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Kunal Garg

Introduction

Calculation

Conclusion

Kunal Garg

National Institute of Science Education and Research

kunal@niser.ac.in

BW Theory

Kunal Garg

Introduction

Calculation

Conclusion

The crucial idea behind the model of Bragg and Williams is the

introduction of the order parameter to describe the degree of

order in the system at various temperatures; the free energy of

the system is then described in terms of this order parameter;

finally, the equilibrium of the system is determined by

minimising the free energy with respect to the order parameter.

More specifically, the order parameter gives the probability of

occupation of the given sites at the given temperature. In more

complex ordered structures, more than one order parameter is

needed to carry out the analysis.

BW Theory

Kunal Garg

Introduction

Calculation

Conclusion

model.

BW Theory

Kunal Garg

Introduction

Calculation

Conclusion

model.

Under certain conditions, BW theory reduces to Landaus

Mean Field theory.

BW Theory

Kunal Garg

Introduction

Calculation

Conclusion

model.

Under certain conditions, BW theory reduces to Landaus

Mean Field theory.

We use it here to determine mps for our model. mps polymer-solvent contacts.

Approach

BW Theory

Kunal Garg

Introduction

Calculation

Conclusion

molecules mix randomly on the surface.

Now to get mps , we need to calculate the probability of

P S contacts for random mixing.

This is called the Bragg Williams Approximation.

The expression for energy of mixing we have is

ss + pp

Umix = Usolution Uunmixed = ps (

) mps

2

Where is the energy of the contact.

Calculation

BW Theory

Kunal Garg

Introduction

Calculation

Conclusion

P =

Nnp

M

Calculation

BW Theory

Kunal Garg

Introduction

Calculation

P =

Nnp

M

Conclusion

contacts is :

Nnp

#of contacts = Z P = Z

M

Calculation

BW Theory

Kunal Garg

Introduction

Calculation

P =

Nnp

M

Conclusion

contacts is :

Nnp

#of contacts = Z P = Z

M

Thus total number of contacts is

Nnp

mps = ns Z

M

BW Theory

Kunal Garg

Introduction

Calculation

Conclusion

ss + pp

Znp N

Umix = ps (

) ns (

)

2

M

BW Theory

Kunal Garg

Introduction

Calculation

ss + pp

Znp N

Umix = ps (

) ns (

)

2

M

Conclusion

ss + pp

Z

ps (

)

=

kT

2

This is a unitless energy parameter.

BW Theory

Kunal Garg

Introduction

Calculation

ss + pp

Znp N

Umix = ps (

) ns (

)

2

M

Conclusion

ss + pp

Z

ps (

)

=

kT

2

This is a unitless energy parameter.

Thus the change in internal energy now reduces to:

Umix ' Hmix =

kTns Nnp

= kb T s p M

M

Concluding Result

BW Theory

Kunal Garg

Introduction

Calculation

expression for free energy of mixing for the regular solution:

Conclusion

p

Gmix

= p s + s lns +

lnp

kTM

N

np N

.

M

Here first term is the enthalpy and second and third term

constitute the entropy.

where p =

BW Theory

Kunal Garg

Introduction

Calculation

Conclusion

in this model.

BW Theory

Kunal Garg

Introduction

Calculation

Conclusion

in this model.

BW can also help to understand phase transitions

appearing in Ising model of ferromagnetic to paramagnetic

transition. This is a second order phase transition.

BW Theory

Kunal Garg

Introduction

Calculation

Conclusion

in this model.

BW can also help to understand phase transitions

appearing in Ising model of ferromagnetic to paramagnetic

transition. This is a second order phase transition.

It also helps in understanding Transition in gravity theories

from ordinary phase (or Anti deSitter phase) to a black

hole phase. This is an example of first order phase

transition.

BW Theory

Kunal Garg

Introduction

Calculation

Conclusion

in this model.

BW can also help to understand phase transitions

appearing in Ising model of ferromagnetic to paramagnetic

transition. This is a second order phase transition.

It also helps in understanding Transition in gravity theories

from ordinary phase (or Anti deSitter phase) to a black

hole phase. This is an example of first order phase

transition.

While in one case, magnetisation works as the order

parameter, for black hole, it is the horizon radius acts as

the order parameter.

BW Theory

Kunal Garg

Introduction

Calculation

Conclusion

Thank You

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