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APL 102

Thermodynamics (equilibrium) and Kinetics: A Review

Concepts: (meta-)stability, enthalpy, entropy, configuration entropy, free energy

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

Mechanical behavior (Elastomers)

 The deformation is non-linear
 Elastomers have ve thermal
expansion coefficient, i.e., they
contract on heating!!
 Concept of stability and metastability
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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

Minimum Energy – STABLE EQUILIBRIUM

Maximum Energy – UNSTABLE EQUILIBRIUM

Global Minimum - Most STABLE

Local Minimum - METASTABLE

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Thermodynamic properties
 Thermodynamic properties
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Intensive properties: independent of mass

Pressure (P)
Temperature (T)

Extensive properties: dependent on mass

Internal energy (U or E)
Enthalpy (H)

What is enthalpy? H = E + PV
 Demonstration of PV term in solid
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Calculation basis: 1 mol. of Cu atoms at 1 atm.

PV = 0.1 x 106 N/m2 x 7.09 x 10-6 m3

= 0.716 J

U = 338.4 KJ

Hence H and U terms can be used interchangeably in case of solids

 Entropy
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Measure of randomness or disorder in a system

The entropy of a system can be defined by two components:

1. Thermal entropy: Temperature dependent

2. Configurational entropy: Temperature independent

No. 2 is only possible in case of crystalline solids

 Thermal Energy
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Any atom can have three kinds of motion

1) Oscillatory

2) Rotational

3) Translational
 Thermal Entropy
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Atoms in solid oscillate about mean position with varying amplitude

and directions

T , frequency

ν = 1013 s-1 around 200 K

This oscillatory energy available can be defined as

— Average energy per atom per mode of oscillation = kT
 Thermal energy
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k = Boltzmann constant
1.38 x 10-23 J/K

Average thermal energy per mole of atoms per mode of

oscillation is
NkT=RT
 Maxwell-Boltzmann Distribution
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n  E  *
 exp  
N  kT 

Fraction of atoms having an energy  E*

at temperature T
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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)!

N=16, n=8, W=12,870

Two ordered arrangements possible, rest all random

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If n>>>1

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

Helmholtz Free Energy

F  U  TS

In solids since H ≈ U,
G and F are used interchangeably
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Gibbs Free Energy
G  H  TS

Condition for equilibrium

≡ minimization of G

Local minimum ≡ metastable equilibrium

Global minimum ≡ stable equilibrium
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G = GfinalGinitial

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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(Lab expt. after Minor 1)

1. A few hundred percent of temporary (recoverable)

deformation on stretching

2. The deformation is non-linear, Stress  strain

3. The stretched elastomers contracts on heating

 Elastomer Elastomer sample
sample under tension
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Tensile force heat

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
 I law of Thermodynamics
 II law of Thermodynamics
 L T
 F → Force applied to stretch
 T → Constant temperature
 L → Length of molecule
 S → Entropy

 Entropy change for stretch

L0 → L  
 Change in number of S  S 0  k ln 
configurations
0 → 
 0 
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1   L
2
 0
L 
S  S 0   N 0 k    2   3
2  L0   L  

Equation
N 0 kT  L   L0  2
 Of
F       State
For a
L0  L0   L   Rubbery
material

Constant at given temperature

 N 0 kT  L   L0  
 2
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F      
L0  L0   L  

F applied tensile force

N0 number of cross-links
k Boltzmann constant
T absolute temperature
L0 initial length (without F)
L final length (with F)

You will explore this in laboratory in much more detail!

 Bond stretching in straightened
out molecules
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Experimental

Theory: Chain uncoiling

N kT  L   L0  2 
F 0      
L0  L0   L  
 Announcement
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 Minor I exam details:

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)