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APL 102
Lecture 14
Recap
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Polymer behavior with temperature Elastomers
T Glass transition (Tg) Mobile segments
Isoprene molecule
mobile
viscous
liquid
Callister,
rubber
Fig. 16.9
Tm
Tm H H3C H
liquid tough
plastic
Tg Rubbery
C=C-C=C
T
partially Tg
crystalline
crystalline H H H
solid
solid
Rigid solid Liquid natural rubber (latex)
Molecular weight
Cross-link points
Typical Tg is 0.4 – 0.75 Tm
1. Metastable
2. Unstable
2
1 3. Stable
3
P.E
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unstable
Mechanical push to overcome
activation barrier Activation
P.E barrier
metastable System automatically
attains the stable state
stable
Configuration
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Otherwise Unstable
Thermodynamic properties
Thermodynamic properties
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What is enthalpy? H = E + PV
Demonstration of PV term in solid
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U = 338.4 KJ
1) Oscillatory
2) Rotational
3) Translational
Thermal Entropy
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T , frequency
k = Boltzmann constant
1.38 x 10-23 J/K
n E *
exp
N kT
Configurational Entropy
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Boltzmann’s
Epitaph
S k ln W
W is the number of
configurations having the
same energy
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N!
W Cn
N
n!( N n)!
Stirling’s Approximation
ln n! n ln n n
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Free energy
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Gibbs Free Energy
G H TS
In solids since H ≈ U,
G and F are used interchangeably
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Gibbs Free Energy
G H TS
G = 0 reversible change
G < 0 irreversible or
spontaneous change
G > 0 impossible
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Kinetics
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Kinetics
Arrhenius plot
Q Q = Activation energy
rate A exp
RT
A = pre-exponential constant
ln (rate)
Q
slope
R
1
T
Mechanical behavior of Elastomers
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straight
Coiled chains chains
Higher Lower
entropy entropy Still lower
entropy
Contracts on
heating
F
Elastomers have ve thermal expansion coefficient, i.e., they CONTRACT on heating!!
S
F T
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Enthalpy change on
stretching = 0
L T
I law of Thermodynamics F → Force applied to stretch
II law of Thermodynamics T → Constant temperature
L → Length of molecule
S → Entropy
Equation
N 0 kT L L0 2
Of
F State
For a
L0 L0 L Rubbery
material
F
L0 L0 L
Experimental
N kT L L0 2
F 0
L0 L0 L
Announcement
IIT Delhi
Date: 31-Aug-17
Venue: LH 121 – (Groups 1A, 1B, 2A, 2B, 3A and 3B)
& LH 308 – (Groups 4A & 4B)
Time: 2:30 to 3:30 pm
Minor I Syllabus: Topics covered till 23rd Aug 17, i.e. Elastomers
Tuesday (29th Aug) Lecture & Lab sessions are on tomorrow (26th
Aug)