1 l3 property estimation 2

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Product Design

Property EstimationChapter 3

Article on Phys. Property Estimation

CHEN 4253

Terry A. Ring

University of Utah


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Types of Properties

Thermodynamic Properties

Transport Proprieties

Kinetic Properties


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Design Methods

Physical Properties Group Contributions

Thermo package in Process Simulator

Process Simulation of Refrigeration cycle Condenser

Vaporizer

Pump

Valve to flash liquid to vapor


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Refrigerant Design

Large negative Joule-Thompson Coefficient

Large Enthalpy of Vaporization

High Liquid Heat Capacity

Low Pressure -Tboil below RT Vapor Pressure > 1.4 Bar to assure no air leaks

High Pressure Compressor/Condensor

Vapor Pressure < 14 Bar to keep compression ratioless than 10


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Solubility Parameter Prediction

Solubility Parameter Solubility of liquid in liquid Solubility of solid in liquid

Solubility of polymer in liquid Group Contributions

Three parameters

Dispersive Polar Hydrogen Bonding


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Flory-Huggins solution theory

The result obtained by Flory[1] andHuggins[2] is

The right-hand side is a function of the number ofmolesn1 andvolume fraction 1 ofsolvent (component 1 or a), the number ofmoles n2 and volume fraction 2 of polymer (component 2 or b),with the introduction of a parameterchi, , to take account of theenergy of interdispersing polymer and solvent molecules.

Molar volume of polymer segment are Hildebrand solubility parameters, =((Hvap-RT)/Vmolar) =(d2 + p2 + h2), linkage to Hansen Solubility parameters
http://en.wikipedia.org/wiki/Flory-Huggins_solution_theoryhttp://en.wikipedia.org/wiki/Flory-Huggins_solution_theoryhttp://en.wikipedia.org/wiki/Function_%28mathematics%29http://en.wikipedia.org/wiki/Mole_%28unit%29http://en.wikipedia.org/wiki/Solventhttp://en.wikipedia.org/wiki/Componenthttp://en.wikipedia.org/wiki/Chi_%28letter%29http://en.wikipedia.org/wiki/Energyhttp://en.wikipedia.org/wiki/Energyhttp://en.wikipedia.org/wiki/Chi_%28letter%29http://en.wikipedia.org/wiki/Componenthttp://en.wikipedia.org/wiki/Solventhttp://en.wikipedia.org/wiki/Mole_%28unit%29http://en.wikipedia.org/wiki/Function_%28mathematics%29http://en.wikipedia.org/wiki/Flory-Huggins_solution_theoryhttp://en.wikipedia.org/wiki/Flory-Huggins_solution_theory


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Hansen Solubility Parameter

Hansen Solubility Parameters were developed by Charles Hansen as a way of predicting if onematerial will dissolve in another and form a solution[1]. They are based on the idea that likedissolves like where one molecule is defined as being 'like' another if it bonds to itself in a similarway.

Specifically, each molecule is given three Hansen parameters, each generally measured in : The energy from dispersion bonds between molecules The energy from polar bonds between molecules The energy from hydrogen bonds between molecules

These three parameters can be treated as co-ordinates for a point in three dimensions also knownas the Hansen space. The nearer two molecules are in this three dimensional space, the morelikely they are to dissolve into each other. To determine if the parameters of two molecules(usually a solvent and a polymer) are within range a value called interaction radius (R0) is given tothe substance being dissolved. This value determines the radius of the sphere in Hansen spaceand it's center is the three Hansen parameters. To calculate the distance (Ra) between Hansenparameters in Hansen space the following formula is used:

Combining this with the interaction radius gives the relative energy difference (RED) of thesystem:

RED < 1 the molecules are alike and will dissolve RED = 1 the system will partially dissolve RED > 1 the system will not dissolve

See Articles Solvents_Data.pdf
http://en.wikipedia.org/w/index.php?title=Charles_Hansen&action=edit&redlink=1http://en.wikipedia.org/wiki/Solubilityhttp://en.wikipedia.org/wiki/Solutionhttp://en.wikipedia.org/wiki/Solubility_parameterhttp://en.wikipedia.org/wiki/Van_der_Waals_forceshttp://en.wikipedia.org/wiki/Polar_bondshttp://en.wikipedia.org/wiki/Hydrogen_bondshttp://en.wikipedia.org/wiki/Hydrogen_bondshttp://en.wikipedia.org/wiki/Polar_bondshttp://en.wikipedia.org/wiki/Van_der_Waals_forceshttp://en.wikipedia.org/wiki/Solubility_parameterhttp://en.wikipedia.org/wiki/Solutionhttp://en.wikipedia.org/wiki/Solubilityhttp://en.wikipedia.org/w/index.php?title=Charles_Hansen&action=edit&redlink=1


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Group Contribution Methods

Group (bond) ContributionMethods ni=number of groups of type

i in polymer repeat unit or

molecule

N= number of group types Ai=group contribution to

property p{n}

Mwi= Molecular weight ofgroup I, sometimes anothergroup contribution property

d=exponent for property

d

N

i

ii

N

i

ii

nMw

nAnp

1

1}{


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Group Contribution Methods

Polymer Glass Transition Temp.

Polymer Molar Volume

Polymer Density Polymer Water Absorption P. 66 of your book


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Liquid Surface Tension/Wetting

Group Contribution Method Contact AngleYoungs Equation cos = (SV- SL)/ LV Wetting when => 0

Predicting Liquid surface tension LV=[LMw-1 (NiPi)]4 Pi=Parachor Value of group

Surface tension in [dyne/cm] Density [gm/cm^3]

Mw [gm/mole] Liquid Mixtures surface tension based upon mole

fraction, Xi

LV= LV_iXi


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Parachor Values

Tables from Ring, Fundamentals of Ceramic Powder

Processing, Academci Press 1999.

CH2=CH O CH3

Groups PiC 3 4.8

H to C 6 17.1

O to ether 1 20

Double Bond 1 23.2

LV=[LMw-1(NiPi)]4


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Select Surfactants for Dispersion

Lower Surface tension of a liquid Detergency

Hydrophilic-lipophilic Balance-HLB HLB = 7+ HiLi

Stabilized Suspension HLB

surfactant= HLB

particle

Tables from Ring, Fundamentals of Ceramic Powder Processing, Academic Press 1999.


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Group Contributions - HLB

Tables from Ring, Fundamentals of Ceramic Powder Processing, Academic Press 1999.

TiO2


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Drago E and C

Used to predict the Heat of mixing, HAB Acid (A) Base (B) Interactions

Good for non-polar solvents

E = Electrostatic Contributions

C = Covalent Contributions

BABAAB CCEEH


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Acids


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Bases

Can be predicted from Infrared or NMR peak shifts due to mixing

See Wettability By John C. Berg


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Wetting - Good Method

Work of Adhesion between to materials,Wa

AB= -(SV-SL)LV Energy toreplace solid-vaporand liquid-vapor interfaces with liquid-vapor interface.

Predicted by

Liquid


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WettingFowkes (Drago) Method

Work of Adhesion

N = moles of interaction functional groups perunit area

f = factor to convert enthalpy to work


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Transport Properties

Molecular Dynamics Calculations Intermolecular Forces

Lennard-Jones Potentials between Atoms

Location of Atoms in Molecule Molecules Free to move Monte Carlo Methods Statistical Analysis

Molecular Structure Determined From Otimization

Drug Molecule Binding DAB=2/t Gives Upper and Lower Bounds of Property


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Drug/Enzyme Target Development


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Bio Concentration

BioConcentration factor=BCF

log BCF = 0.76 log Kow-0.23 K

ow=octanol/water partition factor

Kow =Xo_w/Xw_o=(o_wMwo)/( w_oMww) Easily get this from a liquid-liquid Flash calc.

Toxicity LC50=lethal concentration when 50% are dead

log LC50= -0.87 log Kow - 0.11

p. 73 of your book


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Kinetic Parameter Prediction

Flash Point Tf=0.683 Tboil-119K

Explosive Potential depends upon theflash point

Tboil from flash calc.

p. 73 of your book


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Many Desired Properties of a

Product

1) Determine list of desired properties 2) Use desired properties to determine

Figure of Merit

Grouping of Important Qualities for a productand/or its use.

Minimized Deviations from Ideal PropertyValues

Minimize (Ai-Adesired)2 for various properties, Ai,for product formulations. [p. 49]

Often minimization is carried out with upper andlower bounds on specific properties or in

comparison with competitors product


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Minimization Problem

x,y,z are property axes

Minimize (Ai-Adesired)2

With constraints of |A1-A1,desired| < 0.05 A1,desired |A2-A2,desired| < 0.1 A2,desired


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Overview

Property Estimation Use Thermo-package in Process Simulator

Use Hansen solubility parameters

Use Group Contribution Methods

Use statistical mechanics

1 l3 property estimation 2

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