UANL Dr.

Salvador Tututi

Chemical Reactor Example

Consider the chemical reactor system shown in Fig. 3-6.1. The reactor is a vessel where the
“well-known” reaction 𝐴𝐴 → 𝐵𝐵 occurs. Let us assume that the reaction occurs at constant
volume and temperature. In addition, let’s assume constant physical properties and that the
reactor is well mixed. The rate of reaction is given by the expression

2
𝑟𝑟𝐴𝐴 (𝑡𝑡) = 𝑘𝑘𝑐𝑐𝐴𝐴 (𝑡𝑡)

Figure 3-6.1 Isothermal well-mixed chemical reactor.

where
𝑟𝑟𝐴𝐴 (𝑡𝑡) = rate of reaction of component 𝐴𝐴, 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 of 𝐴𝐴/𝑚𝑚3 𝑠𝑠
𝑘𝑘 =constant of reaction, 𝑚𝑚3 /𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 𝑠𝑠
𝑐𝑐𝐴𝐴 (𝑡𝑡) =concentration of component 𝐴𝐴 in reactor, 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 of 𝐴𝐴/𝑚𝑚3

The objective is to develop the mathematical model, find the transfer functions, and draw
the block diagram, relating 𝑐𝑐𝐴𝐴 (𝑡𝑡) and 𝑐𝑐𝐴𝐴𝐴𝐴 (𝑡𝑡) to the inputs 𝑓𝑓(𝑡𝑡) and 𝑐𝑐𝐴𝐴𝐴𝐴 (𝑡𝑡).

Our procedure calls for first developing the mathematical model. Remember, in our way of
doing things, those input variables, 𝑓𝑓(𝑡𝑡) and 𝑐𝑐𝐴𝐴𝐴𝐴 (𝑡𝑡) in this case, are not considered unknowns.
The control volume includes the valve and reactor. For this process, an unsteady-state mole
balance on component 𝐴𝐴, of the type presented at the beginning of this section, provides the
first equation:

Rate of moles of Rate of moles of Rate of change of Rate of accumulation of

�component 𝐴𝐴 into� − � component 𝐴𝐴 out � + � component 𝐴𝐴 in � = � moles of component 𝐴𝐴 �
control volume of control volume control volume in control volume

or, in equation form,

𝑑𝑑𝑐𝑐𝐴𝐴 (𝑡𝑡)
𝑓𝑓(𝑡𝑡)𝑐𝑐𝐴𝐴𝐴𝐴 (𝑡𝑡) − 𝑓𝑓(𝑡𝑡)𝑐𝑐𝐴𝐴 (𝑡𝑡) + (−1)𝑉𝑉 𝑟𝑟𝐴𝐴 (𝑡𝑡) = 𝑉𝑉 (3.6.1)
𝑑𝑑𝑑𝑑

The rate-of-reaction expression provides another equation:

2
𝑟𝑟𝐴𝐴 (𝑡𝑡) = 𝑘𝑘𝑐𝑐𝐴𝐴 (𝑡𝑡) (3.6.2)

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UANL Dr. Salvador Tututi

Equations 3-6.1 and 3-6.2 constitute the mathematical model for this process. Writing this
model is the first step in our procedure. The second step calls for linearizing the nonlinear
terms in the model. Linearizing the first two terms of Eq. 3-6.1 and Eq. 3-6.2 around the
initial steady state values of, 𝑐𝑐𝐴𝐴𝐴𝐴
̅ , and 𝑐𝑐𝐴𝐴̅ yields

𝑓𝑓(𝑡𝑡)𝑐𝑐𝐴𝐴𝐴𝐴 (𝑡𝑡) ≈ 𝑓𝑓 𝑐𝑐̅ 𝐴𝐴𝐴𝐴 ̅ �𝑓𝑓(𝑡𝑡) − 𝑓𝑓 �̅ + 𝑓𝑓 (𝑐𝑐

̅ + 𝑐𝑐𝐴𝐴𝐴𝐴 ̅ 𝐴𝐴𝐴𝐴 (𝑡𝑡) − 𝑐𝑐𝐴𝐴𝐴𝐴
̅ ) (3.6.3)

𝑓𝑓(𝑡𝑡)𝑐𝑐𝐴𝐴 (𝑡𝑡) ≈ 𝑓𝑓 𝑐𝑐̅ 𝐴𝐴̅ + 𝑐𝑐𝐴𝐴̅ �𝑓𝑓(𝑡𝑡) − 𝑓𝑓 �̅ + 𝑓𝑓 (𝑐𝑐

̅ (𝑡𝑡) − 𝑐𝑐 ̅ )
𝐴𝐴 𝐴𝐴 (3.6.4)
𝑟𝑟𝐴𝐴 (𝑡𝑡) ≈ 𝑟𝑟̅𝐴𝐴 + 2𝑘𝑘𝑐𝑐𝐴𝐴̅ (𝑐𝑐𝐴𝐴 (𝑡𝑡) − 𝑐𝑐𝐴𝐴̅ ) (3.6.5)

Substituting Eqs. (3-6.3), (3-6.4), and (3-6.5) into Eq. (3-6.1) yields

𝑓𝑓 𝑐𝑐̅ 𝐴𝐴𝐴𝐴 ̅ �𝑓𝑓(𝑡𝑡) − 𝑓𝑓 �̅ + 𝑓𝑓 (𝑐𝑐

̅ + 𝑐𝑐𝐴𝐴𝐴𝐴 ̅ 𝐴𝐴𝐴𝐴 (𝑡𝑡) − 𝑐𝑐𝐴𝐴𝐴𝐴
̅ ) − 𝑓𝑓 𝑐𝑐̅ 𝐴𝐴̅ − 𝑐𝑐𝐴𝐴̅ �𝑓𝑓(𝑡𝑡) − 𝑓𝑓 �̅ − 𝑓𝑓 (𝑐𝑐
̅ 𝐴𝐴 (𝑡𝑡) − 𝑐𝑐𝐴𝐴̅ )
𝑑𝑑𝑐𝑐 (𝑡𝑡)
−𝑉𝑉 𝑟𝑟̅𝐴𝐴 − 2𝑉𝑉𝑉𝑉𝑐𝑐𝐴𝐴̅ (𝑐𝑐𝐴𝐴 (𝑡𝑡) − 𝑐𝑐𝐴𝐴̅ ) = 𝑉𝑉 𝐴𝐴 (3.6.6)
𝑑𝑑𝑑𝑑

Equation 3-6.6 is the equation that describes the process around the linearization values. We
can now proceed to obtain the transfer functions. Writing a mole balance at the initial steady
state (Eq. 3.6.7) and subtracting it from Eq. 3-6.6 yield

𝑓𝑓 𝑐𝑐̅ 𝐴𝐴𝐴𝐴
̅ − 𝑓𝑓 𝑐𝑐̅ 𝐴𝐴̅ − 𝑉𝑉𝑉𝑉𝑐𝑐𝐴𝐴
2
̅ =0 (3.6.7)

̅ − 𝑓𝑓 𝑐𝑐̅ 𝐴𝐴𝐴𝐴
𝑓𝑓 𝑐𝑐̅ 𝐴𝐴𝐴𝐴 ̅ �𝑓𝑓(𝑡𝑡) − 𝑓𝑓 �̅ + 𝑓𝑓 (𝑐𝑐
̅ + 𝑐𝑐𝐴𝐴𝐴𝐴 ̅ 𝐴𝐴𝐴𝐴 (𝑡𝑡) − 𝑐𝑐𝐴𝐴𝐴𝐴
̅ ) − 𝑓𝑓 𝑐𝑐̅ 𝐴𝐴̅ + 𝑓𝑓 𝑐𝑐̅ 𝐴𝐴̅ − 𝑐𝑐𝐴𝐴̅ �𝑓𝑓(𝑡𝑡) − 𝑓𝑓 �̅ − 𝑓𝑓 (𝑐𝑐
̅ 𝐴𝐴 (𝑡𝑡) − 𝑐𝑐𝐴𝐴̅ )
𝑑𝑑(𝑐𝑐𝐴𝐴 (𝑡𝑡) − 𝑐𝑐𝐴𝐴̅ )
−𝑉𝑉 𝑟𝑟̅𝐴𝐴 + 𝑉𝑉 𝑟𝑟̅𝐴𝐴 − 2𝑉𝑉𝑉𝑉𝑐𝑐𝐴𝐴̅ (𝑐𝑐𝐴𝐴 (𝑡𝑡) − 𝑐𝑐𝐴𝐴̅ ) = 𝑉𝑉
𝑑𝑑𝑑𝑑

̅ 𝐴𝐴𝐴𝐴 (𝑡𝑡) − 𝑐𝑐𝐴𝐴̅ 𝐹𝐹 (𝑡𝑡) − 𝑓𝑓 𝐶𝐶

̅ 𝐴𝐴 (𝑡𝑡) − 2𝑉𝑉𝑉𝑉𝑐𝑐𝐴𝐴̅ 𝐶𝐶𝐴𝐴 (𝑡𝑡) = 𝑉𝑉 𝑑𝑑𝐶𝐶𝐴𝐴 (𝑡𝑡)
̅ 𝐹𝐹 (𝑡𝑡) + 𝑓𝑓 𝐶𝐶
𝑐𝑐𝐴𝐴𝐴𝐴 (3.6.8)
𝑑𝑑𝑑𝑑

where 𝐹𝐹 (𝑡𝑡) = 𝑓𝑓(𝑡𝑡) − 𝑓𝑓 ,̅ 𝐶𝐶𝐴𝐴𝐴𝐴 (𝑡𝑡) = 𝑐𝑐𝐴𝐴𝐴𝐴 (𝑡𝑡) − 𝑐𝑐𝐴𝐴𝐴𝐴

̅ and 𝐶𝐶𝐴𝐴 (𝑡𝑡) = 𝑐𝑐𝐴𝐴 (𝑡𝑡) − 𝑐𝑐𝐴𝐴̅

Rearranging Eq. (3.6.8) in the standard form

𝑑𝑑𝐶𝐶𝐴𝐴 (𝑡𝑡)
𝑉𝑉 + 𝐶𝐶𝐴𝐴 (𝑡𝑡)�𝑓𝑓 ̅ + 2𝑉𝑉𝑉𝑉𝑐𝑐𝐴𝐴̅ � = 𝐹𝐹 (𝑡𝑡)(𝑐𝑐𝐴𝐴𝐴𝐴 ̅ 𝐴𝐴𝐴𝐴 (𝑡𝑡)
̅ + 𝑐𝑐𝐴𝐴̅ ) + 𝑓𝑓 𝐶𝐶
𝑑𝑑𝑑𝑑
𝑉𝑉 𝑑𝑑𝐶𝐶𝐴𝐴 (𝑡𝑡) (𝑐𝑐 ̅ + 𝑐𝑐𝐴𝐴̅ ) 𝑓𝑓 ̅
+ 𝐶𝐶𝐴𝐴 (𝑡𝑡) = 𝐴𝐴𝐴𝐴 𝐹𝐹 (𝑡𝑡) + 𝐶𝐶𝐴𝐴𝐴𝐴 (𝑡𝑡)
𝑓𝑓 ̅ + 2𝑉𝑉𝑉𝑉𝑐𝑐𝐴𝐴̅ 𝑑𝑑𝑑𝑑 𝑓𝑓 ̅ + 2𝑉𝑉𝑉𝑉𝑐𝑐𝐴𝐴̅ 𝑓𝑓 ̅ + 2𝑉𝑉𝑉𝑉𝑐𝑐𝐴𝐴̅
𝑑𝑑𝐶𝐶𝐴𝐴 (𝑡𝑡)
𝜏𝜏 + 𝐶𝐶𝐴𝐴 (𝑡𝑡) = 𝐾𝐾1 𝐹𝐹 (𝑡𝑡) + 𝐾𝐾2 𝐶𝐶𝐴𝐴𝐴𝐴 (𝑡𝑡)
𝑑𝑑𝑑𝑑
Where

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UANL Dr. Salvador Tututi

𝑉𝑉 (𝑐𝑐 ̅ + 𝑐𝑐𝐴𝐴̅ ) 𝑓𝑓 ̅
𝜏𝜏 = , 𝐾𝐾1 = 𝐴𝐴𝐴𝐴 and 𝐾𝐾2 =
𝑓𝑓 ̅ + 2𝑉𝑉𝑉𝑉𝑐𝑐𝐴𝐴̅ 𝑓𝑓 ̅ + 2𝑉𝑉𝑉𝑉𝑐𝑐𝐴𝐴̅ 𝑓𝑓 ̅ + 2𝑉𝑉𝑉𝑉𝑐𝑐𝐴𝐴̅

Taking the Laplace Transform gives:

𝜏𝜏𝑠𝑠𝑠𝑠𝐴𝐴 (𝑠𝑠) + 𝐶𝐶𝐴𝐴 (𝑠𝑠) = 𝐾𝐾1 𝐹𝐹 (𝑠𝑠) + 𝐾𝐾2 𝐶𝐶𝐴𝐴𝐴𝐴 (𝑠𝑠)
𝐾𝐾1 𝐾𝐾2
𝐶𝐶𝐴𝐴 (𝑠𝑠) = 𝐹𝐹 (𝑠𝑠) + 𝐶𝐶 (𝑠𝑠) (3.6.9)
𝜏𝜏𝜏𝜏 + 1 𝜏𝜏𝜏𝜏 + 1 𝐴𝐴𝐴𝐴
Eq. 3.6.9 is the global transfer function of this system.

From Eq. 3-6.9, the desired individual transfer functions can be obtained. They are

𝐶𝐶𝐴𝐴 (𝑠𝑠) 𝐾𝐾1 𝐶𝐶𝐴𝐴 (𝑠𝑠) 𝐾𝐾2

= and =
𝐹𝐹 (𝑠𝑠) 𝜏𝜏𝜏𝜏 + 1 𝐶𝐶𝐴𝐴𝐴𝐴 (𝑠𝑠) 𝜏𝜏𝑠𝑠 + 1

To obtain the relationships for 𝑐𝑐𝐴𝐴𝐴𝐴 (𝑡𝑡), assuming ideal plug flow and no reaction occurring
in the outlet pipe, we can state
𝑐𝑐𝐴𝐴𝐴𝐴 (𝑡𝑡) = 𝑐𝑐𝐴𝐴 (𝑡𝑡 − 𝑡𝑡0 )
or, in terms of deviation variables,
𝐶𝐶𝐴𝐴𝐴𝐴 (𝑡𝑡) = 𝐶𝐶𝐴𝐴 (𝑡𝑡 − 𝑡𝑡0 )
and

𝐿𝐿𝐴𝐴𝑝𝑝
𝑡𝑡0 =
𝑓𝑓 ̅

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