InterMolecular Forces

(IMF)

Saptarshi Majumdar

Chemical Engineering Department

Indian Institute of Technology, Hyderabad
Recent Activities

Soya Nuggets
GYTI Award 2016

Hydrogel & Films

RSC Advances, 2015 Materials Letters, 2016

Materials and Manufacturing Processes, 2016 Nanofibers
Mat. Sc. & Engg. C, 2017

Chem. Phys. Letts, Controlled Branching in PP

DST Project
2014 (Chem. Engg. J., 2014; PES, 2014)
Polymer: Window to Explore 

Biology

Theory Polymers Industry

Start
Ups
 May we all be protected
May we all be nourished
May we work together with great energy
May our intellect be sharpened
Let there be no Animosity amongst us
Peace (in me), peace (in nature), peace (in divine forces)
- Upanishad

Let us start..
Multiscale Design: At a Glance

Water
Polymer B

Polymer A

Macro
Rheology, Dispersity,
Degradation, Swelling
Micro
Morphology, Crystallinity,
Networks, Surface Interactions
Nano
Particle size, Distribution,
Radius of Gyration, Charges,
Forces, Molecular Interactions
Overview

Expected Learning:
1. Development of understanding
2. Why do ‘Engineers’ require to know about the forces
3. General Aspects
4. Background Thermodynamics
5. Strong intermolecular forces
6. Polar Interactions
7. Induced Interactions
8. Van der Waals Forces
9. Special Interactions: H-bonding, Hydrophobic and Repulsive Interactions

Main References:
• Intermolecular & Surface Forces, Israelachvili
• Molecular Thermodynamics of Fluid Phase Equilibria by Prausnitz
• Thermodynamic Models for Industrial Applications, Kontogeorgis & Folas, Wiley, 2010.
The Course Details

No. Type Final Frequency Remarks

Weightage

1. Evaluation 30 2 Times

2. Class Performance 10 Relative

Grading
1 time=> Full
3. Attendance 10 Marks; After that -2
Relative
mark per class till 0 Grading
Total = 50
(equivalent to 100%)
Development
of
Understanding
&
Few WHYs

First Nano-Science
Demonstration
Why should we know IMF?
Answers can be IMF
What do you know about these molecules?

Methane – CH4
Ethane – CH3CH3
Propane – CH3CH2CH3
Butane - CH3CH2CH2CH3
Pentane - CH3CH2CH2CH2CH3
Hexane - CH3CH2CH2CH2CH2CH3
Heptane - CH3CH2CH2CH2CH2CH2CH3
Octane - CH3CH2CH2CH2CH2CH2CH2CH3

13
What do you know about these molecules?

Methane – gas at standard T & P

Ethane – gas at standard T & P
Propane – gas at standard T & P – Liquid under slight pressure
Butane - gas at standard T & P – Liquid under slight pressure
Pentane - Liquid
Hexane - Liquid
Heptane - Liquid
Octane - Liquid

14
Single Effect – Large Implications
Multi-scale Modeling: Interfacial Tensions (DPD Application)

Empirical Mesoscopic Atomistic Himanshu

(DPD)
Introduction
• Dissipative Particle Dynamics (DPD): Introduced by Hoogerbrugge
and Koelman (Shell) in 1992.
• Dissipative Particle Dynamics (DPD): Off lattice, discrete particle
method for modelling mesoscopic systems.
Rakesh
  
dri  dpi  ri position of particle i
 v;  fi  
dt dt vi  pi / mi velocit y of particle i

 C D R fi force on particle i
f i   f ij  f ij  f ij
j i
mi mass of particle i Prof. P Ray
 Multi-scale Modeling: Interfacial Tensions (DPD Application)

 r r
f ijC  aij 1  ij  ij ( rij  rc ) Conservative
 rc  rij Chemical and physical
information of the system
f ijC  0 ( rij  rc )
Dissipative
D
f ij  d ( rij ) rˆij  vij  rˆij
 motions of the molecules within
beads dissipate energy.

R Random
f ij  r ( rij )ij rˆij stochastic part, random motion of
the molecules

• Dissipative and random forces: Act as thermostat

Molecular Dynamics DPD

 Multi-scale Modeling: Interfacial Tensions (DPD Application)

• Now coarse grain model to be formed

based on averaging of molecular volume
and interaction among molecules

• For Water and Benzene W[5][1]B[1][1]

been chosen.

• The molecular volume of five water

molecules 150 A°3 and for benzene
148A°3. The average molecular volume
of bead kept 149A°3.

 δ δ 
1 2
2
  ρ 2 α  a 11  a 22
 - 2a 12


93.25  9 * 0.1( 25  60.35  2 a 12)
a 12  94.34
δ1  47.8 (J/cm 3 )1 / 2 , δ 2  18.5(J/cm 3 )1 / 2 , ρ  3, α  0.1
Vb  149 A3 , rc  (3 * 149)1 / 3  7.64A  • Fluctuation amplitude, Friction
3 coefficient,
 δ1  δ 2  2  858.49J/cm 3 ,  δ1  δ 2  2 * KrcBT   δ 1  δ 2  2 • System size, Temp, etc.
• Run Simulation.
858.49 * (7.64 * 108 )3
 93.25
1.38 * 1023 * 298
Multi-scale Modeling: Interfacial Tensions (DPD Application)

Interfacial Tension for Non water with Alkanes systems

EG: Ethylene Glycol, FM: Formamide, DMSO: Dimethyl sulfoxide

 Multi-scale Modeling: Interfacial Tensions (DPD Application)

Non-AROMATIC SYSTEMS: Temperature Dependence

ETHYLENE GLYCOL-TETRA DECANE WATER- CYCLO HEXANE

Ref : Inaba et.al Fluid Phase Equilibria 125 (1996) 159-168; E. Mayoral et.al The Journal Of Chemical Physics138, 094703 (2013); M. Alpbaz et.al
Commun .Fac.Sci.Univ.Ank.Serie.B (1988)

H. Goel, R. Chandran P., K. Mitra, S. Majumdar and P. Ray, Chem. Phys. Lett. 600, 62 (2014)
~400 downloads in 10 months worldwide
Fab Four
Development
Mostly Used Potential

LJ Potential
Let us have another
Preliminary Views

-C/rn
Small brings the Large
Properties get affected
Material
Nano-confinement Properties not function of (solid/
Volume of material/ container liquid/gas)
Example of a Basic Calculation

Surface Tension (ϒ) is associated with cohesive energy density (U) and pair potential w(σ).

U=6w(σ) [How this is we will see later]

Radius of molecule (r) = 3ϒ/U

For water: Latent Heat is 40.7 kJ/mole; 1 mole of water occupies 18x10-6 m3 volume.
U in per volume unit => 40.7 x103/ (18x10-6) = 2.3 x 109 J/m3

r = 3 x 0.07/ 2.3 x 109 = 0.09 nm ≈ 1 Å

• Latent Heat is H = U + PV (here PV was not considered)
• Surface energy estimation may have error
• Opposite is also interesting i.e. from ϒ value to r.
What all we have learned

Strong
Quantum Repulsive
Boyle Attractive
Newton Repulsive
Attractive

n < Dimensionality n > Dimensionality

of the System of the System
Long Range Short Range
Next Class

Background
Thermodynamics