Analysis and Design of Chemical Reactors I

1. Introduction
Chemical reactors are the main components of chemical plants. They are
employed in most processes in petroleum, petrochemical, chemical,
biochemical, pharmaceutical and electronic industries. The most
frequently used reactor is the catalytic converter. The objective of the
analysis and design of chemical reactors is to achieve several critical
measures of performance:

♦ Selective production of desired products at maximum productivity

♦ Process and product safety

♦ Environmentally compatible processes and products

♦ Minimization of waste generation

♦ Minimization of investment

♦ Minimization of energy consumption

♦ Operability and control

Design of reactors require detailed consideration of various topics:

♦ Stoichiometry of reactions

♦ Thermodynamics – calculation of chemical equilibrium, heat of

reaction, phase equilibrium, physical and thermodynamic properties

♦ Transport phenomena – calculation of fluid flow, pressure drop,

heat transfer, mass transfer between phases and diffusion

1
 ♦ Kinetics – expressions of the rates of reaction as a function of
concentration and temperature

The scale of chemical reactors in the framework of related topics is

described in Figure 1.

Figure 1. Length and time scale of chemical reactors

Stoichiometry

Stoichiometric coefficients are determined arbitrarily as long as the

chemical reactions are balanced. Usually, the coefficient of the limiting
reactant is normalized to unity. Lets take the following example:

C2H4 + 0.5O2  C2H4O (1.1)

C2H4 + 3O2  2CO2 + 2H2O (1.2)

Those reactions can be expressed as:

2
∑α ij Aj = 0 (1.3)
j

The stoichiometric coefficients in this example are given in the matrix:

i j C2H4, 1 O2, 2 C2H4O, 3 CO2, 4 H2O, 5

1 -1 -0.5 1 0 0

2 -1 -3 0 2 2

Parameters that are used to quantify the progress of the reaction, extent of
reaction ξ i and conversion xj are defined as:

N i j − N i j,0
♦ ξi = ( 1 .4 )
α ij

N j0 − N j
♦ xj = ( 1.5)
N j0

Nij is the number of moles. The extent of reaction is identical for all
components in a specific reaction, while conversion is defined only for
the reactants. Similar definitions are given for continuous reactors in
terms of the molar flowrate Fij. The definition in equations (1.4) and (1.5)
are used to calculate the number of moles or the molar rate of component
j:

N j = N j 0 + ∑ α ijξ i (1.6)
i

F j = F j 0 + ∑ α ijξ i ' (1.7 )

i

3
Types of reactors

Chemical reactors are classified in terms of the type of flow:

♦ mixed or axial flow

and residence of reactants and products:

♦ batch, semibatch, continuous.

The flow characteristics are complex. Two extreme flow regimes are
defined:

•1 Well-mixed – temperature and concentration is identical everywhere

in the reactor. This is accomplished with a good mixing system that
provides a volumetric flowrate in the reactor significantly higher than
the inlet volumetric flowrate. Batch reactors (BR), semibatch (SBR)
and continuous stirred tank reactors (CSTR) are included in this
category.

•2 Plug-flow – turbulent flow with no axial mixing in tubular reactor

(PFR). Temperature and concentration change in axial direction.

Kinetics

Definition of the rates of reaction is essential for analysis and design of

reactors. The rate of reaction is defined as the number of moles reacted
(reactant) or produced (product) per unit time and per extensive unit
(volume, mass). The rate depends of the concentration of reactants,
products and catalyst (in case it is used) and temperature. The

4
mathematical formulation of the reaction rate is defined in kinetic
models. Three types of kinetic expressions are identified:

♦ Theoretical, based on mechanism, like the production of HBr from

bromine and hydrogen:

0.5
k1CH 2 CB r2
r= (1.8)
k2 + CH B r / CB r2

♦ Semi-empirical, partially based on theoretical model and partially

empirical

♦ Power-law, using reaction order, for example the reaction:

A+ B ⇔ R+ S ( α β γ
r = k C A CB − C R CS / K
δ
) ( 1 .9)

The reaction order should be assigned so as to satisfy the chemical

equilibrium expression.

2. Mass balances in isothermal reactors

Four types of reactors were defined:

♦ Continuous PFR and CSTR

♦ Semibatch well-mixed reactor

♦ Batch well-mixed reactor

The need to establish quantitative links between reactor performance and

input and operating variables is essential in optimizing reactor operation,
proper reactor selection and scale-up and interpretation of data from

5
bench and pilot plants. The general formulation of a reactor mass balance
is expressed as:

Rate of input – Rate of output + Rate of generation = Rate of

accumulation

The selection of the control volume in critical. Only single-phase reactors

will be defined. The control volume is normally the volume of the phase
where the reaction takes place. The general mass balance for a well-
mixed reactor is expressed as:

d Nj
F j 0 − Fj + R jV = ( 2.1)
dt

where Rj is the rate of change defined as:

Rj = ∑α r ij i ( 2.2)
i

Then for a batch reactor:

d Nj
R jV = ( 2.3)
dt

For a single reaction, considering the limiting reactant k with α k =-1

and introducing the definition of conversion yields:

dx
Nk0 = rV ( 2 .4 )
dt

Separation of variables and integration gives an expression for the time of

reaction as a function of conversion:

x
dx
t = Nko∫ ( 2.5)
0 rV

Normally the volume is constant. Then:

6
 x
dx
t = Cko ∫ ( 2. 6 )
0 r

The general mass balance for a CSTR at steady-state is expressed as:

Fj − Fj 0 = R jV (2.7)

Repeating the same derivation using conversion and the relationship:

Fk 0 = Q0Cko

yields:

V x
τ= = Ck 0 (2.8)
Q0 r

The concentration changes as a function of axial in PFR. Therefore, the

control volume is ∆ V to give:

dC j
Fj ,V − F j ,V + ∆V + R j ∆ V = ∆ V ( 2. 9)
dt

∂F j ∂C j
lim − + Rj = (2.10)
∆V → 0 ∂V ∂t

at steady-state:

d Fj
= Rj (2.1 1)
dV

Repeating the same procedure using the conversion gives:

V dx
τ = = Ck 0 ∫ (2.12)
Q0 r

The similarity between expression (2.12) for PFR and (2.6) for BR is
evident. τ is called the space time. If the volumetric flowrate is constant
(constant density) then this ratio is the residence time in the reactor, θ .

7
3. Design and analysis of isothermal reactors

The solution of the mass balances requires the expression of the reaction
rate in terms of concentrations and temperature, namely the kinetic
expression. The simplest kinetic expression that fits many practical
systems is first order:
r = kCj 3.1)

For constant density systems, the concentration is a simple function of

conversion:

C j = C j 0 (1 − x) ( 3.2)
Substituting eqn. (3.2) in the mass balance for batch reactors yields:

x = 1 − exp( − kt) ( 3.3)

Similar expressions are derived for PFR and CSTR, respectively:
1
x = 1 − exp( − kθ ) x = 1− (3.4)
1 + kθ

The similarity between BR and PFR is evident. At equal time and

residence time, the conversion in BR and PFR is identical, higher than in
CSTR.

Reactors arranged in series are analyzed relating the conversion to the

inlet of the system. Let consider a first-order reaction carried out in N
CSTRs in series, each one with a volume V/N. The mass balance in the
first reactor is expressed as:

The mass balance for the second reactor i

Fk 1 − F0 = − kCk 1V / N ( 3 .5 )
Repeating the same procedure for the N reactors yields:
Fk1 − Fk 2 = kCk 2V / N ( 3.8)
Q0Ck 0 x1 = kCk 0 (1 − x1 )V / N (3.6)

Fk 0 (1 − x1 ) − Fk 0 (1 − x2 ) = kCk 0 (1 − x2 )V / N ( 3.9)
1
x1 = 1 − 8 ( 3 .7 )
1 + kθ / N
1
x2 = 1 − ( 3.10)
(1 + kθ / N ) 2
Increasing the number of reactors at constant total residence time
increases conversion. At sufficiently large value of N (the required value
of N increases with increasing kθ ) the conversion in N CSTR in series
approaches the PFR conversion.
1
xN = 1− (3.11)
(1 + kθ / N ) N
A similar behavior is reached in PFR with recycle. In the recycle system
several parameters are defined. The recycle ratio is given by the
expression:

Qr(r v e ro )c a ly u t c e m l e e t r i c
R= ( 3 .1 ) 2
Q3(o v u ro ) ta l ute e mt e t r i c
F11 − F12 F10 − F13
xs = xo = ( 3.13)
F11 F10

The single pass and overall conversion are defined as:

The relationship between xs and xo is developed as follows:

Substituting eqns. (3.14) and (3.15) into eqn. (3.13) yields:

F12 = F13 + F1r = F13 (1 + R ) = F10 (1 − xo )(1 + R ) ( 3.14 )

F11 = F10 + F1r = F10 + F10 R(1 − xo ) = F10 [1 + R(1 − xo ) ] ( 3.15 )

As R increases, the single-pass conversion decreases. At the limit, the
recycle reactor approaches CSTR.

The mass balance for the key component, assuming constant density:

xo
xs = 9 ( 3.1 6)
dF1 1 + R( 1 − xo ) F1 F (1 − x )
= − kC1 = − k = k 11 ( 3.17)
dV Q1 Q0 ( 1 + R )
Substituting the definition of conversion and integrating gives:

At R  0, eqn. (3.18) converges to the PFR expression. At the other

kV
− ln( 1 − xs ) = ( 3.18)
Q0 (1 + R )
extreme, R  ∞ yields xs  0. Eqn. (3.18) becomes:

xo kθ
xs = = ( 3.1 9)
1 + R( 1 − xo ) 1 + R

Since R is dominant at the denominator, eqn. (3.19) converges to eqn.

(3.4). Therefore, the performance of the two models, PRF with recycle
and N CSTRs in series provides the link between PFR and CSTR.

4. Expressions for the concentration

Gas phase systems with changing density in continuous reactors require

the derivation of the concentration. A simple expression is:
Fj
C j = y jCt = Ct ( 4.1)
Ft

10
Application of eqn. (4.1) means that the mole flowrate of all components
need to be calculated. However, using the conversion, only the key
component needs to be calculated, assuming α k = -1:

Fj = Fj 0 + α j xFk 0 ( 4 .2 )

Substituting Ft in eqn. (4.1) gives:

Ft = ∑F j = Ft 0 +δxyk 0 Ft 0 ( 4.3)
j

δ = ∑α j ε = δ yk 0 ( 4.4)

The mass balance for PFR for a first order reaction:

If one of the components is condensable, the concentration should be

1 − x Ct
C j = C j0 ( 4 .5 )
1 + ε x Ct 0
dx 1− x
Fj0 = kC j 0 ( 4.6)
dV 1 + εx

kV 1 + εx
=∫ dx = −(1 + ε ) ln(1 − x ) − εx ( 4.7 )
Q0 1− x
adjusted accordingly. First the conditions of condensation are determined,
Pv Fc 0 + α c xc Fk 0
yc = = ( 4 .8 )
P Ft 0 ( 1 + ε xc )
namely the mole fraction of the condensable component at the
condensation point. Then the conversion is calculated:

The molar flowrate of the condensable component remains constant after

condensation starts. Then the total molar flowrate and the concentration

11
of each component are calculated accordingly. An example will be solved
to demonstrate the procedure.

5. Pressure drop in tubular reactors

The general momentum balance for calculating the pressure drop for
gases flowing through pipes is expressed as:

dP du 2 fG 2
= −G − ( 5.1)
dz dz ρ dt

The mass velocity is constant in the reactor. Combining this expression

with the relationships:

uρ = G ( 5.2)

P T0 Ft 0
ρ = ρ0 ( 5.3)
P0 T Ft

and the mass balance in eqns (2.7) provides a model of PFR.

The pressure drop in a packed (fixed) bed reactor is calculated from the
Ergun equation:

dP G 2 1 − ε B 150
=− ( )( + 1.75) ( 5.4)
dz ρ d p ε B 3 Re

Gdp Vp
Re = dp = 6 (5.5)
µ (1 − ε B ) Sx

6. Unsteady-state operation of stirred reactors

1. Startup of a CSTR

12
A simple case is selected to illustrate the procedure to solve this type of
problems: first-order reaction in constant volume reactor. Eqn. (2.1)
becomes:

dCj
C j 0 − C j − kθ C j = θ ( 6.1)
dt

with the initial condition: t = 0 Cj = 0.

Applying the integrating factor method, the solution of eqn. (6.1) is:

C j0 t
Cj = {1 − exp[− (1 + kθ ) ]} ( 6.2)
1 + kθ θ

The time needed to reach 99% of the steady state value is calculated
using the relationship:

t
1 − exp[ −(1 + kθ ) ] = 0. 99 (6.3)
θ

that yields:

θ
tss = 4.6 (6.4)
1 + kθ

2. Semi-batch reactors

The system analyzed here consists of two reactants, A is present in the

reactor and B flows in at the molar rate FB0. Two cases will be
considered:

2.1 . Case I – first-order with respect to A

The mass balance for A:

d NA
= − k CAV ( 6.5)
dt

13
The volume changes with time: V = V0 + Qt

The solution of eqn. (6.5) given that Na = CAV

N A = N A 0 exp(− kt ) C A = C A0 exp(− kt ) /(V0 + Qt ) (6.6)

2.2 . Case II – first-order with respect to B

Mass balance for component B

d NB
= Q CB 0 − kCBV (6.7)
dt

Substituting the derivation of NB = CBV

d NB dV dC
= CB + V B (6.8)
dt dt dt

dCB
CBQ + V = Q CB 0 − kCBV (6.9)
dt

Substituting the relationship θ = θ 0 + t and rearrangement of terms in

eqn. (6.9) yields:

dCB 1 C
+ ( + k )CB = B 0 (6.10)
dθ θ θ

The solution of eqn. (6.10) with t = 0 CB = CBi is:

CB 0 C θ
CB = − ( B 0 − CBi ) 0 exp(− kt) (6.11)
(t + θ 0 )k θ 0 k θ0 + t

7. Heat balances in chemical reactors

The energy balance in the batch reactor is:

14
 .
.
dE ' '
= Q − Ws ( 7.1)
dt

The total energy in the system is expressed as:

E = H − PV = ∑ N j H j − P ∑ N jV j ( 7 .2 )

Differentiating eqn. (7.2) and substituting the pertinent expressions:

dH j dN j dT
∑N j + ∑H j = ∑ N j C pj + ∑ H j ∑αij riV ( 7.3)
dt j dt dt j i

Rearrangement of eqn. (7.3) yields:

dT d ( PV )
∑N C j pj = ∑( − ∆H ) i riV − UA ( T − Ts ) + − Ws' ( 7 .4 )
j dt dt

∆H i = ∑αij H j
where:

A similar derivation for CSTR:

dE
= Q ' − Ws' + ∑ F j 0 H j 0 − ∑ F j H j ( 7.5)
dt

Combination with the mass balance yields:

dT
∑N C j pj + ∑ Fj 0C pj ( T − T0 ) = ∑ ( − ∆H ) i riV
j dt i

d ( PV )
− UA( T − Ts ) − Ws' − ( 7. 6 )
dt

The differential heat balance in a PFR:

dEv
= Q ' − Ws' + ∑ F j H j IV − ∑ F j H j IV + ∆V ( 7 .7 )
dt j j

yields the heat balance:

15
 ∂Ev ∂  
= Qv' − Ws', v −  ∑ Fj H j 
  ( 7.8)
∂t ∂V  j 

A similar derivation including the differentiation of the term in the right

hand side of eqn. (7.8) and substitution of the mass balance gives the
transient form of the heat balance:

∂T ∂T
∑C Cj
j pj
∂t
= −∑ F j C pj
j ∂V
+

∂P
∑( − ∆H ) r − Ua (T − T ) + ∂t
i i s − Ws',v ( 7.9 )

The last two terms on the right hand side of eqn. (7.9) are normally
negligible.

There are two types of reactors:

♦ adiabatic - where there is no heat exchange with the surroundings

♦ non-adiabatic – where there is heat exchange with the surroundings

Isothermal operation of reactors is an ideal case of the latter type. CSTR

can be operated isothermally. Since the rate changes with conversion, it
varies with time (batch) or place (PFR). Thus the rate of heat generation
changes, rendering controlling the temperature constant very difficult.

The preferred method of operation is adiabatic since it does not need

heat-exchanging area. The heat balance for the batch adiabatic reactor
and a single reaction system is:

dT
∑N j C pj = ( − ∆H ) rV ( 7.10)
dt

16
Substituting the mass balance:

dx
N j0 = rV ( 7.11)
dt

yields

dT dx
∑NC j pj = ( − ∆H ) N j 0 ( 7.12)
dt dt

Eqn. (7.12) is rearranged to give the expression for the temperature as a

function of conversion:

( − ∆ H ) N j0
T − Ti = x ( 7.13)
∑NC j pj

The term that multiplies the conversion is called the adiabatic

temperature rise and could be assumed to be essentially constant:

( − ∆H ) N j 0 ( − ∆H ) N j0
∆ Tad = = ( 7.14)
∑N C j pj ∑ W (C j pj / M wj )

Similar expressions are derived for CSTR:

( − ∆ H ) Fj 0 ( − ∆ H ) Fj 0
∆ Tad = = ( 7.15)
∑FC j pj ∑ W (C
j0 pj / M wj )

and PFR:

( − ∆ H ) Fj 0 ( − ∆ H ) Fj 0
∆ Tad = = ( 7.16)
∑FC j pj ∑ W (C
j pj / M wj )

8. Performance of exothermic reversible systems

17
The analysis of exothermic reversible systems is demonstrated with a
simple elementary reaction A ⇔ B. The rate is then expressed as:

r = k (C A − CB / K ) = kCA0 (1 − x − x / K ) ( 8.1)

The conversion at equilibrium decreases with temperature. Therefore this

conversion at a given temperature is the maximum possible value. If we
take a certain conversion well below its maximum value, and increase the
temperature at constant conversion, the reaction rates should increase.
However, as equilibrium is approached, the rate should decrease.
Therefore, there is a point, close to the equilibrium curve that determines
the maximum value of the reaction rate.

The derivation of the maximum rate at constant conversion is done as

follows:

 dr  dk x dK
  = (1 − x − x / K ) +k 2 =0 ( 8.2)
 dT  x dT K dT

where the two derivatives are expressed as:

dk AE
= exp(− E / RT ) (8.3)
dT RT 2

1 dK ∆ H
= (8.4)
K dT RT 2

Substitution into eqn. (8.2) yields:

E ∆H 1
(1 − x − x / K ) 2
+x 2 =0 (8.5)
RT RT K

Rearranging this eqn. gives:

18
 x E − ∆H
K= (8.6)
1− x E

Operation on the maximum rate curve should yield the minimum reactor
volume. Design of an optimal CSTR is feasible since it runs at one
operating set of conditions. However if the designed conversion is
relatively high, a number of adiabatic CSTRs would provide a more
economical proposition.

Design of adiabatic PFRs in series is the best method in many industrial

processes, for example methanol synthesis or sulfur trioxide production.
Inter-cooling is the accepted procedure to adjust the inlet temperature.
This is done with a heat exchanger or by quenching with one of the
reactants.

9. Stability of CSTR operation

The heat balance of CSTR can be divided into rate of heat generated:

Qg = (− ∆ H )rV (9.1)

and the rate of heat removed:

Q r = Ft 0 C p (T − T0 ) + UA(T − Ts ) (9.2)

The expression for the rate of heat generated in case of a first-order

reaction is given as:

kθ
Qg = (− ∆ H ) F10 (9.3)
1 + kθ

19
The curve that describes Qg as a function of T is S-shape with a plateau at
high values of T. Qr as a function of T is given by a straight line
expressed as:

Qr = ( Ft 0C p + UA)(T − Ta ) (9.4)

Ft 0C pT0 + UATs
Ta = (9.5)
Ft 0C p + UA

Three possibilities of the simultaneous solution of mass and heat balances

were identified:

♦ single stable state so that generation of minor perturbations in the

operating conditions do not cause changes in the steady-state condition

♦ two states, one stable and the other unstable

♦ three states, two stable and one, between the two, unstable

The necessary condition for absolute stability of the system is given by

the expression:

dQr  dQg 
≥  (9.6)
dT  dT  m ax

10. Multiple reaction systems

Most organic systems consist of multiple reactions. Some of them are

extremely complex. Oxidation of organic molecules is a good example:

C7H8 + O2 ⇒ C7H6O + H2O

20
C7H8 + O2 ⇒ C6H6 + CO + H2O

C6H6 + 7.5O2 ⇒ 6CO2 + 3H2O

C7H8 + 9O2 ⇒ 7CO2 + 4H2O

Lets consider a simple system of two reactions in parallel:

A⇒D
α1
r1 = k1CA

A⇒U
α2
r2 = k2CA

Several definitions were adopted:

• point selectivity
r1
S= ( 1 0.1)
r2
N D FD
So = = (1 0.2)
NU FU
• • overall selectivity

• yield

N D FD
YD = = (1 0.3)
N A0 FA0

In the case of two parallel reactions, the point selectivity is expressed as:

k1 α 1 − α 2
S= CA (1 0.4)
k2

If α 1 > α 2 , the selectivity increases with increasing concentration of

reactant A. Therefore, the overall selectivity in PFR and BR would be

21
higher than in CSTR. In the opposite case, α 1 < α 2 , CSTR is the
preferred choice.

Lets consider another simple system of two reactions in parallel:

A+B ⇒ D
α1 β1
r1 = k1CA CB

A+B ⇒ U
α2 β2
r2 = k2CA CB

The selectivity is defined as:

k1 α 1 − α 2 β 1 − β 2
S= C A CB (1 0.5)
k2

The most interesting case is α 1 > α 2 , β 1 < β 2 . A special reactor

system would be needed to maximize selectivity.

The temperature has a significant effect on selectivity through the

dependency of k on temperature determined by the activation energy.
Going back to eqn. (3.4), if E1 > E2, then the selectivity increases with
temperature.

The general mass and energy balances have already been developed. In
the case of a single reaction, one mass balance was solved. If N
components and M reactions are present in the system, the maximum
number of mass balances is equal to N. However this number can be
reduced to the number of independent equation in the system Mi. This
number is calculated from the matrix of the stoichiometric coefficients.

For example the reaction between CO, CO2 and H2:

CO + 2H2 ⇒ CH3OH

CO2 + H2 ⇒ CO + H2O

CO2 + 3H2 ⇒ CH3OH + H2O

22
Clearly only two reactions are independent. Therefore only two mass
balances are necessary while all other components are expressed in terms
of the two key components. However writing five mass balances is
correct, although it leads to a more complex system of equations. The
kinetic model may still require all three kinetic expressions.

Lets take a system of two first order reactions in series carried out in an
isothermal batch reactor:

A1 ⇒ A2 ⇒ A3

The two mass balances are expressed as:

dC1
= − k1C1 (10.6)
dt
dC2
= k1C1 − k2C2 (10.7 )
dt

The solution of eqn. (10.6) has been derived:

C1 = C10 exp(− k1t ) (10.8)

Substituting eqn.(10.8) into eqn. (10.7) and solving using the method of
integrating factor yields:

k1C10
C2 = [exp(− k1t ) − exp( −k 2 t )] (10.9)
k 2 − k1

This expression gives a maximum selectivity to A2. The time at the

maximum value of C2 is calculated taking the derivative of eqn. (10.9):

ln(k1 / k 2 )
t m ax = (10.10)
k1 − k 2

The same expression is derived for a PFR. However a different

expression for the maximum is derived for a CSTR.

23
11. Kinetics of reactions

The rate of reaction is a basic constitutive relationship required for

analysis and design of reactors. Three general types of expressions have
been mentioned: theoretical based on mechanism, semi-empirical based
kinetic models and empirical. One of the most important types of kinetic
mechanisms is the group of radical reactions that takes place in thermal
cracking reactions. Those mechanisms consist of a large number of
reactions, included in complex numerical codes. A typical example is the
steam cracking for production of olefins.

Radical reactions are combined of three types of reactions. Each reaction

is considered to be elementary. Lets take the case of ethane cracking to
illustrate the modeling of such systems:

1. initiation

•
C2 H 6 ⇒ 2C H3 A1 ⇒ 2 A2 r1 = k1C1 (11.1)

2. propagation

• •
CH3 + C2 H 6 ⇒ C H4 + C2 H 5 A2 + A1 ⇒ A3 + A4

r2 = k2C1C2 (11.2)

•
C2 H 5 ⇒ C 2 H 4 + H • A4 ⇒ A5 + A6 r3 = k3C4 (11.3)

•
H • + C2 H 6 ⇒ C2 H 5 + H 2 A6 + A1 ⇒ A4 + A7

r4 = k4C1C6 (11.4)

24
 3. termination

• 2
2C2 H 5 ⇒ C4 H1 0 2 A4 ⇒ A8 r5 = k5C4 (11.5)

This system of reactions can be solved simultaneously, for a PFR, given

all the rate constants. However, this system can be greatly simplified if
the assumption of negligible rates of change of the intermediates is
invoked:

R2 = 0 R4 = 0 R6 = 0 (11.6)

Substituting the proper rates of reaction yields closed expressions for the
intermediates:

0 .5
2k  2k 
C4 = k3  1  C1
0.5
C2 = 1
k2  k5 

0.5
k  2k  − 0 .5
C6 = 3  1  C1 (11.7)
k 4  k5 

Given the expressions in (11.7), the rates of change of the main

components can be introduced in the mass balances.

Another type of free radical reactions is polymerization, like polystyrene

or polyvinylchloride production:

I 2 ⇒ 2I rIf = 2 fk 0 I 2 (11.8)

I + M ⇒ S1 ri = k i M I (11.9)

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 S j + M ⇒ S j +1 r j = k p MS j (11.10)

S j + M ⇒ Pj + S1 rmj = k m MS j (11.11)

S j + S k ⇒ Pj + k raj = k a S j S k (11.12)

S j + S k ⇒ Pj + Pk rd = k d S j S k (11.13)

The concentration of the initiator is calculated assuming that its rate of

change is negligible:

2 fk0 I 2
I= (1 1.1 4)
M ki

− RM = k p M ∑ S j = k p MS ∗ (11.15)
j

− R j = k p M ( S j − S j −1 ) + (k a + k d ) S j ∑ Si + k m MS j (11.16)
i =1

∑− R
j =1
j = − Ri + kt ( S ∗ )2 (11.17)

Finally the rate of change of the monomers is:

0.5
 2 fk0 I 2 
− RM k p M   (11.18)
 kt 

Measurement and analysis of kinetic data are essential for derivation of

kinetic expressions. Data are measured in all types of reactors. Batch
reactors are popular for liquid phase reactions. However the rate changes
with concentration. Therefore it changes with time. Working with CSTR
render direct measurement of rates feasible. PFR is used for gas-phase
reactions. In batch and PFR reactors types of measurements are possible:

• differential at low conversion levels so the rate can be considered

approximately to be constant

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 • integral at high conversion levels where analysis of the data is
require to extract the rate expressions

12. Residence time distribution

The analysis of chemical reactors has been based on ideal behavior: ideal
mixing and plug flow. This is an excellent first-order approximation for
most cases of practical interest. However, in many other cases, this
approach is not satisfactory because of the type of flow in the reactor, i.e.
laminar flow, or problems in design and operation, i.e. flow bypass.
Therefore tools are needed to deal with those situations either to analyze
such problems (laminar flow) or to diagnose faulty operation. The most
useful approach for solving those problems is the application of principle
of residence time distribution (RTD).

The flow in the reactors is assumed to consist of lumps of molecules

called elements of flow. Those elements are microunits of flow combined
of a large number of molecules so concentration and temperature are
defined, but much smaller than reactor volume. The simplest example in
plug flow where all elements reside in the reactor identical time.

Measurements and analysis of RTD require the application of a tracer

that defines the flow. Its concentration is normally very small, it does not
disturb the flow and can be clearly identified. The tracer is injected at the
inlet (only one) and is analyzed at the outlet (only one). Two types of
methods are normally used, although others are also employed:

• pulse function where the tracer is introduced in one shot at

infinitely short time defined by the Dirac function:

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 δ (t − θ ) = 0 @ t ≠ θ δ (t − θ ) ≠ 0 @ t = θ (12 .1)

∞ ∞

∫ δ (t − θ )dt = 1
−∞ −∞
∫ f (t )δ (t − θ )dt = f (θ ) (12.2)

• step function where the tracer is injected at constant concentration::

u (t − θ ) = 0 @ t < θ u (t − θ ) = 1@ t ≥ θ (12.3)

Accordingly, two different functions are defined:

• residence time distribution function E(t)dt is the fraction of fluid

elements at the reactor outlet that resided in the reactor between time
t and time t+dt.

• step function F(t) is the fraction of fluid elements at the reactor

outlet that resided in the reactor less than time t

There is a simple relationship between the two functions:

∞ t
dF (t )
∫ E (t )dt = 1
0
∫ E (t )dt = F (t )
0
E (t ) =
dt

∞ ∞
θ = ∫ tE (t )dt σ 2 = ∫ (t − θ ) 2 E (t )dt (12.4)
0 0

For PFR the functions can be defined:

E (t − θ ) = δ (t − θ ) F (t ) = u (t − θ ) (12.5)

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The expression for E(t) is derived from a general mass balance on a pulse
injection:

QCp (t )
ME(t )dt = QCp (t )dt E (t ) = (12.6)
M

Since M is calculated from the mass balance, expression (6.6) becomes:

QCp (t ) C p (t )
E (t ) = ∞
E (t ) = ∞
(12.7)
Q ∫ C p (t )dt ∫C p (t )dt
0 0

The expression for F(t) is derived from a general mass balance on a step
injection:

Cs (t )
F (t ) = (1 2.8)
C0

Clearly each function can be calculated from the other function based on
the relationship (12.4).

Lets develop the two functions for CSTR using a step change:

dC1 dC1
F10 − F1 = V C10 − C1 = θ C1 = 0 @ t = 0 (12.9)
dt dt

C1 1
= F (t ) = 1 − exp(−t / θ ) E (t ) = exp(−t / θ ) (12.10)
C10 θ

It is important to develop the expression for the RTD functions:

1 t −θ p  t −θ p 
E (t ) = exp(− ) F (t ) = 1 − exp  (12.11)
θs θs θ
 s 

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Laminar flow is another case that can be solved using RTD. The
derivation is based on the parabolic velocity profile:

 r 2
 u0
u = u 0 1 −    u= (12.12)
  R   2

L 2L L
t= = tm in = (12.13)
u u0 u0

The function F(t) is defined as:

r   r 2 
r

∫0 2πru (r )dr ∫0 1 −  R  dr  r 2  r 4

r
F (t ) = R = = 2  −   (12.14)
R
  r 2  R R
∫0 2πru (r )dr ∫ r 1 −  R  dr
0   

Finally substituting t for r yields:

θ   r 2  2
θ  θ
= 21 −    F (t ) = 1 −   @ t ≥ (12.15)
t   R    
2t 2

Differentiating this expression yields

θ2 θ
E (t ) = 3
@t ≥ (1 2.16)
2t 2

Calculation of conversion based on RTD requires the assumption of

segregated flow meaning no mass exchange between elements. Therefore
each element is regarded as a small batch reactor:

∞
C j = ∫ C j (t ) E (t ) dt (12.17)
0

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Is has already been demonstrated that a model of N CSTR in series
covers the behavior between CSTR and PFR. The derivation for this
model in terms of RTD uses a pulse function:

C NV
E (t ) = (12.18)
θM

C1V N  Nt 
E1 (t ) = = exp −  (12.19)
θM θ  θ 

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