Development of Dynamic Models

Illustrative Example: A Blending Process

Chapter 2

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 
1
 or d  Vρ 
 w1  w2  w (2-2)
dt
where w1, w2, and w are mass flow rates.

The unsteady-state component balance is:

Chapter 2

d  Vρx 
 w1 x1  w2 x2  wx (2-3)
dt

The corresponding steady-state model was derived in Ch. 1 (cf.

Eqs. 1-1 and 1-2).
0  w1  w2  w (2-4)
0  w1x1  w2 x2  wx (2-5)

2
 Table 2.2. Degrees of Freedom Analysis
1. List all quantities in the model that are known constants (or
parameters that can be specified) on the basis of equipment
dimensions, known physical properties, etc.
2. Determine the number of equations NE and the number of
Chapter 2

process variables, NV. Note that time t is not considered to be

a process variable because it is neither a process input nor a
process output.
3. Calculate the number of degrees of freedom, NF = NV - NE.
4. Identify the NE output variables that will be obtained by
solving the process model.
5. Identify the NF input variables that must be specified as either
disturbance variables or manipulated variables, in order to
utilize the NF degrees of freedom.
6
 Conservation Laws
Theoretical models of chemical processes are based on
conservation laws.

Conservation of Mass
 rate of mass  rate of mass  rate of mass 
Chapter 2

    (2-6)

accumulation   in   out 

Conservation of Component i
rate of component i  rate of component i 
  
 accumulation   in 

rate of component i  rate of component i 

   (2-7)
 out   produced 
7
 Conservation of Energy
The general law of energy conservation is also called the First
Law of Thermodynamics. It can be expressed as:
rate of energy  rate of energy in  rate of energy out 
   
 accumulation   by convection   by convection 
Chapter 2

net rate of heat addition   net rate of work 

   
  to the system from   performed on the system  (2-8)
 the surroundings   by the surroundings 
   

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)

8
 For the processes and examples considered in this book, it
is appropriate to make two assumptions:

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
Chapter 2

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)
  denotes the difference
U int  the internal energy of
between outlet and inlet
the system conditions of the flowing

H  enthalpy per unit mass streams; therefore

w  mass flow rate  
-Δ wH = rate of enthalpy of the inlet
Q  rate of heat transfer to the system stream(s) - the enthalpy
of the outlet stream(s) 9
 The analogous equation for molar quantities is,
dU int
dt

  wH 
  Q (2-11)

where H is the enthalpy per mole and w is the molar flow rate.

In order to derive dynamic models of processes from the general

Chapter 2

energy balances in Eqs. 2-10 and 2-11, expressions for Uint and Ĥ
or H are required, which can be derived from thermodynamics.

The Blending Process Revisited

For constant  , Eqs. 2-2 and 2-3 become:
dV
  w1  w2  w (2-12)
dt
 d  Vx 
 w1x1  w2 x2  wx (2-13)
dt 10
 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
Chapter 2

V   x  w1 x1  w2 x2  wx (2-15)
dt dt
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
  x1  x    x2  x  (2-18)
dt V  V 11
Chapter 2 EXAMPLE 2.1
Chapter 2
Chapter 2
Chapter 2
Chapter 2
Chapter 2
Chapter 2
 Chapter 2

19
 Chapter 2

20
 Chapter 2

21
 Chapter 2

22
 EXAMPLE 2.2
Chapter 2
Chapter 2
 Stirred-Tank Heating Process
Chapter 2

Figure 2.3 Stirred-tank heating process with constant holdup, V.

25
 Stirred-Tank Heating Process (cont’d.)

Assumptions:

1. Perfect mixing; thus, the exit temperature T is also the

Chapter 2

temperature of the tank contents.

2. The liquid holdup V is constant because the inlet and
outlet flow rates are equal.
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.

26
 Model Development - I
For a pure liquid at low or moderate pressures, the internal
energy is approximately equal to the enthalpy, Uint  H , and H
depends only on temperature. Consequently, in the
ˆ =
subsequent development, we assume that UUint ˆ
int H H
and
Chapter 2

where the caret (^) means per unit mass. As shown in

Appendix B, a differential change in temperature, dT,
produces a corresponding change in the internal energy per
unit mass,
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)
27
 Model Development - II
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
Chapter 2

Note that this term appears in the general energy balance of Eq. 2-
10.
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 (see Appendix B). Thus, (2-32) can be
written as:

Hˆ  C T  Tref (2-33)
28
 Model Development - III
For the inlet stream


Hˆ i  C Ti  Tref  (2-34)
Chapter 2

Substituting (2-33) and (2-34) into the convection term of (2-10)

gives:

    
 wHˆ  w C Ti  Tref   w C T  Tref 
     (2-35)

Finally, substitution of (2-31) and (2-35) into (2-10)

dT
V C  wC  Ti  T   Q (2-36)
dt

29
 Degrees of Freedom Analysis for the Stirred-Tank
Model:
3 parameters: V , ,C

4 variables: T , Ti , w, Q
1 equation: Eq. 2-36
Chapter 2

Thus the degrees of freedom are NF = 4 – 1 = 3. The process

variables are classified as:
1 output variable: T
3 input variables: Ti, w, Q

For temperature control purposes, it is reasonable to classify the

three inputs as:
2 disturbance variables: Ti, w
1 manipulated variable: Q 30
 Continuous Stirred Tank Reactor (CSTR)
Chapter 2

Fig. 2.6. Schematic diagram of a CSTR.

31
 CSTR: Model Development
Assumptions:
1. Single, irreversible reaction, A → B.
2. Perfect mixing.
3. The liquid volume V is kept constant by an overflow line.
4. The mass densities of the feed and product streams are equal
and constant. They are denoted by .
Chapter 2

5. Heat losses are negligible.

6. The reaction rate for the disappearance of A, r, is given by,
r = kcA (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).
7. 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.
32
 CSTR: Model Development (continued)
• Unsteady-state mass balance

Because  and V are constant, . Thus, the mass balance is not required.
Chapter 2

• Unsteady-state component balance

33
 Assumptions for the Unsteady-state Energy Balance:
Chapter 2

34
 Chapter 2

35