VOLUMETRIC PROPERTIES

BY: DEBASHISH SHARMA

ROLL NO: 29
 CONTENTS
• INTRODUCTION

• DIFFERENT VOLUMETRIC PROPERTIES

• VAN-DER WAALS VOLUME

• STANDARED MOLAR VOLUMES

MOLAR VOLUMES OF ORGANIC LIQUIDS

MOLAR VOLUMES OF RUBBERY AMORPHOUS POLYMERS
MOLAR VOLUMES OF GLASSY AMORPHOUS POLYMERS
MOLAR VOLUMES OF CRYSTALLINE POLYMERS
MOLAR VOLUMES OF SEMICRYSTALLINE POLYMERS

• CONCLUSION
 WHY VOLUMETRIC PROPERTIES ARE IMPORTANT?

• Mass and packing are the most important fundamental

properties of matter.
• The packing of chains in a polymer can defines other
polymeric properties.
• That is how efficiently the chains have arrange
themselves in a defined space, says a lot about its
behaviour.
 WHAT ARE THE DIFFERENT VOLUMETRIC
PROPERTIES?

• Van der waals volumes

• Specific and Molar Volumes
• Densities
• Specific and Molar thermal expansions
• Specific and Molar melt expansions
• Density is defined as the ratio of molar mass to molar
volume.
 VAN DER WAALS VOLUMES

• Van der Waals volume of a molecule is defined as the volume occupied by the
molecule which is impenetrable to other molecules at ordinary temperatures.
• The Van der Waals volume is assumed to be bounded by outer surface of a
number of interpenetrating spheres.
• The radius of this spheres are assumed to be constant atomic radius, for the
element involved and the distance between the centres of the spheres and the
bond distance.
• The van der Waals volume of a polymer repeat unit can approximately be
calculated as the sum of the van der Waals volumes of the composing structural
groups (group increments):

• The true volume will be slightly different since the group contribution of each
atom (Vvdw,k) in an increment is not constant but depends on the nature of the
surrounding atoms. 

• The volume contribution of each structural group already contains most of the
inbuilt information on the influences of the atomic surroundings with the
exception of the terminal bonds, and therefore, the approximation is valid.

• The crystalline molar volume is approximately equals to 1.43 times the Van der
Waals volume.

• The amorphous molar volume is approximately equals to 1.60 times the Van der
Waals volume.
 STANDARD MOLAR VOLUMES

I. Molar volumes of organic liquids:

• Contributors: Traube (1895), Le Bas(1915), Davis(1960s),Gottlieb(1963),

Harrison(1965)

• Molar volume of organic liquids is given by:

• The ohm (Ω) represent residual volume

• It is a constant with an average value of 24cm3/mol
II. Molar volumes of rubbery amorphous solids
• The rubbery amorphous state of polymers has the greatest correspondence
with the liquid state of organic compound.

• The molar volume of rubbery amorphous polymer is given by:

• Here residual volume is neglected unlike in organic liquids because of high

molecular weight.

• The molar volume can also be calculated by densities, both this molar
volumes are compared between the experimented and calculated values
the inaccuracy of this calculation was too large.

• Another approach was established where a graph between Vr (298)/VW was

done and the ratio of these two was found to be in the range of 1.60±0.035
III. Molar volumes of Glassy Amorphous solids

• Amorphous polymers having glass transition temperature higher than room

temperature are glassy amorphous solids

• For each polymer the molar volume per structure is calculated from density

• Similar to molar volume of rubbery amorphous polymer, a graph of Vg(298)/

Vw is plotted.

• The ratio was almost identical with the ratio of rubbery amorphous polymer.

• The ratio was found to be 1.60 ± 0.045

IV. Molar volume of Crystalline polymers
• Fully crystalline polymers does not exists, except in special case of single crystals.

• Therefore the density of the crystalline polymers cannot be measured directly .

• With the help of X-Ray analysis, the crystal system of crystalline domains and also
the dimensions of the unit cells well as the number of constitutional base units of
the unit cell is determined.

• With this data the density is determined as follows:

• From the help of this crystalline density, molar volume of crystalline polymer V C
(298) is established.

• similar to previous two cases this value is plotted against V W

• The ratio of VC (298)/ VW was found to be 1.435 ± 0.045

V. Molar volumes of semi-crystalline polymers
• Semi-crystalline polymers have both the domains that is amorphous and
crystalline
• The densities of both the domains are known .
• The ratio of their density that is ρc/ρa is taken and found that:
 The ratio is in the range of 1.13 ± 0.08
 For highly crystalline the ratio shifts near 1.2
 For highly amorphous it shifts near to 1.1

• The molar volume equation for semi-crystalline polymer is given by:

where xc is degree of
crystallinity

• Substituting Vc and Va with VW :

• Further solving this and later replacing Van der Waals volume with amorphous
volume we find
 CONCLUSION

Since from the value of Van der Waals volume of a polymer which
was derived from universal value of atomic radii and atomic
distance, it may be concluded that the method of calculation of
different standard molar volumes provides a sound basis for the
estimation of polymer properties under standard conditions.