MATHEMATICAL

MODELING OF
CHEMICAL
PROCESSES
Mathematical modeling of
Chemical Processes
Basic concept and definition
■ Mathematical modelling → mathematical representation of
the essential aspects of an existing process (or a process to
be constructed) in a usable form.
■ Process modelling is both an art and a science. Creativity is
required to make safe assumptions that result in an
appropriate model. Note that the mathematical model
should be made as simple as possible, but no simpler.
■ The model equations are at the best an approximation to the
real process.
Mathematical modeling of
Chemical Processes
■ Classification of mathematical models:
– Theoretical models (mechanistic models)
– Experimental models (empirical models)
– Semi-empirical models (combined approach)

■ Theoretical model → Based on physical/chemical/biological

relationship and conservation laws:
– Material/ Energy balances
– Heat, mass and momentum transfer
– Thermodynamics, chemical kinetics
– Physical property relationships
Mathematical modeling of
Chemical Processes
■ Conservation laws
– Conservation of mass

– Conservation of Component i
Mathematical modeling of
Chemical Processes
– Conservation of Energy
The general law of energy conservation is also called the
First Law of Thermodynamics. It can be expressed as:

The total energy of thermodynamics system is the sum of its

internal energy, kinetic energy and potential energy.
Mathematical modeling of
Chemical Processes
■ Empirical Model :
– Based on curve fitting and analysis of experimental data.
– Requires well-designed experiments.
– Easy to develop and usually quite simple.
– The behaviour is usually correct only around the
experimental conditions considered (dangerous to
extrapolate)
– Parameters of the model may not have physical meaning..
– Used for control design and simplified prediction model.
 Dynamics vs Steady-state
models
■ Dynamic (unsteady-state) model: 𝑑𝐶𝐴
– Describes time behaviour of a process. 𝑉 = 𝐹(𝐶𝐴0 − 𝐶𝐴 )
𝑑𝑡
– Dynamic models of chemical processes consist of
ODE and/or PDE, plus related algebraic equation
(AE).
■ Steady state model:
– No further changes in all variables with time.
– Can be obtained by setting the time derivative term
zero.
– Steady state model of chemical processes consist
of
■ AE if all variable do not change in space
■ DE and AE if some variables change in space.
Dynamics vs Steady-state
models

■ Step change in input to observe

– Starting at steady-state, we made a step change
– The system oscillates and finds a new steady-state
– Dynamics describe the transient behavior
Process Control Modeling

■ For process control applications:

– Modeling objectives is to describe process
dynamics based on the laws of conservation
of mass, energy and momentum
Example 1 :
Holding tank (Surge tank)

■ Modeling objective: Control of tank level

■ Fundamental quantity: Mass
■ Assumptions: Incompressible flow → Constant density
Example 1 :
Holding tank (Surge tank)
Example 2:
Heated stirred tank

■ Modeling objective: Control of tank temperature

■ Fundamental quantity: Mass and Energy
■ Assumptions:
– Incompressible flow
– Constant hold-up (residence time)
– Constant pressure
Example 2:
Heated stirred tank

Constant
volume
Example 2:
Heated stirred tank
Example 2:
Heated stirred tank
Example 2:
Heated stirred tank
Example 3:
Gravity tank

■ Modeling objective: Control height of liquid in the tank

■ Fundamental quantity: Mass and momentum
■ Assumptions:
– Outlet flow is driven by head of liquid in the tank
– Incompressible flow
– Plug flow in outlet pipe
– Turbulent flow
Example 3:
Gravity tank
Solution of ODEs

■ Mechanistic modeling results in (sets of) nonlinear ordinary

differential equations
■ Solution requires numerical integration
■ To get solution, we must first:
– specify all constants
– specify all initial conditions
– specify types of perturbations of the input variables
Study of control system
dynamics
■ Observe the time response of a process output in response to
input changes
■ Focus on specific inputs
– 1. Step input signals
– 2. Ramp input signals
– 3. Pulse and impulse signals
– 4. Sinusoidal signals
– 5. Random (noisy) signals
1. Step Input Signal:
■ a sustained instantaneous change
2. Ramp Input:
■ A sustained constant rate of change
■ e.g. Ramp input at time t=1
3. Pulse:
■ An instantaneous temporary change
e.g. Fast pulse (unit impulse) at t=1
3. Pulses:
■ e.g. Rectangular Pulse
4. Sinusoidal input:
■ e.g.
5. Random Input:
■ e.g. noise
 MODELING EXAMPLE 3.1. MIXING TANK

Textbook Example 3.1: The mixing tank in the figure has

been operating for a long time with a feed concentration of
0.925 kg-mole/m3. The feed composition experiences a step
to 1.85 kg-mole/m3. All other variables are constant.
Determine the dynamic response of a mixing tank to a step
in the inlet concentration of component A.

F
CA0 F
CA CA
CA V ?

Time
 MODELING EXAMPLE 3.1. MIXING TANK
■ Assumption:
– Well-mixed vessel
– Density same for A and solvent
– Constant volume
– Flow in = flow out

𝑑𝐶𝐴
• From Mass balance: 𝑉 = 𝐹𝐶𝐴0 − 𝐹𝐶𝐴
𝑑𝑡
• This equation is valid for all 𝑑𝐶𝐴
time; Rewrite for the initial 𝑉 = 𝐹𝐶𝐴0𝑠 − 𝐹𝐶𝐴𝑠
𝑑𝑡
steady state time : 𝑠
0
 MODELING EXAMPLE 3.1. MIXING TANK

• Deviation variable: 𝑥 ′ 𝑡 = 𝑥 𝑡 − 𝑥𝑠 (𝑡)

• Subtract both equation by taking

𝑑𝐶′𝐴
the definition of deviation 𝑉 = 𝐹𝐶′𝐴0 − 𝐹𝐶′𝐴
variable : 𝑑𝑡
𝑉
• Rearrange the equation by taking 𝜏=
𝐹
𝑑𝐶′𝐴 𝑑𝐶′𝐴 1 1
𝜏 + 𝐶′𝐴 = 𝐶′𝐴0 + 𝐶′𝐴 = 𝐶′𝐴0
𝑑𝑡 𝑑𝑡 𝜏 𝜏

• We can solve the ODE analytically using integrating factor method:

−
𝑡 𝑉 2.1
𝐶′𝐴 = Δ𝐶𝐴0 1 − 𝑒 𝜏 𝜏= = = 24.7
𝐹 0.085
 MODELING EXAMPLE 3.1. MIXING TANK

• We can make the graph to understand the response:

Output conc.
Input conc.
END