Notes 2: Examples of Mathematical Models for Chemical

Processes

In this note we develop mathematical models for a number of elementary

chemical processes that are commonly encountered in practice. We will apply the
methodology to guide the reader through various examples. The goal is to give the
reader a methodology to tackle more complicated processes that are not covered in this
chapter and that can be found in books listed in the reference. The organization of this
note includes examples of systems that can be described by ordinary differential
equations (ODE), i.e. lumped parameter systems followed by examples of distributed
parameters systems, i.e. those described by partial differential equations (PDE). The
examples cover both homogeneous and heterogeneous systems. Ordinary differential
equations (ODE) are easier to solve and are reduced to simple algebraic equations at
steady state. The solution of partial differential equations (PDE) on the other hand is a
more difficult task. But we will be interested in the cases were PDE's are reduced to
ODE's. This is naturally the case where under appropriate assumptions, the PDE's is a
one-dimensional equation at steady state conditions. It is worth to recall, as noted in the
1st class, that the distinction between lumped and distributed parameter models depends
sometimes on the assumptions put forward by the modeler. Systems that are normally
distributed parameter can be modeled under appropriate assumptions as lumped
parameter systems. This notes includes some examples of this situation.

28
2.1 Examples of Lumped Parameter Systems

2.1.1 Liquid Storage Tank

Consider the perfectly mixed storage tank shown in figure 2.1. Liquid stream
with volumetric rate Ff (m3/s) and density f flow into the tank. The outlet stream has
volumetric rate Fo and density . Our objective is to develop a model for the variations
of the tank holdup, i.e. volume of the tank. The system is therefore the liquid in the
tank. We will assume that it is perfectly mixed and that the density of the effluent is the
same as that of tank content. We will also assume that the tank is isothermal, i.e. no
variations in the temperature. To model the tank we need only to write a mass balance
equation.

Ff
f V
Fo
o

Figure 2-1 Liquid Storage Tank

Since the system is perfectly mixed, the system properties do not vary with position
inside the tank. The only variations are with time. The mass balance equation can be
written then on the whole system and not only on a differential element of it. This leads
to therefore to a macroscopic model.

We apply the general balance equation (Eq. 1.2), to the total mass m = V. This yields:

Mass flow in:

f Ff (2.1)

29
Mass flow out:

o Fo (2.2)

Accumulation:

dm d (V )
 (2.3)
dt dt

The generation term is zero since the mass is conserved. The balance equation yields:

d (V )
 f F f  o Fo 
dt (2.4)

For consistency we can check that all the terms in the equation have the SI unit of kg/s.
The resulting model (Eq. 2.4) is an ordinary differential equation (ODE) of first order
where time (t) is the only independent variable. This is therefore a lumped parameter
model. To solve it we need one initial condition that gives the value of the volume at
initial time ti, i.e.

V(ti) = Vi (2.5)

Under isothermal conditions we can further assume that the density of the liquid is
constant i.e. f = o=. In this case Eq. 2.4 is reduced to:

dV
 F f  Fo
dt (2.6)

The volume V is related to the height of the tank L and to the cross sectional area A by:

V = AL (2.7)

30
Since (A) is constant then we obtain the equation in terms of the state variable L:

dL
A  F f  Fo (2.8)
dt

with initial condition:

L(ti) = Li (2.9)

Degree of freedom analysis

For the system described by Eq. 2.8 we have the following information:

 Parameter of constant values: A

 Variables which values can be externally fixed (Forced variable): Ff
 Remaining variables: L and Fo
 Number of equations: 1 (Eq. 2.8)

Therefore the degree of freedom is:

Number of remaining variables – Number of equations = 2 – 1 = 1

For the system to be exactly specified we need therefore one more equations. This extra
relation is obtained from practical engineering considerations. If the system is operated
without control (at open loop) then the outlet flow rate Fo is a function of the liquid
level L. Generally a relation of the form:

Fo   L (2.10)

could be used, where  is the discharge coefficient.

If on the other hand the liquid level is under control, then its value is kept constant at
certain desired value Ls. If Fo is used to control the height then a control law relates Fo
to L and Ls:

31
 Fo = Fo(L,Ls) (2.11)

For instant, if a proportional controller Kc is used then the control law is given by:

Fo = Kc(L − Ls) + Fob (2.12)

Where Fob the bias, i.e. the constant value of Fo when the level is at the desired value
i.e., L = Ls.
Note that at steady state, the accumulation term is zero (height does not change with
time), i.e., dL/dt = 0. The model of the tank is reduced to the simple algebraic equation:

F0 = Ff (2.13)

2.1.2 Stirred Tank Heater

We consider the liquid tank of the last example but at non-isothermal conditions.
The liquid enters the tank with a flow rate Ff (m3/s), density f (kg/m3) and temperature
Tf (K). It is heated with an external heat supply of temperature Tst (K), assumed
constant. The effluent stream is of flow rate Fo (m3/s), density o (kg/m3) and
temperature T(K) (Fig. 2.2). Our objective is to model both the variation of liquid level
and its temperature. As in the previous example we carry out a macroscopic model over
the whole system. Assuming that the variations of temperature are not as large as to
affect the density then the mass balance of Eq. 2.8 remains valid.
To describe the variations of the temperature we need to write an energy balance
equation. In the following we develop the energy balance for any macroscopic system
(Fig. 2.3) and then we apply it to our example of stirred tank heater.
The energy E(J) of any system of (Fig. 2.3) is the sum of its internal U(J), kinetic K(J)
and potential energy (J):

E=U+K+ (2.14)

Consequently, the flow of energy into the system is:

32
 ~ ~ ~
f Ff ( U f  K f   f  (2.15)

where the ( ~
 ) denotes the specific energy (J/kg).

Ff , Tf , f

Q
L

Fo , To , o

Tst
Heat supply

Figure 2-2 Stirred Tank Heater

Q
F1 F1
Inlets
outlets
F2 System F2

Fn
F3
Ws
Figure 2-3 General Macroscopic System

The flow of energy out of the system is:

~ ~ ~
o Fo( U o  Ko  o  (2.16)

The rate of accumulation of energy is:

33
  ~ ~ ~
d V (U  K   )  (2.17)
dt

As for the rate of generation of energy, it was mentioned in Section 1.8.4, that the
energy exchanged between the system and the surroundings may include heat of
reaction Qr (J/s), heat exchanged with surroundings Qe (J/s) and the rate of work done
against pressure forces (flow work) Wpv (J/s), in addition to any other work Wo.
The flow of work Wpv done by the system is given by:

Wpv  Fo Po  Ff Pf (2.18)

where Po and Pf are the inlet and outlet pressure, respectively.

In this case, the rate of energy generation is:

Qe  Qr  (Wo  Fo Po  F f Pf ) (2.19)

Substituting all these terms in the general balance equation (Eq. 1.7) yields:

 ~ ~ ~
d V (U  K  )  ~
~ ~
 ~
 ~ ~
  f F f U f  K f   f  o Fo U o  Ko  o 
dt (2.20)
 Qe  Qr  (Wo  Fo Po  F f Pf )

We can check that all terms of this equation have the SI unit of (J/s). Equation (2.20)
can be also written as:

 ~ ~ ~
d V (U  K  )  ~
~ ~
~
 ~ ~
  f F f U f  K f   f  o Fo U o  K o  o 
dt
P Pf
 Qe  Qr  Wo  Foo o  F f  f (2.21)
o f

34
 ~
The term V  1 /  is the specific volume (m3/kg). Thus Eq. 2.21 can be written as:

 ~ ~ ~
d V (U  K   )  ~
 ~ ~ ~
 ~
 ~ ~ ~
  f F f U f  Pf V f  K f   f   o Fo U o  PoVo  K o  o 
dt (2.22)
 Qe  Qr  Wo

~ ~ ~
The term U  PV that appears in the equation is the specific enthalpy h . Therefore,
the general energy balance equation for a macroscopic system can be written as:

 ~ ~ ~
d V (U  K  )  ~
 ~ ~
 ~ ~
 ~

  f F f h f  K f   f  o Fo ho  Ko  o  Qe  Qr  Wo
(2.23)
dt

We return now to the liquid stirred tank heater. A number of simplifying assumptions
can be introduced:

 We can neglect kinetic energy unless the flow velocities are high.
 We can neglect the potential energy unless the flow difference between the inlet
and outlet elevation is large.
 All the work other than flow work is neglected, i.e. Wo = 0.
 There is no reaction involved, i.e. Qr = 0.

The energy balance (Eq. 2.23) is reduced to:


d VU
~
 ~ ~
  f F f h f  o Fo ho  Qe
(2.24)
dt

Here Qe is the heat (J/s) supplied by the external source. Furthermore, as mentioned in
~ ~
Section 1.12, the internal energy U for liquids can be approximated by enthalpy, h .
The enthalpy is generally a function of temperature, pressure and composition.
However, it can be safely estimated from heat capacity relations as follows:

35
 ~ ~
h  Cp (T  Tref ) (2.25)

~
where Cp is the average heat capacity.
Furthermore since the tank is well mixed the effluent temperature To is equal to process
temperature T. The energy balance equation can be written, assuming constant density
f = o =  , as follows:

C p

~ d V (T  Tref )  ~ ~
 F f C p (T f  Tref )  FoC p (T  Tref )  Qe
(2.26)
dt

Taking Tref = constant for simplicity and since V = AL result in:

~ d LT  ~ ~ (2.27)
C p A  F f C pT f  FoC pT  Qe
dt

or equivalently:

d LT  Q (2.28)
A  F f T f  FoT  ~e
dt C p

Since

d LT  d L  d T  (2.29)
A  AT  AL
dt dt dt

and using the mass balance (Eq. 2.8) we get:

dT Q (2.30)
AL  T ( F f  Fo )  F f T f  FoT  ~e
dt C p

or equivalently:

36
 dT Q
AL  F f (T f  T )  ~e
dt C p (2.31)

The stirred tank heater is modeled, then by the following coupled ODE's:
dL (2.32)
A  F f  Fo
dt

dT Q (2.33)
AL  F f (T f  T )  ~e
dt C p

This system of ODE's can be solved if it is exactly specified and if conditions at initial
time are known,

L(ti) = Li and T(ti) = Ti (2.34)

Degree of freedoms analysis

For this system we can make the following simple analysis:

 Parameter of constant values: A,  and Cp

 (Forced variable): Ff and Tf
 Remaining variables: L, Fo, T, Qe
 Number of equations: 2 (Eq. 2.32 and Eq. 2.33)

The degree of freedom is therefore, 4 − 2 = 2. We still need two relations for our
problem to be exactly specified. Similarly to the previous example, if the system is
operated without control then Fo is related to L through (Eq. 2.10). One additional
relation is obtained from the heat transfer relation that specifies the amount of heat
supplied:

Qe = UAH (Tst−T ) (2.35)

37
U and AH are heat transfer coefficient and heat transfer area. The source temperature Tst
was assumed to be known. If on the other hand both the height and temperature are
under control, i.e. kept constant at desired values of Ls and Ts then there are two control
laws that relate respectively Fo to L and Ls and Qe to T and Ts:

Fo = Fo(L, Ls), and Qe = Qe (T, Ts) (2.36)

2.1.3 Isothermal CSTR

We revisit the perfectly mixed tank of the first example but where a liquid phase
chemical reactions taking place:

k (2.37)
A
 B

The reaction is assumed to be irreversible and of first order. As shown in figure 2.4, the
feed enters the reactor with volumetric rate Ff (m3/s), density f (kg/m3) and
concentration CAf (mole/m3). The output comes out of the reactor at volumetric rate Fo,
density 0 and concentration CAo (mole/m3) and CBo (mole/m3). We assume isothermal
conditions.

Our objective is to develop a model for the variation of the volume of the reactor
and the concentration of species A and B. The assumptions of example 2.1.1 still hold
and the total mass balance equation (Eq. 2.6) is therefore unchanged

Ff
f
CAf V Fo
CBf o
CAo
CBo
Figure 2.4 Isothermal CSTR

38
 The component balance on species A is obtained by the application of (Eq. 1.3)
to the number of moles (nA = CAV ). Since the system is well mixed the effluent
concentration CAo and CBo are equal to the process concentration CA and CB.

Flow of moles of A in:

Ff CAf (2.38)

Flow of moles of A out:

Fo CAo (2.39)

Rate of accumulation:

dn d (VC A )

dt dt (2.40)

Rate of generation: -rV

where r (moles/m3s) is the rate of reaction.

Substituting these terms in the general equation (Eq. 1.3) yields:

d (VC A ) (2.41)
 F f C Af  Fo C A  rV
dt

We can check that all terms in the equation have the unit (mole/s).
We could write a similar component balance on species B but it is not needed
since it will not represent an independent equation. In fact, as a general rule, a system of
n species is exactly specified by n independent equations. We can write either the total
mass balance along with (n −1) component balance equations, or we can write n
component balance equations.

39
Using the differential principles, equation (2.41) can be written as follows:

d (VC A ) d (C A ) d (V ) (2.42)
V  CA  F f C Af  Fo C A  rV
dt dt dt

Substituting Equation (2.6) into (2.42) and with some algebraic manipulations we
obtain:

d (C A ) (2.43)
V  F f ( C Af  C A )  rV
dt

In order to fully define the model, we need to define the reaction rate which is for a
first-order irreversible reaction:

r = k CA (2.44)

Equations 2.6 and 2.43 define the dynamic behavior of the reactor. They can be solved
if the system is exactly specified and if the initial conditions are given:

V(ti) = Vi and CA(ti) = CAi (2.45)

Degrees of freedom analysis

 Parameter of constant values: A
 (Forced variable): Ff and CAf
 Remaining variables: V, Fo, and CA
 Number of equations: 2 (Eq. 2.6 and Eq. 2.43)

The degree of freedom is therefore 3 − 2 =1. The extra relation is obtained by the
relation between the effluent flow Fo and the level in open loop operation (Eq. 2.10) or
in closed loop operation (Eq. 2.11).

The steady state behavior can be simply obtained by setting the accumulation terms to
zero. Equation 2.6 and 2.43 become:

40
 F0 = Ff (2.46)

Ff ( C Af  CA )  rV (2.47)

More complex situations can also be modeled in the same fashion. Consider the
catalytic hydrogenation of ethylene:

A+BP (2.48)

where A represents hydrogen, B represents ethylene and P is the product (ethane). The
reaction takes place in the CSTR shown in figure 2.5. Two streams are feeding the
reactor. One concentrated feed with flow rate F1 (m3/s) and concentration CB1 (mole/m3)
and another dilute stream with flow rate F2 (m3/s) and concentration CB2 (mole/m3). The
effluent has flow rate Fo (m3/s) and concentration CB (mole/m3). The reactant A is
assumed to be in excess.

F1, CB1 F2, CB2

V
Fo, CB

Figure 2-5 Reaction in a CSTR

The reaction rate is assumed to be:

k1CB
r (mole / m3.s)
(1  k2CB )2 (2.49)

41
where k1 is the reaction rate constant and k2 is the adsorption equilibrium constant.
Assuming the operation to be isothermal and the density is constant, and following the
same procedure of the previous example we get the following model:

Total mass balance:

dL
A  F1  F2  Fo
dt (2.50)

Component B balance:

d (C A )
V  F1 ( C B1  CB )  F2 ( C B 2  CB )  rV
dt (2.51)

Degrees of freedom analysis

 Parameter of constant values: A, k1 and k2

 (Forced variable): F1 F2 CB1 and CB2
 Remaining variables: V, Fo, and CB
 Number of equations: 2 (Eq. 2.50 and Eq. 2.51)
The degree of freedom is therefore 3 − 2 =1. The extra relation is between the effluent
flow Fo and the level L as in the previous example.

2.1.4 Gas-Phase Pressurized CSTR

So far we have considered only liquid-phase reaction where density can be taken
constant. To illustrate the effect of gas-phase chemical reaction on mass balance
equation, we consider the following elementary reversible reaction:

A  2B (2.52)

taking place in perfectly mixed vessel sketched in figure 2.6. The influent to the vessel
has volumetric rate Ff (m3/s), density f (kg/m3), and mole fraction yf. Product comes out
of the reactor with volumetric rate Fo, density o, and mole fraction yo. The temperature

42
and volume inside the vessel are constant. The reactor effluent passes through control
valve which regulate the gas pressure at constant pressure Pg.

Ff, f , yf Fo, yo

P, T, V ,y Pg

Figure 2-6 Gas Pressurized Reactor

Writing the macroscopic total mass balance around the vessel gives:

d ( V )
  f F f   o Fo
dt (2.53)

Since V is constant we have:

d
V   f F f   o Fo
dt (2.54)

Writing the component balance, for fixed V, results in:

dCA (2.55)
V  F f C Af  FoC A0  r1V  r2V
dt

The reaction rates for the reversible reaction are assumed to be:

r1 = k1 CA (2.56)

r2  k2CB (2.57)
2

Equations (2.54) and (2.55) define the variations of density and molar concentration.
One can also rewrite the equation to define the behavior of the pressure (P) and mole

43
fraction (y). The concentration can be expressed in term of the density through ideal gas
law:

CA = yP/RT (2.58)

CB = (1 − y)P/RT (2.59)

Similarly, the density can be related to the pressure using ideal gas law:

 = MP/RT = [MAy + MB (1 − y)]P/RT (2.60)

Where MA and MB are the molecular weight of A and B respectively. Therefore one can
substitute equations (2.58) to (2.60) into equations (2.54 & 2.55) in order to explicitly
write the latter two equations in terms of y and P. Or, alternatively, one can solve all
equations simultaneously.

Degrees of freedom analysis:

 Parameters: V, k1, k2, R, T, MA and MB
 Forcing function: Ff, CAf, yf
 Variables: CA, CB, y, P, , F
 Number of equations: 5 (Eqs. 2.54, 2.55, 2.58, 2.59, 2.60)
The degree of freedom is therefore 6 − 5 =1. The extra relation relates the outlet flow to
the pressure as follows:

P  Pg
Fo  Cv
 (2.61)

where Cv is the valve-sizing coefficient. Recall also that Pg is assumed to be constant.

2.1.5 Non-Isothermal CSTR

We reconsider the previous CSTR example (Sec 2.1.3), but for non-isothermal
conditions. The reaction A  B is exothermic and the heat generated in the reactor is

44
removed via a cooling system as shown in figure 2.7. The effluent temperature is
different from the inlet temperature due to heat generation by the exothermic reaction.

Ff , CAf , Tf

Qe V Fo, CA, T

Figure 2-7 Non-isothermal CSTR

Assuming constant density, the macroscopic total mass balance (Eq. 2.6) and mass
component balance (Eq. 2.43) remain the same as before. However, one more ODE will
be produced from the applying the conservation law (equation 2.23) for total energy
balance. The dependence of the rate constant on the temperature:

k = koe-E/RT (2.62)

should be emphasized.

The general energy balance (Eq. 2.23) for macroscopic systems applied to the CSTR
yields, assuming constant density and average heat capacity:

C p

~ d V (T  Tref )  ~ ~
 F f C p (T f  Tref )  FoC p (T  Tref )  Qr  Qe
dt (2.63)

where Qr (J/s) is the heat generated by the reaction, and Qe (J/s) the rate of heat
removed by the cooling system. Assuming Tref = 0 for simplicity and using the
differentiation principles, equation 2.63 can be written as follows:

~ dT ~ dV ~ ~ (2.64)
C pV  C pT  F f C pT f  FoC pT  Qr  Qe
dt dt

45
Substituting Equation 2.6 into the last equation and rearranging yields:

~ dT ~ (2.65)
C pV  F f C p (T f  T )  Qr  Qe
dt

The rate of heat exchanged Qr due to reaction is given by:

Qr = −Hr)Vr (2.66)

where Hr (J/mole) is the heat of reaction (has negative value for exothermic reaction
and positive value for endothermic reaction). The non-isothermal CSTR is therefore
modeled by three ODE's:

dV (2.67)
 F f  Fo
dt

d (C A ) (2.68)
V  F f ( C Af  C A )  rV
dt

~ dT ~ (2.69)
C pV  F f C p (T f  T )  (H r )Vr  Qe
dt

where the rate (r) is given by:

r = koe-E/RTCA (2.70)

The system can be solved if the system is exactly specified and if the initial conditions
are given:

V(ti) = Vi T(ti) = Ti and CA(ti) = CAi (2.71)

Degrees of freedom analysis

 Parameter of constant values: E, R, Cp, Hr and ko
 (Forced variable): Ff , CAf and Tf

46
  Remaining variables: V, Fo, T, CA and Qe
 Number of equations: 3 (Eq. 2.67. 2.68 and 2.69)
The degree of freedom is 5−3 = 2. Following the analysis of example 2.1.3, the two
extra relations are between the effluent stream (Fo) and the volume (V) on one hand and
between the rate of heat exchanged (Qe) and temperature (T) on the other hand, in either
open loop or closed loop operations.

A more elaborate model of the CSTR would include the dynamic of the cooling
jacket (Fig. 2.8). Assuming the jacket to be perfectly mixed with constant volume Vj,
density j and constant average thermal capacity Cpj, the dynamic of the cooling jacket
temperature can be modeled by simply applying the macroscopic energy balance on the
whole jacket:

~ dT j ~ (2.72)
 jC p j V j   j F j C p j (T jf  T j )  Qe
dt

Since Vj, j, Cpj and Tjf are constant or known, the addition of this equation introduces
only one variable (Tj). The system is still exactly specified.

Fj , Tjf

V F o , CA , T

Fj , Tj

Ff , CAf , Tf

Figure 2-8 Jacketed Non-isothermal CSTR

2.1.6 Mixing Process

Consider the tank of figure 2.9 where two solutions 1 and 2 containing materials
A and B are being mixed. Stream 1 has flow rate F1 (m3/s), density 1 (kg/m3), T1 (K),

47
concentration CA1 (mole/m3) and CB1 (mole/m3) of material A and B. Similarly stream 2
has flow rate F2 (m3/s), density 2 (kg/m3), T2 (K), concentration CA2 (mole/m3) and CB2
(mole/m3) of material A and B. The effluent stream has flow rate Fo (m3/s), density o
(kg/m3), To (K), concentration CAo (mole/m3) and CBo (mole/m3) of material A and B. We
assume that the mixing releases heat of rate Q (J/s) which is absorbed by a cooling fluid
flowing in a jacket or a coil.

Our objective is to develop a model for the mixing process. We will assume that
the tank is well mixed. In this case all the effluent properties are equal to the process
properties. We also assume for simplicity that the densities and heat capacities of the
streams are constant and equal:

 = 1 = 2 = o (2.73)

Cp = Cp1 = Cp2 = Cp3 (2.74)

F1, T1, CA1, CB1 F2, T2, CA2, CB2

Fo, To, CAo, CBo

Figure 2-9 Mixing Process

Total mass balance

The mass balance equation yields

d ( V )
 F11  F2  2   Fo  o
dt (2.75)

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Since the densities are equals we have:

 F1  F2   Fo
dV
dt (2.76)

Component balance

The component balance for species A for instant yields:

d (  oC AoV )
 F11C A1  F2  2C A2   Fo  oC Ao
dt (2.77)

Expanding Eq. 2.77 yields:

o V
dV 
  F11C A1  F2  2C A2   Fo oC Ao
dCAo
 C Ao
 dt dt  (2.78)

Substituting Eq. 2.76 into 2.78 yields after some manipulation:

 F1 C A1  C Ao   F2 C A2  C Ao 
dCAo
V
dt (2.79)

A similar equation holds for component B,

d (  oCBoV )
 F11CB1  F2  2CB 2   Fo  oCBo
dt (2.80)

Energy balance

The general energy balance equation (Eq. 2.23) yields, assuming negligible kinetic,
potential energy and since no reaction or shaft work occurs:

49
  ~
d oVho, mix  ~ ~ ~
 1F1h1, mix   2 F2h2, mix  o Fo ho, mix  Q
dt (2.81)

~
where hi , mix (J/kg) is the specific enthalpy of mixture i.

~
The specific enthalpy hmix of n components can be written as:

~ ~
hmix (T , P)  hmix (Tref , P)  Cpmix (T  Tref ) (2.82)

where

n
~
 mix hmix (Tref , P)  Ci hˆi (Ci , Tref , P)  Ck hˆs (Ci , T , P)
i 1 (2.83)

with ĥi (J/mole) being the molar enthalpy of component i and ĥs is the heat of

solution per mole of a key component k. Assume constant process pressure (P) then
we can write the enthalpy of each stream as follows, taking component (A) as the key
component,

~
1h1, mix (T1 )  CA1hˆA  CB1hˆB  CA1hˆ1, s  1Cp1, mix (T1  Tref ) (2.84)

~
 2h2, mix (T2 )  C A2hˆA  CB 2hˆB  C A2 hˆ2, s   2Cp2, mix (T2  Tref ) (2.85)

~
 o ho , mix (T )  C Ao hˆA  CBo hˆB  C Ao hˆo , s   oCpo , mix (T  Tref ) (2.86)

Substituting Eq. 2.86 into the left hand side of Eq. 2.81 and expanding yields:

 ~
d oVho,mix  (2.87)
dt
d (VC Ao ) ˆ d (VC Bo ) d (VC Ao ) dT dV
= hˆA  hB  hˆ o ,s  CpV  CpT
dt dt dt dt dt

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The right hand side of equation (2.81) is equal after some manipulation to:

hˆA (C A1 F1  C A2 F2  C Ao Fo )  hˆB (C B1 F1  C B 2 F2  C Bo Fo )
 (C F hˆ  C F hˆ  C F hˆ )
A1 1 1,s A2 2 2 ,s Ao o o ,s
(2.88)
 Cp ( F1T1  F2T2  FoTo )  Q

Substituting into the right hand side of Eq. 2.87, the total mass balance equation (Eq.
2.76) and the component balance equation for species (A) (Eq. 2.77) and that of B (Eq.
2.80), and equating Eq. 2.87 to Eq. 2.88 yields, after some manipulations:

dT
VCp  C A1F1 ( hˆ1,s  hˆo ,s )  C A2 F2 ( hˆ2,s  hˆo ,s )
dt (2.89)
 Cp F1 (T1  T )  F2 (T2  T )   Q

The mixer is then described by three ODE's Equations (2.76, 2.79, 2.89). To these
relations we should add the relations that give the heats of mixing:

hˆ1, s  f1 (C A1 , C B1 , T1 ) (2.90)

hˆ2, s  f 2 (C A2 , CB 2 , T2 ) (2.91)

hˆo , s  f 3 (C Ao , CBo , To ) (2.92)

Degrees of freedom analysis

 Parameter of constant values: A, Tref, Cp, ĥA and ĥB

 (Forced variable): F1 , F2, CA1, CA2, T1 and T2

 Remaining variables: V, Fo, To, CAo, Q, hˆ1, s , hˆ2, s , hˆo , s

 Number of equations: 6 (Eq. 2.76, 2.79, 2.89 and 2.90-2.92)

51
The degree of freedoms is therefore 8 – 6 = 2. The two needed relations are the
relation between effluent stream Fo and height L and the relation between the heat Q
and temperature To in either open loop or closed-loop operations.

52