Product Design

Property Estimation
Chapter 3
Article on Phys. Property Estimation
CHEN 4253
Terry A. Ring
University of Utah
 Types of Properties
Thermodynamic Properties
Transport Proprieties
Kinetic Properties
 Vapor Pressure of Mixture
VOC Volatile organic content
Flash Calc with Process Simulator
Hand Calc.
Equation of State
Activity Coefficient Equation
Aspen/ProMax
Pick Thermo Package
Several are available
Polar liquids vs non-polar
Aqueous vs non-aqueous
High P vs low P
Input Components
Set up Flash unit with feed streams
Set Feed Stream composition
Run Calc
Vapor
Liquid
Solid
 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
 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 ratio
less than 10
 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
Flory-Huggins solution theory
The result obtained by Flory[1] and
Huggins[2] is

The right-hand side is a function of the number of moles n1 and

volume fraction 1 of solvent (component 1 or a), the number of
moles n2 and volume fraction 2 of polymer (component 2 or b),
with the introduction of a parameter chi, , to take account of the
energy of interdispersing polymer and solvent molecules.

Molar volume of polymer segment

are Hildebrand solubility parameters, =((Hvap-RT)/Vmolar)
=(d 2 + p 2 + h2), linkage to Hansen Solubility parameters
 Hansen Solubility Parameter
Hansen Solubility Parameters were developed by Charles Hansen as a way of predicting if one
material will dissolve in another and form a solution [1]. They are based on the idea that like
dissolves like where one molecule is defined as being 'like' another if it bonds to itself in a similar
way.
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 known
as the Hansen space. The nearer two molecules are in this three dimensional space, the more
likely 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 to
the substance being dissolved. This value determines the radius of the sphere in Hansen space
and it's center is the three Hansen parameters. To calculate the distance (Ra) between Hansen
parameters in Hansen space the following formula is used:

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

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

 Group Contribution Methods
Group (bond) Contribution
Methods
ni=number of groups of type d
N

Ai ni
i in polymer repeat unit or
molecule
N= number of group types
p{n} Ni 1
Ai=group contribution to
property p{n}
Mwi ni
Mwi= Molecular weight of
group I, sometimes another
i 1
group contribution property
d=exponent for property
 Group Contribution Methods
Polymer Glass Transition Temp.
Polymer Molar Volume
Polymer Density
Polymer Water Absorption
P. 66 of your book
 Liquid Surface Tension/Wetting
Group Contribution Method
Contact Angle Youngs 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
Parachor Values
CH2=CH O CH3
Groups Pi
C 3 4.8
H to C 6 17.1
O to ether 1 20
Double Bond 1 23.2

LV=[LMw-1 (NiPi)]4

Tables from Ring, Fundamentals of Ceramic Powder

Processing, Academci Press 1999.
 Select Surfactants for Dispersion
Lower Surface tension of a liquid
Detergency
Hydrophilic-lipophilic Balance-HLB
HLB = 7+ Hi Li
Stabilized Suspension
HLBsurfactant= HLBparticle

Tables from Ring, Fundamentals of Ceramic Powder Processing, Academic Press 1999.
 Group Contributions - HLB

TiO2

Tables from Ring, Fundamentals of Ceramic Powder Processing, Academic Press 1999.
 Drago E and C
Used to predict the Heat of mixing, HAB
Acid (A) Base (B) Interactions
Good for non-polar solvents

H AB EA EB CACB
E = Electrostatic Contributions
C = Covalent Contributions
Acids
 Bases

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

See Wettability By John C. Berg
 Wetting - Good Method
Work of Adhesion between to materials,
WaAB= -(SV-SL) LV Energy to replace solid-vapor
and liquid-vapor interfaces with liquid-vapor interface.
Predicted by

Liquid
 Wetting Fowkes (Drago) Method
Work of Adhesion

N = moles of interaction functional groups per

unit area
f = factor to convert enthalpy to work
 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=<x>2/t
Gives Upper and Lower Bounds of Property
Drug/Enzyme Target Development
 Bio Concentration
BioConcentration factor=BCF
log BCF = 0.76 log Kow-0.23
Kow =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
 Kinetic Parameter Prediction
Flash Point
Tf =0.683 Tboil-119K
Explosive Potential depends upon the
flash point
Tboil from flash calc.

p. 73 of your book
 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 product
and/or its use.
Minimized Deviations from Ideal Property
Values
Minimize (Ai-Adesired)2 for various properties, Ai,
for product formulations. [p. 49]
Often minimization is carried out with upper and
lower bounds on specific properties or in
comparison with competitors product
 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
 Overview
Property Estimation
Use Thermo-package in Process Simulator
Use Hansen solubility parameters
Use Group Contribution Methods
Use statistical mechanics