I.

SIZE AND SHAPE OF

MACROMOLECULAR CHAIN

I.1. Configuration and conformation. Flexibility of

the macromolecular chain.
Describing an organic substance requires taking into account several key
aspects. Firstly, the chemical constitution gives the types and numbers of
different atoms that form the molecule. The brute formulas give the chemical
constitution of the substance as it results from elemental analysis.
The configuration represents the atoms' sequence in a substance, precisely
determined and corresponding to its chemical constitution. In order to separate
the different configuration isomers, structural formulae are used. Identification
of the various groups that point to a given configuration is a more difficult task
and involves either physical (e.g. spectroscopy) or chemical methods (i.e.
reactivity towards given substances, controlled degradation and analysis of the
products, etc.).
The conformation is the spatial arrangement of the atoms, resulted from
rotations around simple chemical bonds ( bonds). Different conformations are
represented using spatial (steric) formulae.
The conformation isomers (or rotational isomers) differ by their respective
potential energies and result by the rotation of atoms around a simple () bond.
For ethane, there are two extreme conformations: the staggered (which is the
most stable) and the eclipsed one (that is the richest in energy). Between those,
an infinite number of intermediate conformations are possible, each differing by
the torsion angle (see figure I.1.). For more complex substances, the number of
possible conformations increases (normal butane for instance possesses 3
eclipsed and 3 staggered conformations).
A conformation transformation implies neither the breaking of chemical
bonds, nor the modification of valence angles (as would be the case in order to
transform an isomer into another), but only gaining an amount of energy

Size and shape of macromolecular chain

superior to the torsion potential (energy barrier for the free rotation). The
torsion potential (U0) depends on the repulsion forces between the substituants
of the atoms that form the simple bond. Table I.1. illustrates the values of the
torsion potential for several simple organic substances.

(I)
(I)

(II)

(III)

Figure I.1. Conformational (rotational) isomers of ethane.

I staggered; II eclipsed; III intermediate, under a torsion angle .

Table I.1.
Torsion potentials for certain organic substances.
No.
1

Substance

H3C

CH3

U0, kcal/mole
2.8

H3C

CH2

CH3

3.4

H3C

CH CH2

1.95

4
5

H3C

CH

CH3
H3C

CH3

0.5
4.2

CH3
6

HOOC

CH2

CH COOH

~ 15

CH3
NO2 HOOC
> 15

COOH O2N

Macromolecular Compounds II - Polymer Properties. Polymer Processing.

The data in table I.1. allow some general remarks regarding the values of
the torsion potential:
The presence of bulky and/or polar groups as substituants leads to strong
repulsions, which increase the torsion potential.
The transition from a conformation to another one occurs by absorption
of energy from the environmental "thermal bath"; if the torsion potential is too
high (typically when it exceeds 15 kcal/mole), the conformational
transformation is no longer possible and the conformational isomers become
"real" isomers. Note that the term "thermal bath" defines any system of particles
(atoms or molecules), at a finite temperature, characterized by perpetual
movement (translation, rotation, vibration, etc., also known as thermal motion or
Brownian motion). The kinetic energy of such molecules is directly proportional
with the temperature of the thermal bath; this energy can be transmitted to other
molecules through successive collisions.
The capability of a molecule to undergo conformational transformations
under the influence of a form of energy is called the macromolecule's
flexibility. The flexibility can be defined from two different aspects:
Thermodynamic flexibility: for a transformation to occur, the internal
energy U2 of the final state must be lower than the energy U1 of the initial state.
Therefore the difference U = U2 - U1 is a measure of the thermodynamic
flexibility of the macromolecule.
Kinetic flexibility. In order to switch from an initial conformation to a
final state, the macromolecule (or the segment) must transit all the intermediate
conformations, each of which differs from the others by the steric hindrance of
the substituants of the atoms that form the main chain.
One of these intermediate states is richer in energy than all the others. Even
if it is not the final state of the transformation, the molecule must posses enough
energy to pass through this intermediate state. The difference between the
energy of this intermediate conformation and the initial state is the torsion
potential U0; therefore, U0 is a measure of the kinetic flexibility of a molecule.

I.2. Macromolecule models

I.2.1. The freely joined chain
In order to explain the conformation of the polymer macromolecules, W.
Kuhn, H. Mark and E. Guth proposed a simple model called the freely joined
chain. They considered a chain formed by n identical atoms linked by covalent
bonds of length L under the following simplifying hypotheses:
The valence angles are not fixed, they may assume any value.
There is no excluded volume, therefore the chain can pass several times
through the same point.
The macromolecule is isolated.

Size and shape of macromolecular chain

If the first atom of the above chain is placed in the centre of a Cartesian
axis system (figure I.2.) then the second atom could be found anywhere on the
surface of a sphere having the centre in the first atom and the radius equal to the
bond length, L. This applies equally to the others atoms: the geometrical locus of
each such atom is the surface of a sphere having the radius L and centred on the
preceding atom in the chain.

x
z
Figure I.2. Model of the freely joined chain.
While very simple as a model, the freely joined chain allows several very
important conclusions regarding the macromolecules' conformation:
1. First, it is obvious that since the chain length is the only restriction
the position of one atom in the chain is practically independent of the position of
all other atoms, with the exception of its nearest neighbours. The most probable
conformation of such a chain is a random entanglement, called macromolecular
coil.
2. Second, this model allows the introduction of a very important notion,
which plays a key role in the further explaining of the physical properties of
polymers: the chain segment. A chain segment is defined as a fragment of a
macromolecule, whose conformation is independent of the conformation of its
neighbours. In other words, a segment is an independent kinetic unit. The chain
segment is a theoretical notion, statistically computed, and has a length of about
30-40 monomer units, depending on the chemical structure of each specific
polymer. A segment can undergo conformational transformation without
affecting the conformation of its neighbouring segments. These transformations
consist of one or several rotations around - type bonds and occur when some
form of energy is transmitted to the macromolecule. The energy triggering the
transformation can be either mechanical (unit stress) or thermal (energy of the
environmental "thermal bath" or provided by a thermal agent).

Macromolecular Compounds II - Polymer Properties. Polymer Processing.

3. Third, the model allows the estimation of the macromolecular coil's

dimensions, using the distance between the two extremities of the chain, called
the gyration radius or the end-to-end distance (r).
Two limit cases can be defined:
a. rmin = 0. The molecule is a perfectly wrapped, rigid coil, with a quasispherical shape.
b. rmax = nL. The molecule is perfectly unwrapped, linear.
These two extreme situations have very low probabilities. The values of the
end-to-end distance, r, will range between rmin and rmax.
The number of possible intermediate conformations is very high (of the
order of magnitude of 104770 for a chain of about 10 000 atoms). A multitude of
different conformations share the same end-to-end distance since they can be
obtained by changing the conformation of one or several segments, without
modifying the overall gyration radius.
Using the statistical model of a random walk, Kuhn, Mark and Guth
showed that the thermodynamic probability for a chain to adopt a conformation
characterised by a given gyration radius is:
3
2

3r 2
3

exp
(1.1)
W ( r ) 4 r
2
2nL2
2

nL

Note that the thermodynamic probability (defined as the number of

identical states from the multitude of possible states, which in this case is the
number of different conformations that have the same gyration radius) is a very
large number, while the mathematical probability is always between 0 and 1.
Relation (1.1) corresponds to a Gaussian probability curve (figure I.3), with
the extreme values rmin and rmax. Accordingly, the freely joined chain is also
known as the Gaussian chain.
A simple method for characterising the distribution curve of the gyration
radius is the use of average values. As in any statistical distribution, several
types of averages may be computed:
The most probable end-to-end distance corresponds to the maximum of
the distribution curve (fig. I.2.):
w( r )
2 2
0
rp
nL
(1.2)
r
3
The average gyration radius is computed as follows:

8
(1.3)
r r w( r )dr
nL2
3

0
The mean square end-to-end distance represents the second-order average
of the gyration radius distribution:
2

2
r 0 ,l

r 2 w( r )dr nL2
0

( r 0 ,l )0.5 nL2

(1.4)

Size and shape of macromolecular chain

W(r)

rp

2 1/2

( r ol )

Figure I.3.
Probability distribution of the gyration radius in the freely joined chain model:
rp - the most probable end-to-end distance;
r - the average end-to-end distance;
r02l 0.5 - the mean square value of the end-to-end distance.
The mean square end-to-end distance is the indicator commonly used to
characterise the dimensions of macromolecular coils. The index 0,l in relation
(1.4) denotes the model of the freely joined chain, to which the values in other
models are usually compared.
Example I.1. Given a linear molecule of polyethylene with the molecular
mass of 120 000 g/mol, compute its mean square end-to-end distance and compare
it with the maximum value.
The mass of the monomer unit in polyethylene is M0 = 28, therefore the
polymerization degree is X = 4285; accordingly, the number of carbon atoms is
n = 8570. The length of a simple C-C bond is L = 1.54 therefore rmax = 1320 nm
and ( r 2 0 l )0.5 14.2 nm . Note that the maximum value is in this case impossible
since it implies an 180 angle between the C-C bonds while this angle is in fact
10928' for an sp3 hybridisation.

I.2.2. The freely rotated chain

A second model of the macromolecular chain, the freely rotated chain, is
obtained if the first of the simplifying hypotheses of the freely joined chain
model is discarded. In the freely rotated chain model, not only the bond length
but also the angle between two covalent bonds is fixed. In a Cartesian
representation (see figure I.4.) where the first atom is placed in the centre of the
axis system, the second atom can also be found anywhere on the surface of an
L-radius sphere centred on the first atom. For the third and the following atoms,

Macromolecular Compounds II - Polymer Properties. Polymer Processing.

the condition of having a fixed angle between the bonds will restrict the
possible positions in space to points of the basis circumference of a cone with
the second (or precedent) atom at the tip and the angle between the generatrix
(of length L) and the precedent bond equal to the angle between the bonds.
The resulting conformation will also be a coil. However, this coil will be
significantly less tightly wrapped than a freely rotated chain. It has been shown
that the mean square value of the gyration radius in this case is given by:

r r0 ,l

1 cos
1 cos
nL2
1 cos
1 cos

(1.5)

Example I.2. For the linear polyethylene molecule in example I.1., the angle
between bonds is 10928' hence cos = - 0.333 and r 20.1 nm , about 40%
more than the value predicted by the model of the freely joined chain.

z
Figure I.4. Model of the freely rotated chain.

I.2.3. The hindered rotation chain

The hindered rotation model takes into account the fact that the place
occupied by an atom is no longer available for placing another atom. Moreover,
between atoms there are steric repulsions that lead to an additional increase of
the volume of the macromolecular coil, as compared to the former models. The
mean square value of the gyration radius is given by:

r nL2

1 cos 1

1 cos 1

(1.6)

Size and shape of macromolecular chain

where < 1 is a parameter that quantifies the steric hindrances.

The presence of the substituants of the main chain further hinders bond
rotation, thus increasing the excluded volume and thereby the gyration radius.
These are quantified by using a steric factor, , whose value typically ranges
between 1.5 and 2.5:
1 cos 1
r f nL2

(1.7)
1 cos 1

I.3. Real chains

Relation (1.7) gives the dimensions of unperturbed polymer chains, i.e. of
isolated polymer molecules. Real chains however, have a larger volume because
in real chains molecules are not isolated, but fragments of different molecules
interpenetrate. The chain's entanglement increases the excluded volume leading
to a gyration radius larger than that computed for theoretical models. The ratio:

C r 2 r02,l

(1.8)

is used to characterise the stiffness of a polymer chain. Some values of the

parameter C are given in table I.2.
Table I.2.
Typical values of C for some common polymers.
Polymer
Polyethylene
Polystyrene
Poly(methylmethacrylate)
Polybutadiene 1,4 cis

C
6.8
10.8
8.6
4.8

Polymer
Isotactic polypropylene
Poly(vinyl chloride)
Poly(ethylenoxyde)
Poly(hexamethylenadipamide)

C
5.5
6.7
4.1
5.9

A macromolecular chain is flexible provided it is capable of undergoing

conformational transformations under the influence of a form of energy. If these
transformations are not possible, then the chain is rigid. The rigidity (or the
stiffness) of a chain depends on the environmental conditions (temperature,
pressure, external forces), but also on the chemical nature of the chains:
Bulky substituants are more hindered, hence the torsion potential and
consequently the chain rigidity are higher.
The polarity of the substituants and the existence of inter- and intramolecular physical bonds lead to an increased stiffness (e.g. polyvinyl alcohol,
polyacrylonitrile, polyamides). In extreme cases, these factors can even affect
the random coil form and transform it into a regular structure, such as the double
helix of the nucleic acids.

Macromolecular Compounds II - Polymer Properties. Polymer Processing.

The stiffness of the network structures increases with the cross-linking

density. If the distance between two cross-linking points is of the same order of
magnitude as the segment dimensions, the segments can still undergo
conformational transformations and the network is flexible and elastic (for
instance the vulcanized rubber, using 2-3% sulphur as a cross-linking agent); if
the cross-linking points are closer to each other, a rigid network is obtained (for
instance ebonite, a rubber vulcanized with 30% sulphur).
Note also that the increase of the chain length multiplies the number of the
possible conformations and therefore increases the probability for the molecule
to adopt the shape of a random coil.

I.3. Relation between the chain's conformation

and the physical state of polymers
The random coil conformation of the macromolecules and the
polidispersity of synthetic polymers are the main factors affecting the order on
molecular level in polymer samples. Therefore, most polymers are in the
amorphous state. The amorphous state is a sub-state of the liquid phase,
characterized by order at short distance and disorder at long distance. Depending
on the mobility of both the chain segments and the whole molecule, in the
amorphous state several sub-states (glassy, rubbery or visco-elastic fluid) are
distinguished, as will be presented in chapter II.
There are also polymers - characterized by a very regular structure - that
can present zones of crystalline phase, obtained by the parallel disposition of
several chain segments. These are biphasic polymers, in which the amorphous
and crystalline states coexist. In order to be able to crystallize, a polymer chain
must be linear, tactic and formed of units resulted from the same type of
addition. Strong intermolecular physical bonds and the presence of orientation
forces during the cooling of molten polymers favour the crystallization.
In the liquid state, the cohesion between the individual molecules is given
by the presence of physical bonds; these have low energy as compared to the
chemical bonds. An increase in temperature will lead to the breaking of the
physical bonds, allowing individual molecules to pass in the vapour (gas) state.
For polymers, the number of physical bonds per molecule in very high. Even if
these bonds have low energy (1-3 kcal/mol, calculated for "molar units"
corresponding to a length of 5 of the main macromolecular chain) their total
energy will greatly exceed the energy of a covalent bond ( 80 kcal/mol for C-C
bonds). Therefore, by heating a polymer, the C-C bonds will be broken before
the destruction of all the physical bonds occurs. Hence, a polymer cannot exist
in the gas state since it decomposes before evaporation.
In order to characterize the intensity of the intermolecular forces in
polymers, an indicator called the cohesion energy for a length of 5 (E5) is

10

Size and shape of macromolecular chain

used. The commonly encountered values of E5 are 1-2 kcal/mol for rubbers,
2-5 kcal/mol for thermoplastics and higher than 6 kcal/mol for the synthetic
fibres.
Example I.3.
Suppose a chain of polyethylene (PE) characterised by weak intermolecular
forces, Van der Waals type (with of energy of about 1 kcal/mole for 5 ) and with
a very low molecular weight (i.e. 56000 g/mol). Since the mass of the repeating
unit is 28 g/mol, the corresponding polymerization degree is DP=2000. The
above number of repeating units means that in a macromolecule there are
n = 4000 C-C bonds, each of them having a length of 1.54 . Consequently, the
real length of the chain will be 4000x1.54 6000 . Therefore, the total energy of
the physical bonds will be (6000/5)x1=1200 kcal/mol macromolecules. The
simple observation that 1200 kcal >>80 kcal shows that when heating the
polymer, first the value of 80 kcal/mol will be reached, meaning the thermal
decomposition of the polymer. Note that the above computation was made for
quite unfavourable conditions (low values for both the strength of the physical
bonds and the chain length). Accordingly, we cannot conceive polymers as gases
when starting from polymers as such.

Macromolecular Compounds II - Polymer Properties. Polymer Processing.

11

Glossary
Constitution - types and numbers of atoms that form a molecule.
Configuration succession of atoms in a molecule, in accordance to its
chemical constitution.
Conformation spatial disposition of the atoms resulting from the rotation
around a simple () bond.
Torsion potential (energetic barrier of the free rotation)- difference between
the energy levels of the richer and poorer in energy conformations of a
molecule.
Macromolecular coil random conformation of a macromolecule.
Gyration radius (end-to-end distance) distance between the extremities of a
macromolecular chain, in a coil conformation; it is used to characterize the
dimensions of macromolecular coils.
Freely joined chain model of the macromolecular coil having as the only
restriction the fixed value of the bond's length.
Freely rotated chain model of the macromolecular coil with restrictions
linked to the bond's length and valence angle's value.
Hindered rotation chain model of the macromolecular coil taking into
account the bonds length, the valence angles values and the excluded volume.
Entanglement of the macromolecular coils random interpenetration of the
chains in polymer samples.
Chain segment fragment of a macromolecular chain whose conformation is
independent of the neighbours' conformation.
Flexibility of a macromolecule capability of a molecule to undergo
conformational transformations through absorption of a certain amount of
energy.
Thermodynamic flexibility difference between the energy levels of the final
and initial state in a conformation transformation.
Kinetic flexibility difference between the energy levels of the richest in energy
intermediate state and the initial state in a conformational transformation.