Theoretical Models of

Chemical Processes
ABDUL HALIM
CHEMICAL ENGINEERING
UNIVERSITAS INTERNASIONAL SEMEN INDONESIA
What will you learn
• Persamaan konservasi
• Degree of Freedom
• Dinamika model
The process control is affected by process
dynamics

The process is modelled by several model

derived from physical and chemical law
WHAT IS MODEL?
Model is a representation of natural and social phenomena

Unsteady state model are referred to dynamic model

Why model is important?
• Improve understanding of the process
• Train plant operating personnel
• Develop a control strategy for a new process
• Optimize process operating conditions
Type of model
• Theoretical models
• Empirical models
• Semi empirical models
 Neraca massa total

Example 𝑎𝑘𝑢𝑚𝑢𝑙𝑎𝑠𝑖 = 𝑖𝑛𝑝𝑢𝑡 − 𝑜𝑢𝑡𝑝𝑢𝑡

𝑑𝑚
= 𝑤1 + 𝑤2 − 𝑤
𝑑𝑡
𝑑 𝑉𝜌
= 𝑤1 + 𝑤2 − 𝑤
x1, w1 x2, w2 𝑑𝑡

Neraca massa komponen

𝑎𝑘𝑢𝑚𝑢𝑙𝑎𝑠𝑖𝐴 = 𝑖𝑛𝑝𝑢𝑡 𝐴 − 𝑜𝑢𝑡𝑝𝑢𝑡 𝐴

𝑑𝑚𝐴
= 𝑚𝐴1 + 𝑚𝐴2 − 𝑚
𝑑𝑡
𝑑𝑚𝐴
= 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥
𝑑𝑡
x, w 𝑑𝑚 × 𝑥
= 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥
𝑑𝑡
𝑑 𝑉𝜌𝑥
= 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥
𝑑𝑡
 Neraca massa total

Steady 𝑎𝑘𝑢𝑚𝑢𝑙𝑎𝑠𝑖 = 𝑖𝑛𝑝𝑢𝑡 − 𝑜𝑢𝑡𝑝𝑢𝑡

0=𝑤
ഥ1 + 𝑤
ഥ2 − 𝑤
ഥ

Neraca massa komponen

x1, w1 x2, w2
𝑎𝑘𝑢𝑚𝑢𝑙𝑎𝑠𝑖𝐴 = 𝑖𝑛𝑝𝑢𝑡 𝐴 − 𝑜𝑢𝑡𝑝𝑢𝑡 𝐴
0=𝑚
ഥ𝐴1 + 𝑚
ഥ𝐴2 − 𝑚
ഥ

0=𝑤
ഥ1 𝑥1 + 𝑤
ഥ2 𝑥2 − 𝑤𝑥
ഥ

x, w
All models are wrong, but some are useful
Do not choose model that
• Rigorous but excessively complicated

• Overly simplistic models

Approach to develop dynamic models
• State the modeling objectives and the end use of the model
• Determine the required levels of model detail and accuracy
• List all of the assumptions involved in developing the model
• Determine whether spatial variations of process variables are important
• Write appropriate conservation equations
• Introduce equilibrium relations and other algebraic equations
• Perform a degrees of freedom analysis to ensure that the model can be
solved
• Simplify the model
• Classify inputs as disturbance variables or as manipulated variables
Conservation Laws
• Mass conservation
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑚𝑎𝑠𝑠 𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
= 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑚𝑎𝑠𝑠 𝑖𝑛 − 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑚𝑎𝑠𝑠 𝑜𝑢𝑡

𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛 𝑖 𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛

= 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖 𝑖𝑛 − 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖 𝑜𝑢𝑡
+ 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑
− 𝑟𝑎𝑡𝑒 𝑜𝑓𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑
Conservation Laws
• Energy conservation

𝑟𝑎𝑡𝑒 𝑜𝑓 𝑒𝑛𝑒𝑟𝑔𝑦 𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛

= 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑒𝑛𝑒𝑟𝑔𝑦 𝑖𝑛 − 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑢𝑡
+ 𝑛𝑒𝑡 𝑟𝑎𝑡𝑒 𝑜𝑓 ℎ𝑒𝑎𝑡 𝑎𝑑𝑑𝑖𝑡𝑖𝑜𝑛 𝑡𝑜 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠
+ 𝑛𝑒𝑡 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑤𝑜𝑟𝑘 𝑝𝑒𝑟𝑓𝑜𝑟𝑚𝑒𝑑 𝑜𝑛 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝑏𝑦 𝑡ℎ𝑒 𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠
Blending process example
 Neraca massa total

Example 𝑎𝑘𝑢𝑚𝑢𝑙𝑎𝑠𝑖 = 𝑖𝑛𝑝𝑢𝑡 − 𝑜𝑢𝑡𝑝𝑢𝑡

𝑑𝑚
= 𝑤1 + 𝑤2 − 𝑤
𝑑𝑡
𝑑 𝑉𝜌
= 𝑤1 + 𝑤2 − 𝑤
x1, w1 x2, w2 𝑑𝑡
𝑑𝑉
𝜌 = 𝑤1 + 𝑤2 − 𝑤
𝑑𝑡

x, w
Neraca massa komponen

𝑎𝑘𝑢𝑚𝑢𝑙𝑎𝑠𝑖𝐴 = 𝑖𝑛𝑝𝑢𝑡 𝐴 − 𝑜𝑢𝑡𝑝𝑢𝑡 𝐴 𝑑𝐴𝐵 𝑑𝐵 𝑑𝐴

=𝐴 +𝐵
𝑑𝑚𝐴 𝑑𝑡 𝑑𝑡 𝑑𝑡
= 𝑚𝐴1 + 𝑚𝐴2 − 𝑚
𝑑𝑡
𝑑 𝑉𝑥 𝑑 𝑥 𝑑 𝑉
𝑑𝑚𝐴 𝜌 = 𝜌𝑉 + 𝜌𝑥
= 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥 𝑑𝑡 𝑑𝑡 𝑑𝑡
𝑑𝑡
𝑑 𝑥 𝑑 𝑉
𝑑𝑚 × 𝑥 𝜌𝑉 + 𝜌𝑥 = 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥
= 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥 𝑑𝑡 𝑑𝑡
𝑑𝑡
𝑑 𝑉𝜌𝑥
= 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥 𝑑𝑉
𝑑𝑡 𝜌 = 𝑤1 + 𝑤2 − 𝑤
𝑑𝑡
𝑑 𝑉𝑥
𝜌 = 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥 𝑑 𝑥 𝑑 𝑉
𝑑𝑡 𝜌𝑉 + 𝑥𝜌 = 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥
𝑑𝑡 𝑑𝑡
𝑑 𝑥
𝜌𝑉 + 𝑥 𝑤1 + 𝑤2 − 𝑤 = 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥
𝑑𝑡
𝑑 𝑥
𝜌𝑉 + 𝑥𝑤1 + 𝑥𝑤2 − 𝑥𝑤 = 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥
𝑑𝑡
 𝑑 𝑥 𝑑𝑉
𝜌𝑉 + 𝑥𝑤1 + 𝑥𝑤2 − 𝑥𝑤 = 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥 𝜌 = 𝑤1 + 𝑤2 − 𝑤
𝑑𝑡 𝑑𝑡

𝑑𝑥 𝑑𝑉 1
𝜌𝑉 + 𝑥𝑤1 + 𝑥𝑤2 − 𝑥𝑤 = 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥 = 𝑤 + 𝑤2 − 𝑤
𝑑𝑡 𝑑𝑡 𝜌 1

𝑑𝑥 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑥𝑤2 − 𝑥𝑤1
=
𝑑𝑡 𝜌𝑉

𝑑𝑥 𝑤1 𝑥1 − 𝑥𝑤1 + 𝑤2 𝑥2 − 𝑥𝑤2
=
𝑑𝑡 𝜌𝑉

𝑑𝑥 𝑤1 𝑥1 − 𝑥 + 𝑤2 𝑥2 − 𝑥
=
𝑑𝑡 𝜌𝑉
𝑑𝑥 𝑤1 𝑤2
= 𝑥 −𝑥 + 𝑥 −𝑥
𝑑𝑡 𝜌𝑉 1 𝜌𝑉 2
Dynamic Model
A stirred-tank blending process with a constant liquid holdup of 2 m3 is used to blend two
streams whose densities are both approximately 900 kg m-3. The density does not change
during mixing.
a. Assume that the process has been operating for a long period of time with flow rates
of 𝑤2 =200 kg/min and 𝑤1 =500 kg/min, and feed compositions (mass fractions) of
𝑥1 = 0.4 and 𝑥2 = 0.75. what is the steady state value of 𝑥?
b. Suppose that 𝑤1 changes suddenly from 500 to 400 kg/min and remains at the new
value. Determine an expression for 𝑥 𝑡 and plot it.
c. Repeat part (b) for the case where 𝑤2 , instead of 𝑤1 , changes suddenly from 200 to
100 kg/min and remains there.
d. Repeat part (c) for the case where 𝑥1 suddenly changes from 0.4 to 0.6 (in addition to
the change in 𝑤2 ).
e. For parts (b) through (d), plot the normalized response 𝑥𝑁 𝑡 ,
𝑥 𝑡 −𝑥 0
𝑥𝑁 𝑡 = 𝑥 ∞ −𝑥 0
where 𝑥 0 is the initial steady-state value of 𝑥 𝑡 and 𝑥 ∞ represents the final
steady-state value, which is different for each part.
 a)
0=𝑤
ഥ1 𝑥1 + 𝑤
ഥ2 𝑥2 − 𝑤𝑥
ഥ
0 = 500 0.4 + 200 0.75 − 700 𝑥
0 = 200 + 150 − 700 𝑥
0 = 350 − 700 𝑥
x = 0.5
b)
𝑑 𝑉𝑥 𝑑𝑥 𝑤1 𝑥1 + 𝑤2 𝑥2
𝜌 = 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥 𝜏 +𝑥 =
𝑑𝑡 𝑑𝑡 𝑤

𝑑𝑥 𝑤1 𝑥1 + 𝑤2 𝑥2 𝑤
ഥ1 𝑥ҧ1 + 𝑤
ഥ2 𝑥ҧ2
𝜌𝑉 + 𝑤𝑥 = 𝑤1 𝑥1 + 𝑤2 𝑥2 ≈C≜
𝑑𝑡 𝑤 𝑤
ഥ
𝑑𝑥
3 + 𝑥 = 0.517
𝑑𝑡
𝜌𝑉 𝑑𝑥 𝑤1 𝑥1 + 𝑤2 𝑥2
+𝑥 = 3𝑑𝑥 = 0.517𝑑𝑡 − 𝑥𝑑𝑡
𝑤 𝑑𝑡 𝑤 𝑑𝑥
3 = 0.517 − 𝑥
𝑑𝑡
𝑑𝑥 𝑤1 𝑥1 + 𝑤2 𝑥2
𝜏 +𝑥 =
𝑑𝑡 𝑤 𝑥 𝑡 = 0.5𝑒 −𝑡/3 + 𝐶 1 − 𝑒 −𝑡/3

𝜌𝑉ത 900 × 2 1800 𝑤

ഥ1 𝑥ҧ1 + 𝑤
ഥ2 𝑥ҧ2 400 0.4 + 200 0.75
𝜏≜ = = =3 C≜ = = 0.517
𝑤ഥ 400 + 200 600 𝑤
ഥ 600

𝑥 0 = 𝑥ҧ = 0.5 𝑥 𝑡 = 0.5𝑒 −𝑡/3 + 0.517 1 − 𝑒 −𝑡/3

c)
𝑑 𝑉𝑥 𝑑𝑥 𝑤1 𝑥1 + 𝑤2 𝑥2
𝜌 = 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥 𝜏 +𝑥 =
𝑑𝑡 𝑑𝑡 𝑤

𝑑𝑥 𝑤1 𝑥1 + 𝑤2 𝑥2 𝑤
ഥ1 𝑥ҧ1 + 𝑤
ഥ2 𝑥ҧ2
𝜌𝑉 + 𝑤𝑥 = 𝑤1 𝑥1 + 𝑤2 𝑥2 ≈C≜
𝑑𝑡 𝑤 𝑤
ഥ
𝑑𝑥
3 + 𝑥 = 0.458
𝑑𝑡
𝜌𝑉 𝑑𝑥 𝑤1 𝑥1 + 𝑤2 𝑥2
+𝑥 = 3𝑑𝑥 = 0.458𝑑𝑡 − 𝑥𝑑𝑡
𝑤 𝑑𝑡 𝑤 𝑑𝑥
3 = 0.458 − 𝑥
𝑑𝑡
𝑑𝑥 𝑤1 𝑥1 + 𝑤2 𝑥2
𝜏 +𝑥 =
𝑑𝑡 𝑤 𝑥 𝑡 = 0.5𝑒 −𝑡/3 + 𝐶 1 − 𝑒 −𝑡/3

𝜌𝑉ത 900 × 2 1800 𝑤

ഥ1 𝑥ҧ1 + 𝑤
ഥ2 𝑥ҧ2 500 0.4 + 100 0.75
𝜏≜ = = =3 C≜ = = 0.458
𝑤ഥ 500 + 100 600 𝑤
ഥ 600

𝑥 0 = 𝑥ҧ = 0.5 𝑥 𝑡 = 0.5𝑒 −𝑡/3 + 0.458 1 − 𝑒 −𝑡/3

d)
𝑑 𝑉𝑥 𝑑𝑥 𝑤1 𝑥1 + 𝑤2 𝑥2
𝜌 = 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥 𝜏 +𝑥 =
𝑑𝑡 𝑑𝑡 𝑤

𝑑𝑥 𝑤1 𝑥1 + 𝑤2 𝑥2 𝑤
ഥ1 𝑥ҧ1 + 𝑤
ഥ2 𝑥ҧ2
𝜌𝑉 + 𝑤𝑥 = 𝑤1 𝑥1 + 𝑤2 𝑥2 ≈C≜
𝑑𝑡 𝑤 𝑤
ഥ
𝑑𝑥
3 + 𝑥 = 0.625
𝑑𝑡
𝜌𝑉 𝑑𝑥 𝑤1 𝑥1 + 𝑤2 𝑥2
+𝑥 = 3𝑑𝑥 = 0.625𝑑𝑡 − 𝑥𝑑𝑡
𝑤 𝑑𝑡 𝑤 𝑑𝑥
3 = 0.625 − 𝑥
𝑑𝑡
𝑑𝑥 𝑤1 𝑥1 + 𝑤2 𝑥2
𝜏 +𝑥 =
𝑑𝑡 𝑤 𝑥 𝑡 = 0.5𝑒 −𝑡/3 + 𝐶 1 − 𝑒 −𝑡/3

𝜌𝑉ത 900 × 2 1800 𝑤

ഥ1 𝑥ҧ1 + 𝑤
ഥ2 𝑥ҧ2 500 0.6 + 100 0.75
𝜏≜ = = =3 C≜ = = 0.625
𝑤ഥ 500 + 100 600 𝑤
ഥ 600

𝑥 0 = 𝑥ҧ = 0.5 𝑥 𝑡 = 0.5𝑒 −𝑡/3 + 0.625 1 − 𝑒 −𝑡/3

e)
𝑥 𝑡 −𝑥 0
𝑥𝑁 𝑡 =
𝑥 ∞ −𝑥 0
0.5𝑒 −𝑡/3 + 𝐶 1 − 𝑒 −𝑡/3 − 0.5
𝑥𝑁 𝑡 =
𝐶 − 0.5
Degree of freedom

𝑁𝐹 = 𝑁𝑉 − 𝑁𝐸

𝑁𝐹 = 0 exactly specified
𝑁𝐹 > 0 underspecified
𝑁𝐹 < 0 overspecified
• 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 and so on
• 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
• Calculate the number of degrees of freedom
• Identify the NE output variables that will be obtained by solving the process
model
• 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
 Example of degree of freedom
Analyze the degrees of freedom for the blending model of below
equation for the special condition where volume V is constant
𝑑 𝑉𝜌𝑥
= 𝑤1 𝑥1 + 𝑤2 𝑥2 − 𝑤𝑥
𝑑𝑡
x1, w1 x2, w2
2 parameters: V, ρ, 𝑥2 1 output: x
4 variables (NV): x, x1, w1, w2 2 disturbance variable: x1, w1
1 equation (NE): 3 input: x1, w1, w2
1 manipulated: w2

x, w
𝑁𝐹 = 𝑁𝑉 − 𝑁𝐸 = 4 − 1 = 3
 Example of degree of freedom
Analyze the degrees of freedom for the blending system model of
below equation.
𝑑𝑉 1 𝑑𝑥 𝑤1 𝑤2
= 𝑤 + 𝑤2 − 𝑤 = 𝑥 −𝑥 + 𝑥 −𝑥
𝑑𝑡 𝜌 1 𝑑𝑡 𝑉𝜌 1 𝑉𝜌 2

x1, w1 x2, w2
1 parameters: ρ
2 output: V, x
7 variables (NV): V, x, x1,
x2, w, w1, w2 3 disturbance variable: x1, x2, w1
5 input: w, x1, x2, w1,
2 equation (NE):
w2 2 manipulated:w, w2

𝑁𝐹 = 𝑁𝑉 − 𝑁𝐸 = 7 − 2 = 5
x, w
T1, x1, w1 T2, x2, w2

T, x, w
Dynamic Model of Representative Process
Stirred-Tank Heating Process: Constant
Holdup
Stirred-Tank Heating Process: Variable Holdup
Electrically Heated Stirred Tank
Steam-Heated Stirred Tank
Liquid Storage Systems
The Continuous Stirred-Tank Reactor (CSTR)
Stage Systems (a 3-Stage Absorber)
Fed-Batch Bioreactor