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Z. Suo
FREELY-JOINTED CHAIN
A strand of polymer is a chain of a large number of repeating units, the
monomers. The monomers are joined by covalent bonds. Two bonded
monomers may rotate relative to each other. At a finite temperature, the
monomers rotate relative to one another, and the polymer rapidly changes from
one configuration to another. When the two ends of the polymer are pulled by a
force, the distance between the two ends changes. The polymer chain is an
entropic spring.
Boltzmann distribution. For a reminder see the notes on the
Boltzmann distribution (http://imechanica.org/node/293). Here we list the key
results.
A small system is in thermal
Reservoir of energy, kT
contact with a large system. To keep
track of names, we call the small system
just the system, and call the large system
System
the reservoir of energy, or just reservoir
U1, U2,
for brevity. The system and the reservoir
exchange energy by heat. All other
modes of interactions between the
system and the reservoir are blocked: no
exchange of matter, and no exchange
energy by work.
The reservoir is much larger than the system. Consequently, when the
reservoir exchanges energy with the system, the temperature of the reservoir is
held at a fixed value. The situation is analogous to a reservoir of water. When we
use a cup to take a small amount of water out of the reservoir of water, the level of
the reservoir of water changes negligibly. In this analogy, water is analogous to
energy, and the level of the reservoir of water is analogous to the temperature of
the reservoir of energy. Denote the temperature of the reservoir of energy by kT.
The system flips rapidly and ceaselessly among a set of states. We label
the states of the system as 1, 2, , s..., and denote the energy of the states by
U 1 ,U 2 ,...,U s ,... Because the system is not isolated, these states may have different
amounts of energy, and are not equally probable. After the system and the
reservoir are in thermal contact for a long time, the system and the reservoir in
combination reach thermal equilibrium. In equilibrium, the probability for the
system to be in any state s is proportional to
" U %
exp $$ s '' .
# kT &
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Z. Suo
Because the system has to be in one of its state, the sum of the probabilities of
states is unity. Thus, the probability for the system in any state s is
" U %
exp $$ s ''
# kT &
.
Ps =
" U %
i
exp $$ kT ''
#
&
The sum is taken over all states of the system.
known as the Boltzmann distribution.
Y = PiYi .
The sum is over all states of the system.
For example, energy is a property of a system. When the system is in
states 1, 2,, energy of the system takes values U 1 ,U 2 ,... The mean value of
energy of the system is
" U %
i
U exp $$ kT ''
i
U =
" U %
exp $$ kTi ''
#
&
&
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Z. Suo
f~
kT
.
b
f~
(1.38 10
23
)(
J/K 300K
) = 4.14 10
N.
10 m
In this estimate, we have assumed that the reservoir is at room temperature, T =
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12
Z. Suo
300 K, and that the length of the rod is b = 1 nm. This pico-Newton force is used
in experiments with individual polymer chains.
The mean value of the displacement. The displacement associated
with the force equals the length of the rod projected onto the axis of the force:
y = bcos .
The orientation of the rod fluctuates, and so does y.
The number of states is proportional to the area of the element on the unit
sphere, 2 sin d . The mean value of y is given by
y =
,
force
where
fb
.
kT
Integrating, we obtain that
" 1
1%
y = b$
'.
# tanh &
displacement
y =
fb2
.
3kT
"
1 %
y = b $1
'.
fb / kT &
#
The large force prevails over the temperature, and the rod will be nearly vertical,
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Z. Suo
y b.
Exercise. Carry out the integral. Confirm the two limits.
y =
g kT , f
f
).
g = kT log
.
sinh
w = g+ y f .
giving
!
$
w = kT #
+ log
&.
sinh %
" tanh
Freely jointed chain. A strand of polymer consists of a large number of
monomers joined together by covalent bonds. The freely jointed chain model
represents a polymer by a chain of n links, each link being of length b. Two
neighboring links can rotate freely relative to each other. The chain is pulled at
the two ends by a constant force f in a fixed direction. Every link is subject to the
same force f, and behaves in the same way as a rigid rod.
Let y be the length of the entire chain projected onto the axis of the force.
The mean value of the displacement is given by
" 1
1%
y = nb $
',
# tanh &
where = fb / kT is the normalized force.
The Helmholtz free energy of the single strand of polymer is
!
$
w = nkT #
+ log
&.
sinh %
" tanh
Exercise. Calculate the stiffness of a polymer chain.
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Z. Suo
REFERENCES
W. Kuhn and F. Grun, Kolloidzschr. 101, 248 (1942).
H.M. James and E. Guth, Theory of the elastic properties of rubber. The
Journal of Chemical Physics 11, 455 (1943).
L.R.G. Treloar, The Physics of Rubber Elasticity, Third Edition, Oxford
University Press, 1975.
B. Erman and J.E. Mark, Structures and Properties of Rubberlike
Networks. Oxford University Press, 1997.
J.E. Rubberlike Elasticity, 2nd edition, Cambridge University Press, 2007.
M. Rubinstein and R. Colby, Polymer Physics. Oxford University Press,
2003.
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