Theoretical Models of

Chemical Processes
Chapter 2

Mathematical Model (Eykhoff, 1974)

“a representation of the essential aspects of an existing
system (or a system to be constructed) which
represents knowledge of that system in a usable form”

Everything should be made as simple as possible, but

no simpler.
 General Modeling Principles
• The model equations are at best an approximation to the real
process.
• Adage: “All models are wrong, but some are useful.”
• Modeling inherently involves a compromise between model
Chapter 2

accuracy and complexity on one hand, and the cost and effort
required to develop the model, on the other hand.
• Process modeling is both an art and a science. Creativity is
required to make simplifying assumptions that result in an
appropriate model.
• Dynamic models of chemical processes consist of ordinary
differential equations (ODE) and/or partial differential equations
(PDE), plus related algebraic equations.
 Table 2.1. A Systematic Approach for
Developing Dynamic Models
1. State the modeling objectives and the end use of the model.
They determine the required levels of model detail and model
accuracy.
Chapter 2

2. Draw a schematic diagram of the process and label all process

variables.
3. List all of the assumptions that are involved in developing the
model. Try for parsimony; the model should be no more
complicated than necessary to meet the modeling objectives.
4. Determine whether spatial variations of process variables are
important. If so, a partial differential equation model will be
required.
5. Write appropriate conservation equations (mass, component,
energy, and so forth).
 Table 2.1. (continued)
6. Introduce equilibrium relations and other algebraic
equations (from thermodynamics, transport phenomena,
chemical kinetics, equipment geometry, etc.).
7. Perform a degrees of freedom analysis (Section 2.3) to
Chapter 2

ensure that the model equations can be solved.

8. Simplify the model. It is often possible to arrange the
equations so that the dependent variables (outputs) appear
on the left side and the independent variables (inputs)
appear on the right side. This model form is convenient
for computer simulation and subsequent analysis.
9. Classify inputs as disturbance variables or as manipulated
variables.
 Modeling Approaches
 Physical/chemical (fundamental, global)
• Model structure by theoretical analysis
 Material/energy balances
 Heat, mass, and momentum transfer
Chapter 2

 Thermodynamics, chemical kinetics

 Physical property relationships
• Model complexity must be determined
(assumptions)
• Can be computationally expensive (not real-
time)
• May be expensive/time-consuming to obtain
• Good for extrapolation, scale-up
• Does not require experimental data to obtain
(data required for validation and fitting)
 • 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 
 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:

Utot  Uint  U KE  U PE (2-9)

  Black box (empirical)
• Large number of unknown parameters
• Can be obtained quickly (e.g., linear regression)
• Model structure is subjective
Chapter 2

• Dangerous to extrapolate
 Semi-empirical
• Compromise of first two approaches
• Model structure may be simpler
• Typically 2 to 10 physical parameters estimated
(nonlinear regression)
• Good versatility, can be extrapolated
• Can be run in real-time
 • linear regression
y  c0  c1 x  c2 x 2
• nonlinear regression
y  K 1  et / 
Chapter 2

• number of parameters affects accuracy of model,

but confidence limits on the parameters fitted must
be evaluated
• objective function for data fitting – minimize sum of
squares of errors between data points and model
predictions (use optimization code to fit
parameters)
• nonlinear models such as neural nets are
becoming popular (automatic modeling)
 Number of
births (West
Germany)
Chapter 2

Number of sightings of storks

Uses of Mathematical Modeling

• to improve understanding of the process
• to optimize process design/operating conditions
• to design a control strategy for the process
• to train operating personnel
Chapter 2
Chapter 2
 •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 
 d Vρ 
or
 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 
 w1x1  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)
 The Blending Process Revisited
For constant  , Eqs. 2-2 and 2-3 become:
Chapter 2

dV
  w1  w2  w (2-12)
dt
 d Vx 
 w1x1  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
Chapter 2

V   x  w1x1  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
 Example 2.1
 Stirred-tank blending process w/ 2m3
 ρ = 900 kg/m3
(a) w1=500kg/min, w2=200kg/min, x1=0.4, x2=0.75
Chapter 2

st-st value of x ?
(b) w1 changes from 500 to 400 kg/min
determine an expression for x(t) and plot it
(c) w2 changes from 200 to 100 kg/min
(d) x1 changes from 0.4 to 0.6
(e) Plot the normalized response xN (t)
𝑥 𝑡 − 𝑥(0)
𝑥𝑁(𝑡) =
𝑥 ∞ − 𝑥(0)
Chapter 2
Chapter 2 Stirred-Tank Heating Process

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

 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.
 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)
 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 subsequent
 
development, we assume that Uint = H and U int  H where the
Chapter 2

caret (^) means per unit mass. As shown in Appendix C, a

differential change in temperature, dT, produces a corresponding
change in the internal energy per unit mass, dUˆ int ,

 
d U int  d H  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:

Uint  VUˆ int (2-30)

 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,
 
H  H ref  C (T  T ) (2-32)
ref

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

assume that Hˆ ref  0 (see Appendix C). Thus, (2-32) can be
written as:

Hˆ  C T  Tref  (2-33)
 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
 2.4.2. Stirred-Tank Heating Process
: variable Holdup - 1
 Assumption: tank holdup varies with time
 overall mass balance,
d (V )
Chapter 2

 wi  w (2-36)
dt
 Uint= H for liquid,
 
dU int dH d ( V H ) d (V H )
   (2-38)
dt dt dt dt

  
 (w H )  wi H  w H  wi C (Ti  Tref )  wC (T  Tref ) Integrating
(2-29)
 2.4.2. Stirred-Tank Heating Process
: variable Holdup - 2

dU int 
 ( w H )  Q (2-10)
dt
Chapter 2


d (V H ) 
  ( w H )  Q
dt
 wi C (Ti  Tref )  wC (T  Tref )  Q (2-40)

d (V ) dV
 )  wi  w   (2-41)
dt dt

 by Chain rule,
 
d (V H ) d (H )  d (V )
  V H (2-42)
dt dt dt
 2.4.2. Stirred-Tank Heating Process
: variable Holdup - 3

d (V H ) d (T )  
  VC  H ( wi  w) Using H  C (T  Tref ) (2-33)
dt dt
Chapter 2

dT
 VC  C (T  Tref )(wi  w) (2-43)
dt

d (V H )
  wi C (Ti  Tref )  wC (T  Tref )  Q (2-40)
dt

dT wi Q
 (Ti  T )  (2-46) Can be solved for,
dt V CV 2 outputs (V, T)

If the 2 parameters (ρ, C)

dV 1
 ( wi  w) (2-45) 4 inputs (wi, w, Ti, Q) are
dt  known function of time
 2.4.3. Electrically Heated Stirred Tank
 Electrical heating rate Q directly affects the temperature of
element
 Assume that the element has a uniform temperature, Te
Chapter 2

(2-36) VC dT  wC (Ti  T )  Q

dt
 Me : mass of metal in the heating element
 Ce : specific heat of metal in the heating element
Q  he Ae T  he Ae (Te  T )

(2-36) mC dT  wC (Ti  T )  he Ae (Te  T ) (2-47)

dt
dTe
mCe  Q  he Ae (Te  T )
dt
 2.4.5. Liquid Storage Systems - 1

d ( V ) (2-53)
 qi  q
dt

Assume constant density(  )

Chapter 2

dh
A  qi  q (2-54)
dt

h  qRv h: head, Rv= resistance of the line or valve

(similar to E=IR)
1
q h : Flow-head equation
Rv

dh 1
A  qi  h (2-57)
dt Rv
 2.4.5. Liquid Storage Systems - 2
dh 1
A  qi  h (2-57)
dt Rv

 Pressure drop across valve,

Chapter 2

P  P  Pa P: pressure of tank bottom

Pa : pressure at the end of exit line
(assume ambient P)

 by Bernoulli equation,

P  Pa
q  Cv
*
 (2-59) gc :
gravitational
conversion factor
g
P  Pa  h (2-60)
gc
 2.4.5. Liquid Storage Systems - 3

dh
A  qi  q (2-57)
dt
Chapter 2

P  Pa
 qi  Cv
*


dh  q  C h Where, Cv  Cv* g
A i v gc
dt
 2.4.6. The Continuous Stirred-Tank
Reactor (CSTR) - 1
A→B : 1st order of component A
r  kCA
Chapter 2

r = rate of reaction of A per volume,

k = reaction rate constant
CA = molar concentration of species A

usually determined by fitting experimental data

 by Arrhenius relation, → Thus, semi-empirical relations.

k  ko exp(  E / RT ) ko = frequency factor

E = activation energy
R = gas constant
 2.4.6. The Continuous Stirred-Tank
Reactor (CSTR) - 2
 Assumptions,
1. CSTR is perfectly mixed
Chapter 2

2. mass densities of feed and product are equal and constant (ρ)

3. liquid volume, V in the reactor is kept constant by an overflow line

 Unsteady-steady mass balance,

d ( V )
 qi  q
dt

 V, ρ are constant,
q  qi
 2.4.6. The Continuous Stirred-Tank
Reactor (CSTR) - 3
 by reaction kinetics,
d (C A )
 q(C Ai  C A )  VkCA
dt
Chapter 2

4. Thermal capacity of the coolant and cooling coil are negligible compared
to the thermal capacitance of the liquid in the tank
5. All of the coolant is at a uniform temperature, Tc
6. The rate of heat transfer from the reactor contents to the coolant is given by
Q=UA(Tc-T)
7. Enthalpy change associated with the mixing of the feed and the liquid
in the tank is negligible compared to the enthalpy change for the chemical
reaction.
8. Shaft work and heat losses to the ambient can be neglected
 2.4.6. The Continuous Stirred-Tank
Reactor (CSTR) - 4

 CSTR Energy Balance,

Chapter 2

dT
VC  wC (Ti  T )  (H R )VkCA  UA(TC  T )
dt
Chapter 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.
Chapter 2

2. Determine the number of equations NE and the number of

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.
 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
 HW
Exercise
2.1
2.3
Chapter 2

2.7