Modeling & Simulation in

Chemical Engineering
Prerequisite: CHE 232
Lecture(5)
Example 1:
Suppose we have the same macroscopic system as above except that now consecutive
reactions occur. Reactant “A” goes to “B” at a specific rate reaction “k1”, but B can react
at a specific rate k2 to form a third component “C”.
k1 k2
A → B → C
Assuming first order reactions, the component continuity equations for component A, B
and C.
Required:
1- write clearly all assumption?
2- find component continuity equation for A, B and C?
3- find the change of A, B and C with time?

Solution
Basis:
component continuity equation ( there is chemical reaction
Assumptions:
1- perfect mixing FO
2- first order reaction CAO F
3-Constant temperature CBO CA
Mathematical model: CB
C CO CC
For “A” component
flow of mole of A into system= FO CAO
flow of mole of A out the system= F CA
Rate of formation of A inside the system = - rv = - k1CA V
Time of change of A inside system =d(CA V)/dt
Substitute in component continuity equation
FO CAO - F CA - - k1CA V = d(CA V)/dt
For “B” component
low of mole of B into system= FO CBO
flow of mole of B out the system= F CB
Rate of formation of B inside the system = - rv = + k1CA V – k2CB V
Time of change of B inside system =d(CB V)/dt
Substitute in component continuity equation
FO CBO - F CB - + k1CA V- k2CB V = d(CBV)/dt
For “c” component
flow of mole of C into system= FO CCO
flow of mole of C out the system= F CC
Rate of formation of C inside the system = - rv = k2CB V
Time of change of C inside system =d(CC V)/dt
Substitute in component continuity equation
FO CCO - F CC - + k2CB V = d(CCV)/dt
Example 2:
Instead of fluid flowing down a pipe , suppose the pipe is a tubular reactor in which the
same reaction A→B . As a slice of moves down the length of the reactor the
concentration of reactant CA decreases as A is consumed. Density ρ, velocity v, and
concentration CA can all vary with time and axial position Z. We still assume plug-flow
conditions, so that there are no radial gradients in velocity, density, or concentration .
The concentration of A fed to the inlet of the reactor at z=0 is defined as
CA (t, O) = CAO( t)
The concentration of A in the reactor effluent z=L is defined as
CA (t, L) = CAL( t)
We now want to apply the component continuity equation for reactant A to a small
differential slice of width dz, as shown in figure. the inflow terms can be split into two
types: bulk flow and diffusion. Diffusion can occur because of the concentration
gradient in the axial direction. It is usually much less important than bulk flow in most
practical systems, but we include it here to see what it contributes to the model. We
will say that the diffusive flux of A , NA (moles of A per unit time per unit area), is given
by a Fick’s law type of relationship.
WA = - DA (𝝏 CA /𝝏𝒁)
Where DA is a diffusion coefficient due to both diffusion and turbulence in the fluid
flow(so - called” eddy diffusivity”). DA has units of length per unit time.
Required:
Apply component continuity equation for reactant A
dz
CAO (t) CAL( t)

Z=0 Z Z+dz Z=L

Solution 3- Motion Equation

Basis:
Component continuity equation ( there is chemical reaction)
Assumptions:
1- plug- flow conditions
2- no radial gradient in velocity, density or concentration
3- first order reaction
4- constant temperature ( isothermal)
Mathematical model consistency:
Flow of moles of A into boundary at Z= diffusion flow + bulk flow
• Diffusion flow ( as a result of concentration difference)
• Bulk flow ( as a result of velocity o)
Calculation of diffusion flow by Fick’s law
 NA= -DA (dCA/dz)
NA = diffusive flux (mole/ time. Area)
DA = diffusion coefficient due to diffusion (turbulence& eddy diffusivity)

• Flow of moles of A into boundary at Z= diffusion flow + bulk flow

Diffusion flow : NA . A [(mole/ time. Area). area]→ mole/time
Bulk flow: CA . A. v [ (mole/ m3)(m2) (m/time) → mole/time
= NA . A + CA . A. v ❷
• Flow of moles of A at boundary at (Z+dZ)
Calculation by Taylor expansion :
F(Z+dZ) = f(Z) + (𝝏 𝒇(𝒁)/𝝏𝒁) dz
= [NA . A + CA . A. v + [(𝝏(NA . A + CA . A. v)/𝝏𝒁) dz] ❸

• Rate of formation of A inside system = -k CA V = -k CA A dz ❹

• Time rate of change of A inside system = 𝝏(CA . A. dz)/𝝏𝒕 ❺

Substitute in component continuity equation:

NA . A + CA . A. v - [NA . A + CA . A. v + [𝝏(NA . A + CA . A. v/𝝏𝒁) dz] - k CA A dz
= 𝝏(CA . A. dz)/𝝏𝒕
→ - [𝝏(NA . A + CA. A. v/𝝏𝒁) dz] - k CA A dz = 𝝏(CA . A. dz)/𝝏𝒕

→ - [𝝏(NA . A + CA. A. v/𝝏𝒁) dz] - k CA A dz - 𝝏(CA . A. dz)/𝝏𝒕 = 0.0 ÷𝑨

−𝝏[(NA dz) + (CA. v dz)]/ 𝝏𝒁 - k CA dz - 𝝏(CA. dz)/𝝏𝒕 =0.0 ÷ − 𝒅𝒛

⇛ 𝝏 (NA + CA. v)/ 𝝏𝒁 + k CA + 𝝏CA/𝝏𝒕 =0.0

⇛ 𝝏 NA/ 𝝏𝒁 + 𝝏 CA. v/ 𝝏𝒁 + k CA + 𝝏CA/𝝏𝒕 =0.0

But NA= -DA (dCA/dz)

− 𝝏/ 𝝏𝒁 [DA (dCA/dz)] + 𝝏 CA. v/ 𝝏𝒁 + k CA + 𝝏CA/𝝏𝒕 =0.0

𝛛 𝛛CA 𝛛 𝛛
C . v + k C + = 𝛛𝐙 (DA𝛛𝐙 CA )
𝛛𝐙 A A 𝛛𝐭

(Mathematical model)
Example 3:
To illustrate the application of energy equation to a microscopic system, let us return
to the plug-flow tubular reactor and now keep track of temperature changes as the
fluid flows down the pipe. We will again assume no radial gradients in velocity,
concentration, or temperature( a very poor assumption in some strong exothermic
system if the pipe diameter is not kept small). Suppose that the reactor has a cooling
jacket around it as shown in the figure . Heat can be transferred from the process
fluid reactants and products at temperature T to the metal wall of the reactor at
temperature Tm. The heat is subsequently transferred to the cooling water. For a
complete description of the system we would need energy for the process fluid, the
metal wall, and the cooling water. Here we will concern ourselves only with the
process energy equation.
Looking at a little slice of the process fluid as our system, we can derive each of the
terms of energy equation. Potential energy and kinetic energy terms are assumed
negligible and there is no work term. The simplified forms of the internal energy and
enthalpy are assumed . Diffusive flow is assumed negligible compared to bulk flow.
We will include the possibility for conduction of heat axially alone the reactor due to
molecular or turbulence condition .
Required : write the energy equation for this system water ( in)

water (out)
Solution
Basis:
Energy equation
Assumptions:
1- no radial gradient in velocity , concentration or temperature.
2- potential , kinetic energy terms are assumed negligible, there no work.
3- diffusive flow is negligible compared with bulk flow.
Mathematical model consistency:
dz
v
z z+dz
• Flow of energy (enthalpy)into boundary at z due to bulk flow
• = ρ v A CP T(Btu/min) ❷
• Flow of energy (enthalpy ) out of boundary (z+dz)= ( in this case we will use Taylor
expansion)
𝛛
F(Z+dZ) = f(Z) + 𝒇(𝒁) dz
𝛛𝐙
𝛛
= ρ v A CP T + ( ρ v A CP T ) dz ❸
𝛛𝐙
• Heat generated by chemical reaction= - k CA V = -k CA A dz ʎ ❹

• Heat transferred from system to metal by convection = - hT A ( T- Tm)

= - hT 𝜋 𝐷dz ( T- Tm)❺
hT : heat transfer film coefficient ( Btu/min. ft. °R)
D: diameter of pipe
• Heat conduction into boundary z = Qx . A ❻

𝛛
Q x = - KT T ( Fourier’s law), KT : effective thermal conductivity ( Btu/min. ft. °R)
𝛛𝐙
𝛛
• Heat conduction into boundary z+dz = Qx . A + Qx . A . Dz ❼
𝛛𝐙

𝛛
• Rate of change of internal energy (enthalpy of system) = (ρ v A CP T ) ❽
𝛛𝐭

• 2, 3,4,5,6,7,8 in energy equation

𝛛 𝛛 𝛛 𝛛
• (ρ CP T ) + (ρ v CP T ) + k CA ʎ + (4 hT/ 𝐷) ( T- Tm) = (KT T)
𝛛𝐭 𝛛𝐙 𝛛𝐙 𝛛𝐙

(Mathematical model