II Show how the unsteady-state Model (dynamic model) was derived using fundamental modelling

procedure for each of the following chemical processes

I. Stirred-Tank Heating Process: Constant Holdup

II. Stirred-Tank Heating Process: Variable Holdup

III. Electrically Heated Stirred Tank

IV. Steam-Heated Stirred Tank

V. Liquid Storage Systems

VI. The Continuous Stirred-Tank Reactor (CSTR)

VII. Staged Systems (a Three-Stage Absorber)

VIII. Distributed Parameter Systems (the Double-Pipe Heat Exchanger)

IX. Fed-Batch Bioreactor

Note: In the determination of dynamic model (mathematical model), there are steps to be
systematically followed (called fundamental modelling procedure) until the differential equation is
reached. That differential equation is the unsteady-state model or dynamic model or the
mathematical model of the chemical process. Of course, the differential equation has properties or
characteristics that we will be discussing as we go through the modules. It is a challenging task for
the chemical engineer to determine this differential equation. Every chemical process has its
unique differential equation.
An a. Stirred-Tank Heating Process: Constant Holdup
s
Consider the stirred-tank heating system shown in the figure below:

The liquid inlet stream consists of a single component with a mass flow rate wi and an inlet
temperature Ti. The tank contents are agitated and heated using an electrical heater that provides
a heating rate, Q. A dynamic model will be developed based on the following assumptions:
1. Perfect mixing; thus, the exit temperature T is also the temperature of the tank contents.
2. The inlet and outlet flow rates are equal; thus, wi = w and the liquid holdup V is constant.

3. The density ρ and heat capacity C of the liquid are assumed to be constant. Thus, their
temperature dependence is neglected.
4. Heat losses are negligible.

In general, dynamic models are based on conservation laws. For this example, it is clear that we
should consider an energy balance, because thermal effects predominate. A mass balance is not
required in view of Assumptions 2 and 3. Next, we show how the general energy balance can be
simplified.

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 subsequent
development, we assume that Uint = H and Û int = Ĥ where the caret (̂) means per unit mass. A
differential change in temperature, dT, produces a corresponding change in the internal energy
per unit mass, dÛ int,

where C is the constant pressure heat capacity (assumed to be constant). The total internal
energy of the liquid in the tank can be expressed as the product of Û int and the mass in the tank,
ρV:

An expression for the rate of internal energy accumulation can be derived from the equations
above:

Note that this term appears in the general energy balance of

Next, we derive an expression for the enthalpy term that appears on the right-hand side of the
equation above. Suppose that the liquid in the tank is at a temperature T and has an enthalpy, Hˆ .
Integrating

from a reference temperature Tref to T gives

Similarly, for the inlet stream:

Substituting these two equations into the convection term of the general energy balance gives

Finally, substitution of

and

Into the general material balance gives the desired dynamic model of the stirred-tank heating
system:

dT
VpC =wC ( T i −T ) +Q
dt

Note that the Tref terms have canceled, because C was assumed to be constant, and thus
independent of temperature. A degrees of freedom analysis for this model gives:

3 parameters: V, ρ, C

4 variables: T, Ti, w, Q
For control purposes, it is reasonable to classify the three inputs as:

2 disturbance variables: Ti, w

1 manipulated variable: Q

b. Stirred-Tank Heating Process: Variable Holdup

Now we consider the more general situation in which the tank holdup can vary with time. This
analysis also is based on Assumptions 1, 3, and 4 of the previous section. Now an overall mass
balance is needed, because the holdup is not constant. The overall mass balance is

The energy balance for the current stirred-tank heating system can be derived from the general
energy balance in analogy with the derivation of dynamic model of Stirred-Tank Heating Process:
Constant Holdup. We again assume that Uint = H for the liquid in the tank. Thus, for constant ρ,

From the definition of −Δ(wĤ ) and the equations previously mentioned above, it follows that

−Δ(wĤ ) = wiĤ i − wĤ = wiC(Ti − Tref) −wC(T − Tref)

where wi and w are the mass flow rates of the inlet and outlet streams, respectively. These
equations into the general energy balance gives

Next we simplify the dynamic model. Because ρ is constant, the overall mass balance equation
can be written as

The chain rule can be applied to expand the left side of this equation
for constant C and ρ:

From these equations:

or

it follows that dĤ/dt = CdT/dt. Substituting this expression and these equations

and

and into this equation:

Gives

Substituting the equation above into

and
C( T – Tref)(wi – w) + pCV dT/dt = wiC (Ti – Tref) – wC (T- Tref) + Q

Rearranging the equations previously mentioned above provides a simpler form for the dynamic
model:

dV 1
= ( w −w )
dt ρ 1

dT w1 Q
= ( T 1−T ) +
dt Vρ ρCV
These two equations above provide a model that can be solved for the two outputs (V and T) if the
two parameters (ρ and C) are known and the four inputs (wi, w, Ti, and Q) are known functions of
time (i.e., there are four remaining degrees of freedom).

c. Electrically Heated Stirred Tank

The unsteady-state energy balance for the tank and the heating element can be written as:

Differentiating the equation:

d. Steam-Heated Stirred Tank

e. Liquid Storage Systems

Mass balance equation:

In analogy to Ohm’s Law for electrical circuit:

Rearranging the equation:

Substituting the previous equation:

f. The Continuous Stirred-Tank Reactor (CSTR)

Continuous stirred-tank reactors (CSTR) have widespread application in industry and embody
many features of other types of reactors. CSTR models tend to be simpler than models for other
types of continuous reactors such as tubular reactors and packed-bed reactors. Consequently, a
CSTR model provides a convenient way of illustrating modeling principles for chemical reactors.

Consider a simple liquid-phase, irreversible chemical reaction where chemical species A reacts to
form species B. The reaction can be written as A → B. We assume that the rate of reaction is first-
order with respect to component A,

(6-1) r =kc A

where r is the rate of reaction of A per unit volume, k is the reaction rate constant (with units of
reciprocal time), and cA is the molar concentration of species A. For single-phase reactions, the
rate constant is typically a strong function of reaction temperature given by the Arrhenius relation,

(6-2)

−E
k =k 0 exp ⁡( )
RT

where k0 is the frequency factor, E is the activation energy, and R is the gas constant. The
expressions in Eqs. 6-1 and 6-2 are based on theoretical considerations, but model parameters k0
and E are usually determined by fitting experimental data. Thus, these two equations can be
considered to be semi-empirical relations.

The schematic diagram of the CSTR is shown below.

The inlet stream consists of pure component A with molar concentration, cAi. A cooling coil is used
to maintain the reaction mixture at the desired operating temperature by removing heat that is
released in the exothermic reaction. Our initial CSTR model development is based on three
assumptions:

1. The CSTR is perfectly mixed.

2. The mass densities of the feed and product streams are equal and constant. They are denoted
by ρ.
3. The liquid volume V in the reactor is kept constant by an overflow line.
For these assumptions, the unsteady-state mass balance for the CSTR is

(6-3)

d ( ρV )
= ρq 1−ρqBecause V and ρ are constant, Eq. 6-3 reduces to
dt

(6-4)

q=q i

Thus, even though the inlet and outlet flow rates may change due to upstream or downstream
conditions, 6-4 must be satisfied at all times. In the schematic diagram, both flow rates are
denoted by the symbol q. For the stated assumptions, the unsteady-state component balances for
species A (in molar concentration units) is

(6-5)
This balance is a special case of the general component balance in Eq. 6-5.

dCA
V =q ( C Ai−C A ) −Vk C A
dt
Next, we consider an unsteady-state energy balance for the CSTR. But first we make five
additional assumptions:
4. The thermal capacitances of the coolant and the cooling coil wall are negligible compared to the
thermal capacitance of the liquid in the tank.

5. All of the coolant is at a uniform temperature, Tc. (That is, the increase in coolant temperature
as the coolant passes through the coil is neglected.)
6. The rate of heat transfer from the reactor contents to the coolant is given by

(6-6)

Q=UA ( T c −T )where U is the overall heat transfer coefficient and A is the heat transfer area.

Both of these model parameters are assumed to be constant.

7. The enthalpy change associated with the mixing of the feed and the liquid in the tank is
negligible compared with the enthalpy change for the chemical reaction. In other words, the heat
of mixing is negligible compared to the heat of reaction.
8. Shaft work and heat losses to the ambient can be neglected.
The following form of the CSTR energy balance is convenient for analysis and can be derived from
Eqs. 6-1 and 6-2 and Assumptions 1–8.

dT
VρC =wC ( T I −T ) + (−∆ H R ) Vk C A +UA ( T C −T )
dt

g. Staged Systems (a Three-Stage Absorber)

A simple linear relation is often assumed for stage i:

Assuming constant liquid hold-up. The compenent material balance for any stage i is:

Substituting the two equations:

h. Distributed Parameter Systems (the Double-Pipe Heat Exchanger)

Using conservation law:
Arranging this equation for the yield:

Considering the energy balance for the wall:

Arranging previous equations:

Where:

Using backward difference approximation for the derivative of the yield:

Arranging previous equations:

i. Fed-Batch Bioreactor
A broad class of bioreactions can be represented in simplified forms as:

The following yield coefficients are based on the reaction stoichiometry:

A standard reaction rate expression to describe the rate of cell growth with a single limiting
substrate is given by:

The dynamic model of the fed-batch bioreactor consists of individual balances for substrate, cell
mass and product plus overall mass balance. The general form of each balance is:
 The overall mass balance is:

III Hint: To determine the variable to be maintained and controlled through its mathematical model,
look for a variable that changes with time (ex. if the dynamic model contains dx/dt then the
variable that changes with time is x). Here, x is the controlled variable).
An III.
s a. Stirred-Tank Heating Process: Constant Holdup Dynamic Model

Controlled Variable: T (Temperature)

b. Stirred-Tank Heating Process: Variable Holdup Dynamic Model

Controlled Variable: T (Temperature), V (Volume)

c. Electrically Heated Stirred Tank

Controlled Variable: T (Temperature at Initial Condition)

d. Steam-Heated Stirred Tank

Controlled Variable: T (Temperature)

e. Liquid Storage Systems

Controlled Variable: h (Liquid level or Head)

f. The Continuous Stirred-Tank Reactor (CSTR)

Controlled Variable: T (Temperature)

g. Staged Systems (a Three-Stage Absorber)

Controlled Variable: x 1 , x 2 , x 3

h. Distributed Parameter Systems (the Double-Pipe Heat Exchanger) Dynamic Model

Controlled Variable: : T L1 , T L2 , T w 1, T w 2
 i. Fed-Batch Bioreactor

Controlled Variable: V (Volume), XV (Cells), PV (Product), SV (Substrate)

IV Each of the dynamic model in no. 2 was derived based on the use of the fundamental theories or
laws such as conservation of mass, energy and momentum. There are, of course, many
approaches to understand physical systems the behavior of anything we encounter in our lives)
but engineers, tend to favor fundamental models. Cite the three (3) reasons for this tendency of
engineers.
An There are several reasons as to why engineers tend to stick with the fundamental theories and
s laws currently in existence. Some of the specific reasons are:
1. Fundamental models are based on repeated experiments and observations. Meaning to
say, it is as accurate and as correct than other approaches in existence.
2. These fundamental models are backed up with mathematical computations, which
engineers can use for finding specific values for different variables or which they can use
to predict an outcome of an experiment.
3. Fundamental models are backed up with mathematical computations (as stated in number
2). All these existing mathematical computations is accompanied with several statements
and equations that makes computations for unknown variables faster and more
convenient that other approaches.

End of Assignment No 2