CHAPTER

2
Prepared by Dr. Suhadat
Chapter Overview & Learning Outcomes
2.1 Dynamic process model and principles
2.2 Development of dynamic models
2.3 Laplace transform
2.4 ODE and partial fraction expansion 

At the end of this chapter, YOU should be able to:

•1.Apply and derive unsteady-state models (dynamic model)
of chemical processes from physical and chemical principles.
2. Develop a dynamic process model in a systematic approach with
degree of freedom analysis
3. Apply convert Laplace transform, F(s) to function of time, f(t) or
vice verse
4. Solve linear differential equation using Laplace Transform
technique involved with partial fraction expansion
1.1 Dynamic process model and principles
 In this chapter, we consider the derivation of unsteady-state
models of chemical processes from physical and chemical
principles.
 Unsteady-state model also referred to as dynamics models,
where it is derived from first principle of conservation laws

Why dynamic models is needed??....Role of dynamic models in

process dynamics and control;

1.
 2.

3.

4.

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 General modelling principles
Principle of conservation;
Accumulation S
= Inlet S – Outlet S + Generation S – Consumption S

The quantity of S can be any of  the following fundamental 
quantities:

Total mass, Mass of individual components,

Total energy, Momentum

*Total mass and energy cannot be 
generated, neither do they  disappear

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 Conservation Laws in dynamic models;
1. Conservation of total Mass

 rate of mass  rate of mass  rate of mass 

    (2-6)
accumulation   in   out 

Depends on the information given;

or

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 Conservation of Component i

- /consumed

Based on Mass i
component
Depends on the information given;

Based on Mole i
component

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 Conservation of total Energy
The general law of energy conservation is also called the First
Law of Thermodynamics. It can be expressed as:

The total energy of a thermodynamic system, Utot, is the sum of

its internal energy, kinetic energy, and potential energy:
U tot  U int  U KE  U PE (2-9)

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 Two assumptions for processes with energy conservation:
1. Changes in potential energy and kinetic energy can be
neglected because they are small in comparison with changes
in internal energy.
2. The net rate of work can be neglected because it is small
compared to the rates of heat transfer and convection.

For these reasonable assumptions, the energy balance in

Eq. 2-8 can be written as;
dU int 
dt
  wH  Q  
(2-10)
By convection
  denotes the difference
U int  the internal energy of
between outlet and inlet
the system conditions of the flowing
 streams; therefore
H  enthalpy per unit mass 
w  mass flow rate  
-Δ wH = rate of enthalpy of the inlet
stream(s) - the enthalpy
Q  rate of heat transfer to the system
of the outlet stream(s)

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 Illustrative example on modeling of a dynamic model:
A Blending Process

Assumption:
1.Perfect mixing
(composition outlet
stream same as in the
tank)
2.Constant density
Figure 2.1. Stirred-tank blending process.
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 An unsteady-state mass balance for the blending system:
rate of accumulation   rate of   rate of 
    (2-1)
 of mass in the tank   mass in   mass out 

d  Vρ 
 w1  w2  w (2-2)
dt
where w1, w2, and w are mass flow rates.

The unsteady-state component balance is:

d  Vρx 
 w1 x1  w2 x2  wx (2-3)
dt
The corresponding steady-state model was derived in Chp. 1
(Eq. 1-1 and 1-2).
0  w1  w2  w (2-4)
0  w1 x1  w2 x2  wx (2-5)
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 For constant  , Eqs. 2-2 and 2-3 become:
dV
  w1  w2  w (2-12)
dt
 d  Vx 
 w1 x1  w2 x2  wx (2-13)
dt

Equation 2-13 can be simplified by expanding the accumulation

term using the “chain rule” for differentiation of a product:

d  Vx  dx dV
  V  x (2-14)
dt dt dt

Substitution of (2-14) into (2-13) gives:

dx dV
V  x  w1x1  w2 x2  wx (2-15)
dt dt

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 Substitution of the mass balance in (2-12) for  dV/dt
in (2-15) gives:
dx
V  x  w1  w2  w   w1x1  w2 x2  wx (2-16)
dt
After canceling common terms and rearranging (2-12) and (2-16),
a more convenient model form is obtained:
dV 1
  w1  w2  w  (2-17)
dt 
dx w1 w2
  1 
x  x   x2  x  (2-18)
dt V  V

*The dynamics model in eqs 2.17 and 2-18 is based on only two
assumptions (perfect mixing and constant density).
*For special situations, the liquid volume V is constant (overflow line
exist), which dV/dt =0, therefore inlet flow rate = outlet flow rate
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 1.2 Development of dynamic models
Degree of Freedom Analysis

 To simulate a process, we must ensure that its model

equations constitute a solvable set of relations.
 DOF is conducted for a complex equations in order to
determine whether the model have a unique solution or
not
 A unique solution is where the number of unknown
variables must equal to the number of independent model
equations.

DOF  NV  NE
*NV=number of variables
*NE= number of equations

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  DOF=0,
- system can be solved with exactly specified, unique solution
- Number of equations is equal to number of process variables
- set of equations has a solution

 IF DOF > 0
– system under specified

– Number of variables more than equations

– Need more equation/solution

 IF DOF < 0
– system over specified

– Number of equations more than variables

– No solution

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 Dynamic models of representative processes
1. Liquid storage system- constant density and area

Resistance
valve with
Fixed valve with
turbulence flow
turbulence flow

3 variables: fo, f, h or qi, q, h

1 equation: mass balance eq
Thus the degrees of freedom are DOF = 3 – 1 = 2.
The process variables are classified as:
1 output variable: h (solvable by 1 eq)
2 input variables: fo(DV) f (MV) or qi (DV), q (MV)-utilized DOF
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 1. Mass balance: accumulation = in - out
d ( V ) dV
  0 f 0  f At constant density;  f0  f
dt dt

dV d ( Ah) dh
2. Tank volume with constant area: V = Ah,  A
dt dt dt
3. Flow through a valve:
fixed valve with turbulence flow, f  CV h
Or Resistance flow valve, q =

dh
Therefore, substitute 2 and 3 into 1; f0  CV h  A
dt
Revise on previous DOF
NV= 3 (fo, f, h)
NE=3 (mass balance, Tank volume eqn, Valve flow eqn)
DOF = NV-NE = 0
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 2. Stirred-Tank Heating Process- constant holdup V

Assumptions:
1. Perfect mixing; thus, the exit temperature T is also the
temperature of the tank contents.
2. The liquid holdup V is constant because the inlet and outlet
flow rates are equal.(overflow line)
3. The density and heat capacity C of the liquid are assumed to
be constant. Thus, their temperature dependence is neglected.
4. Heat losses are negligible.

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 Mass conservation (from eq 2-6)

Energy conservation (from eq 2-10)

dU int
 

  wH  Q (2-10)
dt

1. For a pure liquid at low or moderate pressures, the internal

H
energy is approximately equal to the enthalpy, Uint , and
H depends only on temperature.
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 2. Consequently, we assume that Uint = H and Uˆ int  Hˆ where

dUˆ int  dHˆ  CdT (2-29)

where C is the constant pressure heat capacity (assumed to be
constant). The total internal energy of the liquid in the tank is:

U int  VUˆ int (2-30)

An expression for the rate of internal energy accumulation can be

derived from Eqs. (2-29) and (2-30):

dU int dT
 VC (2-31)
dt dt

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 Suppose that the liquid in the tank is at a temperature T and has
an enthalpy, Ĥ . Integrating Eq. 2-29 from a reference
temperature Tref to T gives,


Hˆ  Hˆ ref  C T  Tref  (2-32)

where Hˆ ref is the value of Ĥ at Tref. Without loss of generality, we

assume that Hˆ ref  0 .Thus, (2-32) can be written as:


Hˆ  C T  Tref  (2-33)

For the inlet stream;


Hˆ i  C Ti  Tref  (2-34)

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 Substituting (2-33) and (2-34) into the convection term of (2-10)
gives:
   
 wHˆ  wi C Ti  Tref   w C T  Tref  (2-35)
     
From mass conservation derivation where w = wi is substitute into
eq 2-35, expand and rearranged;

= wCTi - wCTref – wCT + wCTref (2-35 rearranged)

Finally, substitution of (2-31) and (2-35 rearranged) into (2-10)
dT
V C  wC  Ti  T   Q (2-36)
dt

Simplified;
22

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 3. Stirred-Tank Heating Process- variable holdup V
 Now we consider tank holdup can vary with time. This
analysis based on the previous assumption except for liquid
holdup V (varies).
 Now, an overall mass balance is needed because the
holdup is not constant
The overall mass balance; d (V ) (2-37)
 wi  w
dt

The energy balance for the current stirred-tank heating system

can be derived from Eq. 2-10 in analogy with the derivation of
Eq. 2-36. We again assume that Uint = H for the liquid in the tank.
Thus, for constant ;
d (U int ) dH d ( VHˆ ) d (VHˆ )
   (2-38)
dt dt dt dt

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 where wi and w are the mass flow rates of the inlet and outlet
streams, respectively. Substituting (2-38) and (2-39) into (2-10)
gives;
d (VHˆ )
  wi C (Ti  Tref )  wC (T  Tref )  Q (2-40)
dt

Next we simplify the dynamic model. Because ρ is constant,

Eq (2-37) can be written as;
dV
  wi  w (2-41)
dt

The ‘chain rule’ can be applied to expand the left side of (2-40)
for constant C and ;

d (VHˆ ) dHˆ ˆ dV
  V  H (2-42)
dt dt dt

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 From Eq. 2-29 or 2-33, it follows that dHˆ /dt  CdT/dt.
Substituting this expression and Eq. 2-33 and 2-41 into Eq. 2-42
gives;
d (VHˆ ) dT
  C (T  Tref )(wi  w)  CV
dt dt (2-43)

Substituting (2-43) into (2-40) and rearranging give;

dT
C (T  Tref )(wi  w)  CV  wiC (Ti  Tref )  wC (T  Tref )  Q (2-44)
dt

Rearranging (2-41) and (2-44) provides a simpler form for the

dynamic model;
dV
  ( wi  w) (2-45)
dt
dT w Q
 i (Ti  T )  (2-46)
dt V CV 25

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 4. Continuous Stirred-Tank Reactor- CSTR

Assumptions:
1. Perfect mixing (concentration outlet stream same as in tank).
2. The liquid volume V is kept constant by an overflow line.
3. The mass densities of the feed and product streams are equal
and constant. They are denoted by ρ.
4. Heat losses are negligible.

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 * The reaction can be written as irreversible reaction, A → B.
The rate of reaction is first order with respect to component A,
(2-62)
where r  =  moles of A reacted per unit time, per unit volume, cA
is the concentration of A (moles per unit volume), and k is the rate
constant (units of reciprocal time).

The rate constant has an Arrhenius temperature dependence:

k = k0 exp(-E / RT ) (2-63)
where k0 is the frequency factor, E is the activation energy,
and R is the the gas constant.

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 • Unsteady-state
mass balance:
(2-64)

Because  and V are constant,

(2-65)
• Unsteady-state
component balance:
(2-66)

• Unsteady-state Energy balance for CSTR with assumptions:

1.

2.

3.

Q=UA(Tc-T) (2-67)

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 4.

5.

* The following form of the CSTR energy balance is convenient for

analysis and can be derived from Eq 2-62 and 2-36

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 2.3 Laplace transform
 In previous chapter, we developed a number of mathematical
models that describe the dynamic operation of selected
processes.
 Solving such models, requires either analytical or numerical
integration of the differential equations.
 One important class of models includes systems described by
linear differential equations.
 In this chapter, we introduce a mathematical tool, the Laplace
transform, that can significantly reduce the effort required to
solve linear differential equation models analytically.
 A major benefit is that this transformation converts differential
equations to algebraic equations, which can simplify the
mathematical manipulations required to obtain a solution.
 Advantageous for block diagram analysis

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 Laplace transform
 The Laplace transform of a function, f(t), is defined as;

F ( s )  L  f (t )   f  t  e st dt (3-1)
0

where F(s) is the symbol for the Laplace transform, L is the

Laplace transform operator, and f(t) is some function of time, t.

Note:
When the integration is performed, where L operator
transform a time domain function f(t) into an s domain
function, F(s). s is a complex variable:
s = a + bj,

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 Inverse Laplace Transform, L-1:

 By definition, the inverse Laplace transform operator, L-1,

converts an s-domain function, F(s) to the corresponding
time domain function, f(t).

f  t   L1  F  s  

 One of the important properties of the Laplace transform

and the inverse Laplace transform is that they are linear
operators.

L  ax  t   by  t    aL  x  t    bL  y  t  
 aX  s   bY  s  (3-3)

 Laplace transforms table (3.1) for various time-domain

function
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  Need to be able to use tables 3.1 to convert to s
domain and convert back to t domain

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 Example of Laplace Transforms of Common Functions


Standard Formula for Laplace L(f (t)) =  f (t)e -st dt

0

1.

2. Proved in
Table 3.1

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 3.

4.

initial condition at t = 0

Other transform:

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 General steps to solve ODE using Laplace

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 2.4 ODE (Ordinary differential equation)
and partial fraction expansion 
Procedure to solve ODE:
1. Take the L of both sides of
the ODE.
2. Rearrange the resulting
algebraic equation in the s
domain to solve for the L
of the output variable, e.g.,
Y(s).
3. Perform a partial fraction
expansion.
4. Use the L-1 to find y(t)
from the expression for
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 Partial fraction expansion
 The high-order polynomial in a Laplace transform solution
arises from the ODE terms (its characteristic polynomial).
 The factors of the characteristic polynomial correspond to the
roots of the characteristic polynomial set equal to zero.
 Once the factors are obtained, the Laplace transform is then
expanded into partial fraction.
Example: Laplace transform eq given by;

Where α1 and α2 are unspecified coefficients that must be satisfied eq 3-42

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  In general, for every partial fraction expansion, there will
be a unique set of α1 and α2 that satisfy the equation.
 There are several methods for calculating the appropriate
values of α1 and α1 in eq 3-42.

Method 1;

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 Method 2; Heaviside expansion

(s+5)/(s+4) = α1 + α2 (s+1)/(s+4)

Sub s = -1

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 Therefore,

Then, proceed to inverse

Laplace (L-1) for the Laplace
equation obtained to get in time
domain y(t)

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 Example 3.1: Solve question with ODE to time domain

Find the time domain, y(t) for the given ODE;

dy
5  4y  2 y  0  1 (3-26)
dt
First, take L of both sides of (3-26), 2
5  sY  s   1  4Y  s  
s
5s  2
Rearrange, Y  s  (3-34)
s  5s  4 

Take L-1,
1 
5s  2  Proved using partial
y t  L   fraction expansion or
 s  5 s  4   directly solved From
Table 3.1 (line 11) or
(line 5 &13)
y  t   0.5  0.5e0.8t (3-37)
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 Solution example 3.1 using heavy side partial fraction ;

1  5s  2 
y t  L  
 
s 5 s  4 

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 Example 3.2 d3y d2y dy
3
 6 2
 11  6y  4
dt dt dt
y( 0 )= y( 0 )= y( 0 )= 0 system at rest (s.s.)

Step 1 Take L.T. (note zero initial conditions)

4
s 3Y(s)+ 6s 2Y(s)+11sY(s)  6Y (s ) =
s
Rearranging,
4
Y(s)=
( s 3  6s 2  11s  6) s
Step 2a. Factor denominator of Y(s)
s(s 3+6s 2+11s+6 )=s(s+1 )(s+2 )(s+3 )
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 Step 2b. Use partial fraction decomposition
4 α α α α
 1 2  3  4
s(s +1 )(s + 2 )(s + 3 ) s s  1 s  2 s  3

Multiply by s, set s = 0 4  α α α 
 α1  s  2  3  4 
(s +1 )(s + 2 )(s + 3 ) s 0  s  1 s  2 s  3  s 0
4 2
 α1 
1 2  3 3

For a2, multiply by (s+1), set s=-1 (same procedure for a3, a4)

2 2 2 2 2/3
α2  2, α3  2 , α4   (Y(s)=  +  )
3 3s s 1 s  2 s3

Step 3. Take inverse of L.T.

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 Important Properties of Laplace Transforms

1. Final Value Theorem

It can be used to find the steady-state value of a closed loop
system (providing that a steady-state value exists)..
* will discuss in chapter 3 and 4

lim y  t   lim  sY  s  
Statement of FVT: t  s 0

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 Example:
5s  2
Suppose, Y  s  (3-34)
s  5s  4 
Then,  5s  2 
y     lim y  t   lim    0.5
t  s 0  5s  4 

2. Time Delay
Time delays occur due to fluid flow, time required to do an
analysis (e.g., gas chromatograph). The delayed signal can be
represented as
y  t  θ θ  time delay
Also,
L  y  t  θ    eθsY  s 

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 Revisited: Steps to solve ODE using Laplace

Laplace
ODE eq, F(s)

complex
L-1, F(s) to f(t) expression
for Y(s) into
simpler
terms

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 Task (clone exam)

1. The following figure show a liquid storage with a fixed valve

( turbulence flow) . Analyze the degree of freedom with the
related equations for the liquid-level storage model

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 2. A small BBQ cylinder is attached to a large Liquefied
petroleum gas (LPG) gas supply through a valve. The mass
flowrate of gas (min) into the cylinder is proportional to the
difference in pressure between the cylinder (P) and the gas
supply (Ps) and inversely proportional to the resistance of the
valve (RV). Initially the cylinder is empty, and assume that the
temperature is constant.
 
Derive a differential equation which relates the pressure (P) in
the cylinder to the volume of the cylinder (V), the supply
pressure (Ps) and the resistance of the valve (RV).

(Hint: write an expression for the mass of gas using the ideal gas
law, PV = nRT)

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