter represents
the product viscosity at one reciprocal second, 94.93 Pa.sec at rest (1s-1). (ii) Flow index n:
This parameter determines the flow behavior of the cough syrup. When n <1 the product shows
shear thinning behavior (means that the apparent viscosity decreases as the shear rate
increases). When n is close to 0, the stronger the shear-thinning behavior of the product. When
n ˃ 1 the product shows shear thickening behavior (means that the apparent viscosity increases
as the shear rate increases). When n =1 the product shows Newtonian flow behavior (that
means the viscosity is independent of the shear rate).

(2) The viscosity of ointments and lotions, for example has an important impact on several stages
in production: It must be possible to pump them, pack them and squeeze them out of the

44
 packing easily, and also to apply them on the target body area. Ointments have to show shear
thinning flow behavior, because the viscosity has to decrease when a force is applied, e.g.
during squeezing it out of a tube or applying it to the skin. In order to prevent ointments from
flowing out of the tube when no force is applied, the yield point (the force or stress required to
initiate flow) has to be analyzed.
(3) The most common viscosity desired in an ophthalmic solution is between 25 -50 cps. Viscosity
enhancers are used in ophthalmic solutions to increase their viscosity. This enable the
formulation to retain in the eye longer and gives more time for the drug to exert its therapeutic
activity or undergo absorption. For example if methylcellulose of grade number 25 cps is used,
a 1% solution will create viscosity 25cps, similarly 0.25% solution of methylcellulose (of grade
number 100cps) provides viscosity of 25cps.

(4) Throat paints are liquid preparations applied in mucous surfaces. They may be aqueous or
alcoholic solutions more viscous due to high content of glycerin and prolong the action of
medicaments. They used in mouth or throat infection and may contain antiseptic or analgesic
medicaments.

(5) In suspensions as the viscosity of the dispersion medium increases, the terminal velocity
decreases thus the dispersed phase settles at a lower rate and remain dispersed for longer time
and give high stability to the suspension. Therefore, the viscosity of the suspension should be
maintained within optimum range to give stable and easily pourable suspension.

(6) In oil-based cosmetic products, the viscosity is an essential parameter to be determined. Since
many pure oils show a freezing point close to ambient conditions, their viscosity has a crucial
influence on the handling and processing of the ingredients.

(7) Injectable suspensions provide an insoluble drug in a form suitable for intramuscular or
subcutaneous administration. The concentration of solid particles in these preparations range
0.5%-30%. These preparations have low viscosity because viscosity affects ease of injection.

(8) In IV infusions, increase in viscosity of the solution decreases flow through catheter. Therefore
viscosity have to maintain in IV infusions. For example viscosity of Lactated Ringers (1.0 cP),
Hetastarch (4.0 cP) and 5% albumin (40.0 cP).

(9) Viscosity of blood and urine may help in diagnosis of a number of diseases. For example in
polycythemia the blood viscosity is approximately doubled and in dehydration the viscosity of
urine increases than normal (0.00802 Pa.sec).

(10) It can be used to check the purity of a substance. For example % purity of honey sample can
be determined by using Falling sphere viscometer.

45
 DENSITY / SPECIFIC GRAVITY

Density (Lat. Densus, thick): The density, of a substance is its mass per volume. The symbol
most commonly used for density is 𝜌 (Greek letter rho), although the Latin letter D.
𝑚
𝜌=
𝑉
Where 𝜌 = density, m = mass and V = volume.
Units of density: g/cm3 (cgs) or g/ml and Kg/m3 (SI) or Kg/dm3 or Kg/L. Other units are lb /gal
and lb / ft3.

Absolute density: It is the density of a substance in its “closest packed form” is known as absolute
density of that substance.

Apparent density/Volumetric density/Mass density: It is the density of a substance with respect

to bulk volume (including voids) of the substance. It is always less than absolute density. For
example apparent density of water at 25°C is 0.99618 g/cm3 or 1 g/cm3 or 8.34 lb /gal or
62.4 lb /ft3.

Relative density (R.D)/Specific gravity (S.G): It is the ratio of density of the substance to that of
a standard substance (water). It has no unit because it is a ratio of densities of two substances.
𝑔
𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝐴 𝑐𝑚3 𝑔 𝑐𝑚3
𝑅. 𝐷 𝑜𝑟 𝑆. 𝐺 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝐴 = = 𝑔 = × = 𝑛𝑜 𝑢𝑛𝑖𝑡
𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑐𝑚3 𝑔
𝑐𝑚 3

𝑔𝑟𝑎𝑚𝑠 𝑜𝑓 𝐻𝐶𝑙 (𝑐𝑜𝑛𝑐. ) 119𝑔

5𝑐𝑚 3 3
𝑅. 𝐷 𝑜𝑟 𝑆. 𝐺 𝑜𝑓 𝐻𝐶𝑙 = = 100𝑐𝑚
𝑔𝑟𝑎𝑚𝑠 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 100𝑔
𝑐𝑚3
5 100𝑐𝑚3
119𝑔 100𝑐𝑚3
= 100𝑐𝑚3 × = 1.19
100𝑔

The R.D or S.G of concentrated HCl is 1.19 or 1.19.times heavier than equal volume of water.
Molar density: The molar density, of a substance is its number of moles per volume and its unit
is mole/m3 or mole/dm3.
Determination of density of liquid:
Determination of density (or apparent density) of liquid by Pycnometer:
A pycnometer is a glass flask with a close-fitting ground glass stopper with a capillary hole through
it. This fine hole releases a spare liquid after closing a top-filled pycnometer and allows for
obtaining a given volume of measured and/or working liquid with a high accuracy.

46
Procedure:
● Weigh empty cleaned and dried Pycnometer (of volume V) on calibrated balance (m1).
● Fill the pycnometer with liquid and place the stopper in order to release spare liquid and weigh
the pycnometer again (m2).
Observations:
Mass of liquid = m2 (g) - m1 (g) = m3 (g)
Volume of liquid = V (cm3)

Calculation:
𝑚3 (𝑔)
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 = = 𝑧 𝑔/𝑐𝑚3
𝑉(𝑐𝑚3 )
Q. When dry and empty, a certain pycnometer had a mass of 27.314g. When filled with distilled
water at 25°C, it weighted 36.842g. When filled chloroform, the apparatus weighted 41.428g.
At 25°C, the density of water is 0.99704 g/cm3.
(a) What is the volume of the pycnometer? (b) What is the density of chloroform?
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 (𝑔)
(a) 𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 = 𝑉(𝑐𝑚3 )

Mass of water = 36.842g – 27.314g = 9.528g

Density of water = 0.99704 g/cm3
Volume of pycnometer = V (cm3) =?
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 (𝑔)
𝑉 (𝑐𝑚3 ) = 𝑔
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 ( )
𝑐𝑚3

9.528 (𝑔) 𝑐𝑚3

Volume of pycnometer = 𝑔 = 9.556 (𝑔 × ) = 9.556𝑐𝑚3
0.99704 ( ) 𝑔
𝑐𝑚3

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑐ℎ𝑙𝑜𝑟𝑜𝑓𝑜𝑟𝑚(𝑔)
(b) 𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑐ℎ𝑙𝑜𝑟𝑜𝑓𝑜𝑟𝑚 =
𝑉(𝑐𝑚3 )

Mass of chloroform = 41.428g – 27.314g = 14.114g

V (cm3) = 9.556 cm3
14.114(𝑔)
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑐ℎ𝑙𝑜𝑟𝑜𝑓𝑜𝑟𝑚 = 9.556(𝑐𝑚3 ) = 1.477 𝑔/𝑐𝑚3

Determination of relative density (R.D) / specific gravity (S.G) by R.D. bottle method:
R.D is specifically used to determine relative density because it is specially designed to hold
accurate volume of the substance. The stopper of the bottle contains capillary, and when we place
stopper gently on the completely filled bottle, the liquid does not split outside but raises into the
capillary tube and the bottle holds the accurate volume ( as written on the R.D bottle) of the liquid.
Procedure:

47
● Weigh a cleaned and dried empty R.D bottle with stopper on a calibrated balance (m1).
● Fill the R.D bottle completely with liquid and place the stopper gently (liquid should not split
out) and weigh the bottle again (m2).
● Remove liquid from the bottle make it clean and dried and fill water into the bottle and repeat
the same procedure to get m3.
Observations:
Mass of liquid = m2 (g) – m1 (g) = m4 (g)
Mass of water = m3 (g) – m1 (g) = m5 (g)

Calculation:
Since volume of liquid and water are same therefore:
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 𝑚4 (𝑔)
𝑅. 𝐷 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 = = =𝑍
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑚5 (𝑔)
Q. Propylene glycol is used as a food additive and in cosmetics. Its density is 8.65 lb /gal. The
density of water is 8.34 lb /gal. Calculate specific gravity of propylene glycol.
We know that:
𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝐴 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑝𝑟𝑜𝑝𝑦𝑙𝑒𝑛𝑒 𝑔𝑙𝑦𝑐𝑜𝑙 8.65 (𝑙𝑏/𝑔𝑎𝑙)
𝑆. 𝐺 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝐴 = = = =
𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 8.34(𝑙𝑏/𝑔𝑎𝑙)
8.65 𝑙𝑏 𝑔𝑎𝑙
= ( × ) = 1.037
8.34 𝑔𝑎𝑙 𝑙𝑏
Q. Trichloroethylene is a common dry-cleaning solvent. Its specific gravity is 1.47 measured at
20°C. What is its density in g /cm3
𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑇𝑟𝑖𝑐ℎ𝑙𝑜𝑟𝑜𝑒𝑡ℎ𝑦𝑙𝑒𝑛𝑒
𝑆. 𝐺 𝑜𝑓 𝑇𝑟𝑖𝑐ℎ𝑙𝑜𝑟𝑜𝑒𝑡ℎ𝑦𝑙𝑒𝑛𝑒 = 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟

𝑔 𝑔
𝐷𝑒𝑛𝑠𝑖𝑡𝑦𝑜𝑓 𝑇𝑟𝑖𝑐ℎ𝑙𝑜𝑟𝑜𝑒𝑡ℎ𝑦𝑙𝑒𝑛𝑒 ( ) = 𝑆. 𝐺 𝑜𝑓 𝑇𝑟𝑖𝑐ℎ𝑙𝑜𝑟𝑜𝑒𝑡ℎ𝑦𝑙𝑒𝑛𝑒 × 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 ( 3 )
𝑐𝑚3 𝑐𝑚
𝑔 𝑔
= 1.47 × 1 ( ) = 1.47
𝑐𝑚3 𝑐𝑚3

Hydrometer Pycnometer / R.D bottle with stopper

48
Determination of specific gravity (or R.D) by Hydrometer:
Construction & working principle:
It is usually made of glass and consists of a small diameter cylindrical stem and a large diameter
float section weighted with mercury or lead shot (sealed with wax) to make it float upright. The
stem contains rolled paper marked with the scale being used. Hydrometer is based on the
Archimedes principle that a solid suspended in a fluid will be buoyed up by a force equal to the
weight of fluid displaced. The large diameter float section is used to provide the displacement
volume needed for the proper buoyancy of the hydrometer. The lighter the liquid (less specific
gravity), the deeper the body sink because a greater amount of liquid is required to equalize the
body’s weight.
Procedure & reading:
● The liquid to be tested is taken in a measuring cylinder.
● The hydrometer is gently lowered into the liquid until it floats freely.
● The point at which the surface of the liquid touches the stem of the hydrometer is noted.
● The stem contains rolled paper marked with scale inside the stem, so that specific gravity can be
read directly.
Determination of true and bulk density of powder:
An amount of powder m (g) is taken into measuring cylinder. Volume (cm3) of the m (g) of powder
without tapping the cylinder (bulk volume = VB) and with tapping the cylinder (true volume = VT)
is noted from the measuring cylinder.

𝑚
𝑡𝑟𝑢𝑒 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑝𝑜𝑤𝑑𝑒𝑟 = = 𝑧 𝑔/𝑐𝑚3
𝑉𝑇
𝑚
𝑏𝑢𝑙𝑘 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑝𝑜𝑤𝑑𝑒𝑟 = = 𝑦 𝑔/𝑐𝑚3
𝑉𝐵

Determination of density of solid:

A graduated cylinder containing a known volume of liquid (initial volume = Vi) in which solid is
insoluble is tared on the balance. The solid is added into the cylinder, and total mass is weighted
again to determine the mass of solid (ms). Addition of the solid causes an upward displacement of
the liquid resulting in a new volume reading (final volume = Vf).
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑖𝑑 = 𝑉𝑠 = 𝑉𝑓 − 𝑉𝑖 s
𝑚𝑠
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑜𝑙𝑖𝑑 = = 𝑧 𝑔/𝑐𝑚3
𝑉𝑠
Factors affecting density of liquids:
Intermolecular attraction:
Greater the molecular attraction more the density of liquid. For example water has greater
intermolecular attraction (double hydrogen bonding) than ethanol (single hydrogen bonding)
therefore density of water is 0.997g/cm3 and ethanol is 0.789 g/cm3 at 25°C.
Molecular weight of liquid:

49
In general greater the molecular weight more the density of substance. For example density of
ethanol (MW = 46) is 0.789g/cm3 and of propanol (MW = 60) is 0.804g/cm3 at 25°C. In some
cases substance of lower molecular weight has greater density than substance with higher
molecular weight, due to greater intermolecular attraction or atoms being tightly packed in the
molecules for example water (MW = 18) and ethanol (MW = 46).
Temperature:
In general with increasing temperature the intermolecular forces decreases therefore density of the
liquid also decreases. For example density of water at different temperature is as follow:
Temperature (°C) 10 21 50 60 100
Density (g/cm3) 0.99975 0.99802 0.98870 0.98338 0.95865
With decreasing temperature density should increase but water has abnormal behavior and its
density increases from 10°C - 4°C due to decreasing in hydrogen bonding and closeness of the
molecules and becomes maximum at 4°C. After 4°C it decreases due to expansion of water into
ice.
Temperature (°C) 10 4.4 4 0 -10 -20
Density (g/cm3) 0.99975 0.99999 1.00000 0.99987 0.99817 0.99355
Density of specific gravity are temperature dependent therefore it is always mentioned with respect
to temperature. For example density of water at 50°C is 0.98870 g/cm3.
Applications of density or specific gravity in pharmacy:
(1) Concentration determination of binary solutions: The density of a solution depends on the
concentration of the dissolver substance (solute). If density or specific gravity of the solution
is known, the concentration of the solution can be determined. For example specific gravity of
normal saline is 1.0046 at 22°C.
𝑔
𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 ( 3 )
𝑆𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑔𝑟𝑎𝑣𝑖𝑡𝑦 𝑜𝑓 𝑛𝑜𝑟𝑚𝑎𝑙 𝑠𝑎𝑙𝑖𝑛𝑒 = 𝑐𝑚
𝑔
𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓𝑤𝑎𝑡𝑒𝑟 ( 3 )
𝑐𝑚
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑛𝑜𝑟𝑚𝑎𝑙 𝑠𝑎𝑙𝑖𝑛𝑒 = 𝑆. 𝐺 𝑜𝑓 𝑛𝑜𝑟𝑚𝑎𝑙 𝑠𝑎𝑙𝑖𝑛𝑒 × 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟
𝑔 𝑔
= 1.0046 × 1.0 (𝑐𝑚3 ) = 1.0046 𝑐𝑚3
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 100 𝑐𝑚3 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 + 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑁𝑎𝐶𝑙/100𝑐𝑚3
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑎𝑙𝑖𝑛𝑒 =
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
100𝑔 + 0.9𝑔
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑎𝑙𝑖𝑛𝑒 =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 + 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑁𝑎𝐶𝑙
100.9𝑔
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑎𝑙𝑖𝑛𝑒 =
𝑐𝑚3
100𝑐𝑚3 + 0.9𝑔 × 2.16 ( 𝑔 )

100.9𝑔
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑎𝑙𝑖𝑛𝑒 = = 1.0048𝑔/𝑐𝑚3
100.417𝑐𝑚3
50
 0.9𝑔
𝐺𝑟𝑎𝑚𝑠 𝑜𝑓 𝑁𝑎𝐶𝑙/100𝑐𝑚3 = 𝑔 × 𝑂𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
1.0046 ( 3 )
𝑐𝑚
(2) Filling volume control: Most of the products are prepared by weight and are dispensed by
volume. A well-proven procedure is to measure the weight of a liquid product with a balance,
followed by calculating the filling volume by using the density of the sample. For example a
batch of cough syrup has 95kg weight and its density is 0.95g/ml. How many bottles of cough
syrup of 250ml each can be filled?
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑦𝑟𝑢𝑝(𝑔) 95000𝑔
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑜𝑢𝑔ℎ 𝑠𝑦𝑟𝑢𝑝 (𝑚𝑙) = 𝑔 = 𝑔
𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑦𝑟𝑢𝑝 ( ) 0.95 ( )
𝑚𝑙 𝑚𝑙
= 100000𝑚𝑙
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑜𝑢𝑔ℎ 𝑠𝑦𝑟𝑢𝑝(𝑚𝑙) 100000𝑚𝑙
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑏𝑜𝑡𝑡𝑙𝑒𝑠 𝑚𝑎𝑦 𝑓𝑖𝑙𝑙𝑒𝑑 = = = 400
250𝑚𝑙/𝑏𝑜𝑡𝑡𝑙𝑒 250𝑚
(3) To determine %w/w of mineral acids:
Mineral acids such as hydrochloric acid, sulfuric acid are prepared by dissolving HCl gas, and
SO3 gas in water respectively and strength of acid is mentioned on label in %w/w. For example
5L bottle of concentrated H2SO4 has a label of 95%w/w and specific gravity 1.84. Using acid
time to time the fumes escaped from the bottle and the strength of acid may reduce. To check
what is the strength of acid (%w/w) is? If it is going to use several time for the last 2 months.
It can be checked simply by determining specific gravity (S.G) of the acid sample (using for
the last 2 months) by using the following table:
% w/w of H2SO4 S.G (at 16°C) % w/w of H2SO4 S.G (at 16°C)
81.30 1.74700 94.00 1.83810
83.34 1.76830 95.00 1.84070
85.66 1.79010 96.00 1.84270
86.33 1.79570 97.00 1.84370
87.04 1.80120 98.00 1.84370
87.81 1.80680 99.00 1.84240
88.65 1.81250 100.00 1.83910
89.59 1.81820
90.60 1.82390
91.80 1.82970
93.19 1.83540
93.77 1.83730
If the specific gravity of acid sample (using for the last 2 months) is found 1.83. The strength of
acid sample is 91.80 %w/w.

(4) To determine %w/v, molarity and normality of mineral acids:

51
 Labels of mineral acids contain %w/w and density (or S.G). For example H2SO4, 37%w/w and
density 1.28g/cm3.
Specific gravity is given to convert %w/w into %w/v.
𝑤 𝑤
% ( ) = % ( ) × 𝑆. 𝐺
𝑣 𝑤
37𝑔𝐻𝐶𝑙 1.28𝑔 𝐻𝐶𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
= 100𝑔 𝐻𝐶𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 × 1𝑐𝑚3 𝑜𝑓 𝐻𝐶𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 47.36𝑔𝐻𝐶𝑙/100𝑐𝑚3
= 47.36% 𝑤/𝑣
Molarity and normality have w/v relationship and can be calculated by % w/v.
𝑤
%( )×10 47.36 ×10
𝑣
𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 = 𝑔𝑟𝑎𝑚 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = = 4.83𝑀
98

𝑤
%( )×10 47.36 ×10
𝑣
𝑁𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦 = 𝑔𝑟𝑎𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 = = 9.66𝑁
𝑚𝑎𝑠𝑠 49

(5) Flow properties and compressibility of powder:

True density of powder is used to predict both flow properties and compressibility of powder
material. Compressibility is concerned with the durable solid form and dissolution
characteristics whereas flow property affects capsule filling performance.

(6) Density and dispensing pharmacy:

Density of the substance is commonly used in dispensing pharmacy to calculate the desire
strength. For example formula for 100g zinc oxide ointment is as follow:
Liquid paraffin (density = 0.88g/ml) 20ml
Zinc oxide 15g
Yellow soft paraffin to: 100g (ointment)
Calculate amount (in grams) of yellow soft paraffin is needed to dispense 25g of the ointment.
Liquid paraffin is in volume (ml) and other substances are in grams. We have to convert volume
(ml) of liquid paraffin into grams first for proper calculation.

Liquid paraffin 20ml x 0.88g/ml = 17.6g 17.6g x 1/4 4.4g

(density = 0.88g/ml)

Zinc oxide 15g 15g x 1/4 3.75g

Yellow soft paraffin to: 100g (ointment) 100g x 1/4 25g (ointment) – (4.4g + 3.75g) = 16.85g

(7) Diagnosis of diseases:

Adults generally have a specific gravity of urine in the range of 1.010-1.030. Increase in specific
gravity (hypersthenuria: increased concentration of solutes in urine) may be associated by
dehydration, diarrhea, emesis, excessive sweating, urinary tract/bladder infection, glucosuria,
renal artery stenosis, hepatorenal syndrome and decrease blood flow to the kidney. Decrease in
specific gravity (hyporsthenuria: decreased concentration of solutes in urine) may be associated

52
 with renal failure, pyelonephritis, diabetes insipidus, acute tubular necrosis and intestinal
nephritis.

(8) Density separation of minerals:

Density separation is based on the fact that different minerals have different densities. Typical
mineral densities range from about 2.2g/cm3 to as much as 8.0g/cm3 but are generally between
2.5g/cm3-3.5g/cm3 for silicate minerals. The mixture of minerals with different densities is
placed in a separating funnel with a liquid of intermediate density (most commonly liquids used
for separation are bromoform, density = 2.48g/cm3 and di-iodomethane, density = 3.31g/cm3),
the grains with densities less than that of the liquid float and grains with densities greater than
liquid sink. Different layers are collected separately, washed and examined optically for purity.

(9) To identify and to check purity of the substance:

Density or specific gravity is characteristic physical property. Two pure substances cannot have
same density or specific gravity, therefore it can be used to identify the substance and to check
the purity of the substance.

(10) To determine the osmotic pressure of the solution:

The solution is taken into the tube. The wider end of the funnel-shaped tube is covered with a
semipermeable membrane. The tube is placed into the container of the solvent. In the tube the
height of the solution begin to increase until a maximum height is reached. Difference of two
heights is h and d is the density of solution and g is the gravitational acceleration.

𝑂𝑠𝑚𝑜𝑡𝑖𝑐 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝜋) = 𝑑𝑔ℎ

h solution

membrane

solvent

before osmosis osmosis completed

53