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Lecture 6:

Paramagnetism and elasticity


Applications of statistical methods
Aims:
Spin paramagnetism:
Paramagnetic salts
Curies Law.

Entangled polymers
Role of entropy in rubber elasticity.

February 07

Lecture 6

Paramagnetism
Spin systems
Some atoms in salts have a permanent
magnetic moment.
Example: Gd2(SO4) 3.8H2O, where the Gd3+
ions have a spin moment, S=7/2.

General case:
Angular-momentum, quantum number, J, gives
paramagnetic moment

g B [J ( J + 1)]

12

1<Land
1<Land factor<2
factor<2

Bohr
Bohr magneton
magneton ==e

2me

Component of magnetic moment is quantised

= m J g B ,

J mJ J
J=3

-3 -2

February 07

-1 m +1 +2
J
H
Lecture 6

+3

Spin paramagnetism
Simplest system: a spin-paramagnet.
In this case there is no orbital, angular
momentum so J=S. Since S=, there are only 2
values of mJ.
Only two energy levels to consider, with energy
+/-B.

B
mJ = -1/2

+1/2

Calculate the expectation value of the moment


from the weighting given by the Boltzmann
Distribution,

i exp( U B kT )

=
i

February 07

exp( U B kT )
i

Lecture 6

Curies Law
Spin paramagnetism
There are 2 states and, hence, 2 terms in each
summation.
Average moment, at temperature, T.

= {e ( B kT ) e ( B kT ) } {e ( B kT ) + e ( B kT ) }
= tanh (B kT )
tanh(B/kT)

In the limit of hightemperature and/or


low field
2 B kT
B << kT

-2

-1

2
B/kT

high-T,
low-B limit

The magnetic susceptibility can be measured


B = o ( H + M )
== nn <<>>
= o ( 1 + )H

2 kT

February 07

Curies
Curies Law
Law

Lecture 6

Paramagnetic salts
Experiment
Curves at different temperatures and fields
scale to lie on the curve given by Curies Law.

3+,, S=7/2
Gd
Gd3+
S=7/2

3+,, S=5/2
Fe
Fe3+
S=5/2

<>/
<>/BB

3+,, S=3/2
Cr
Cr3+
S=3/2

B/T
B/T (Tesla
(Tesla KK-1-1))
Waldram Theory of Thermodynamics Ch 15, p187
February 07

Lecture 6

Pierre Curie
and Magnetism
Curies Law
The subject of Pierre Curies doctoral thesis,
1895, the same year as his marriage to Marie.

Ferromagnetic to paramagnetic transition at Tc.


Paramagnetism in salts ~ 1/T (Curies Law)
Diamagnetism is temperature independent.

Died 1906, after a street accident.


February 07

Lecture 6

2-state system: heat capacity


Thermal properties of a 2-state system
Thermal Energy

Z = exp(B ) + exp( B )
ln(Z ) = B + ln (1 + exp( 2 B ))

= ln Z
= B tanh( B / kT )

Heat Capacity

B
C=
=k
sech 2 (B kT )
T
kT

Note the drop at both high and low temperature.


An exception to the rule that systems tend to
the classical, equipartition limit at high T

February 07

Lecture 6

Entropic contribution to
elasticity
Classical treatment:
Any stretched string (metal or rubber)

Length, l; Tension f(T,l).


Tension, f, and other thermodynamic quantities
depend on l and T.

Start from the First Law:

dU =
dU =

dQ
T dS

+
+

dW
f dl

AA

S
S
=T
dT + T
+ f dl
T l
l T
U
dT
T l
February 07

Lecture 6

U
dl
l T
8

Maxwell relation
Classical analysis continued
Need to relate entropy and tension.
From previous results, differentiating gives

U
S
=T
T l
T l
U
S
=T
+f
l T
l T

2U
2S
=T
lT
lT
2 x
2x
=
yz zy

2U
2 S S
f
=T
+
+
Tl
Tl l T T

2S
2 S S
f
T
=T
+
+
lT
Tl l T T l
We have derived a Maxwell relation, which
connects the entropy to measurable quantites.

f
S
=
T l
l T
February 07

Lecture 6

BB

Elasticity: general case


and metal wire
What determines the tension?
f may be a function of l and T. Eq. A gives

f (l , T ) =

U
S
T
l T
l T

Direct
Direct contribution
contribution to
to
internal
internal energy.
energy.
For
For example
example through
through
the
the stretching
stretching of
of
intermolecular
intermolecular bonds.
bonds.

Entropic
Entropic contribution.
contribution.
For
For example
example through
through
the
the ordering
ordering of
of
intermolecular
intermolecular bonds
bonds

Using B we get

U
f
f (l , T ) =
+T
T l
l T
Metal wire:
Elastic modulus: (T) = o(1+(T-To)).
Unstretched length: lo(T) = loo(1+(T-To)).
and are ~10-5.

T f
<< 1
f T l

Effect is due to the U/l term. Entropy is


unimportant.
February 07

Lecture 6

10

Rubber elasticity
Rubber:
Generally have large elastic strain.
In simple cases

f (l , T ) AT (l lo )
f
f
T
From which,
T l

constants
constants

U
f
f (l , T ) =
+T
l T
T l
f
S
T
T
T l
l T

Tension in rubber is an effect of entropy.

d Q = dU f d l
T d S = Cl d T AT (l lo ) d l
T
1
S = Cl ln
A(l lo )2
To
2

Band shortens on heating (at constant f).


Band heats on sudden stretching (constant S)
Entropy decreases on stretching (molecules
unfold).
February 07

Lecture 6

11

Rubber elasticity
1-D statistical model
Take molecules to have 2N links, of length, a.
Each link points right or left.

N+r point Right; N-r point Left.


Length of the stretched molecule, l = 2ra.
Entropy (from k ln g)
(2 N )!
S (r ) = k ln
( N + r )!( N r )!
= k (2n ln(2 N ) ( N + r ) ln( N + r ) ( N r ) ln( N r ) )
We know TdS = dU - fdl and UU(l).

dS
1 dS
= T
dl
2a d r
kT
r
r
=
ln 1 +
ln 1
2a
N
N
kTr 2kT l

=
Na
a lmax

f = T

Expand
Expand lns
lns for
for small
small r/N
r/N

Note:
Note: TT and
and ll dependence
dependence
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Lecture 6

12

Elasticity in rubber
Molecular model
Without strain

With strain

Experiment
X-ray diffraction from un-strained and strained
samples of rubber.

Note the diffraction spots showing enhanced


order in the strained sample.
February 07

Lecture 6

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