Lecture Notes :BASIC LAWS IN

MODELING
Principles of Formulation of model:
•Basis
•Assumptions
•Mathematical consistency of model
•Solution of the model equations
•Verification
Transport Equation:
• The transport laws are all have the form of a flux (rate of
transfer per unit area.
• Being proportional to a driving force (a gradient in temperature,
concentration or velocity).
• The proportionality constant is a physical property of the system
e.g. thermal conductivity, diffusivity or viscosity.
• For transport on a molecular level, the laws bear the familiar
names of Fourier, Fick and Newton.
• Transfer relationships of a more macroscopic overall form are
also used e.g. film coefficient and overall coefficient in heat
transfer.
 Transport laws used in developing models.
Quantity Heat Flux Momentum
Flux q NA  rz
Molecular Transport
Driving T C A v z
force z z r
Law Fourier Fick’s Newton’s
Property Thermal Diffusivity Viscosity
Conductivity
KT DA μ
Overall Transport
Driving T CA P
force
Relationship q= hTT NA=kLCA Friction factor
correlations
Equation of State:
To write mathematical models we need equations that tell us
how the physical properties primarily density and enthalpy
change with temperature, pressure and composition.
• Liquid density =L=f (P,T, xi)
• Vapor density =v=f (P,T, yi)
• Liquid enthalpy =h=f (P,T, xi)
• Vapor enthalpy =h=f (P,T, yi)
Simple enthalpy balance equations

h  C pT
H  C pT  v
The next level of complexity would be to make the Cp’s
functions of temperature.
T
h   C p (T ) dT
T0

A polynomial in T is often used for Cp

C p (T )  A1  A2T

Combining the above two equation we get

T2 T A2 2
h  [ AT     
2
1 A2 ]T0 A1 (T T0 ) (T T0 )
2 2
 For mixture of components the total enthalpy can be
calculated as follows neglecting heat of mixing.

NC

x h M
j 1
j j j

h NC

x M
j 1
j j

Where, xj= mole fraction of jth component.

Mj= molecular weight of jth component.
hj = pure component enthalpy of jth component, energy
per unit mass.
 • Liquid densities can be assumed constant in many
systems unless large changes in composition and
temperature.
• Vapor densities usually cannot be considered
invariant and some sort of PVT relationship is almost
always required.
• The simplest and most often used is the perfect gas
laws.
PV  nRT
• Rearranging an equation for density of a perfect gas
with a molecular weight M (mass per moles) is

nM MP
v  
V RT
Equilibrium:
The second law of thermodynamics is the basis for the
equation that tell us the conditions of a system when
equilibrium conditions prevails.
• Chemical equilibrium: Equilibrium occurs in a reaction
system at the following condition.
NC

v 
j 1
j j 0
Where vj = Stoichiometric coefficient of the jth component
with reactants having a negative sign and products a
positive sign.
j= chemical potential of the jth component .
• The usual way to work with this equation is in terms of an
equilibrium constant for a reaction e.g. consider a reversible
gas-phase reaction of A to form B at a specific rate k1 and B
reacting back to A at a specific reaction rate k2.
• The stoichiometry of the reaction is such that va moles of A
react to form vb moles of B.

k
Va A 
1
Vb B
k2
The above equation says equilibrium will occur when,

vb  B  va  A  0
The chemical potential for a perfect gas mixture can be written
as below, where j0 is the standard chemical potential of the jth
component and function of temperature only.
 j   j  RT ln p j
0
• Substituting in stoichiometric relation we get

vb (  B0  RT ln PB )  va (  A0  RT ln PA )  0

RT ln( PB )vb  RT ln( PA )va  va  A0  vb  B0

( PB )vb
va   vb 
0 0
ln va
 A B

( PA ) RT
• The RHS of this equation is a function of temperature only.
The term in parenthesis on the LHS is defined as
equilibrium constant KP, and it tells us the equilibrium
ratios of products and reactants.
vb
( PB )
K p  ln
( PA )va
• Phase equilibrium: Equilibrium between two phases occurs
when the chemical potential of each component is the same
in two phases.
j  j
I II

Where jI is chemical potential of the jth component in phase I

and jII is the chemical potential of the jth component in phase
II.
In chemical engg. systems liquid and vapor phases are there
so many vapor-liquid equilibrium relationships are used.
• Our need is to calculate vapor composition if we know the
liquid composition or vice versa.
• The most common problem is a bubble point calculation:
calculate the temperature T and vap. composition yJ given
the pressure P and the liquid composition. This involves a
trial-error iterative solution.
• Sometimes the bubble point calculation starts from values of
xj and T and we want to find P and yj.
• Dew point calculations must be made when we know the
composition of the vapor yj and P (or T) and want to find the
liquid composition xj and T (or P).
• Flash calculations must be made when we know neither xj or
yj and must combine phase equilibrium relationships,
component balance equations and an energy balance
equation to solve for all the unknowns.
• We will assume ideal vapor-phase behavior in our examples
i.e. the partial pressure of the jth component in the vapor is
equal to the total pressure P times the mole fraction of the jth
component in the vapor yi (Dalton’s law)

Pj  Pyi
In the liquid phase several approach are widely used.
1. Raoult’s Law: Liquid that obey Raoult’s law are called
ideal. Where Pjs is the vap. pressure of pure component j.
Vapor pressure are functions of temperature only. This
dependence is often described by the following equations.
NC
P   xjP j
s

j 1
s
xjP
yj 
j

P
Aj
ln P 
j
s
 Bj
T
• Relative volatility: The relative volatility xij of component I
to component j is defined as below.
yi
xi
 ji 
yj
xj
• Relative volatilities are fairly constant in a no. of
systems. They are convenient so they are frequently
used.
• In a binary system the relative volatility  of the
more volatile component compared with less
volatile component is as below.

y
 x
(1  y )
(1  x)
x
y
1  (  1) x
 Activity coefficient: For non ideal liquids, Raoult’s law
must be modified to account for the non ideality in the
liquid phase. The non ideality expressed as activity
coefficients.

P   x j Pjs j

Where j is the activity coefficient for the jth component .

• The activity coefficient is equal to 1 if the component is
ideal .
• The activity coefficients are functions of composition
and temperature.
Chemical kinetics:
• Arrhenious temperature dependence.

k  e  E / RT

Where k is the specific reaction rate

E is the activation energy and
 is the pre exponential factor.
This gives the non linearity in the chemical engg. System.
• Law of mass action

1  dn j 
R  
v jV  dt  R

Where vj is the stoichiometric coefficient + ve for products

and – ve for reactants.
N.B. Need to know the rate expressions based on reaction
kinetics.