Chemical Reaction Engineering 285

TABLE 6.2
Concentration of Bromine versus Time
t (min) C Br2  (gmol/dm3) t (min) C Br2 (gmol/dm3)
0 0.3335 19.60 0.1429
2.25 0.2965 27.00 0.1160
4.50 0.2660 30.00 0.1053
6.33 0.2450 38.00 0.0830
8.00 0.2255 41.00 0.0767
10.25 0.2050 45.00 0.0705
12.00 0.1910 47.00 0.0678
13.50 0.1794 57.00 0.0553
15.60 0.1632 63.00 0.0482
17.85 0.1500

The built-in function diff can be used to execute the numerical differentiation of data. Then the
linear regression method is employed to calculate n and k. The relation x = (ATA)−1ATb can be
used in the linear regression where x(1) = n and x(2) = ln (k). The script rnk performs the calcula-
tion procedure.

% rnk.m
t = [0 2.25 4.50 6.33 8.00 10.25 12.00 13.50 15.60 17.85 ...
19.60 27.00 30.00 38.00 41.00 45.00 47.00 57.00 63.00];
Cb = [0.3335 0.2965 0.2660 0.2450 0.2255 0.2050 0.1910 0.1794 0.1632 ...
0.1500 0.1429 0.1160 0.1053 0.0830 0.0767 0.0705 0.0678 0.0553 0.0482];
dCb = diff(Cb)./diff(t); dCb = [dCb dCb(end)];
n = length(t); A = [(log(Cb))' ones(n,1)];
x = (A'*A)^-1*A'*(log(-dCb))'
n = x(1), k = exp(x(2))

The script rnk produces the following outputs:

>> rnk
x =
1.5128
-2.4454
n =
1.5128
k =
0.0867

6.3.2 SEMIBATCH REACTORS

One of the best reasons to use semibatch reactors is to enhance selectivity in liquid-phase reactions.9
For example, consider the following two simultaneous reactions being carried out in a semibatch
reactor. The desired product is D:

kD
A + B ® D, rD = kDC A2C B

kU
A + B ® U , rU = kU C AC B2
286 Chemical Engineering Computation with MATLAB®

B, v0, CB0
A+B C+D

FIGURE 6.7 Semibatch reactor.

the instantaneous selectivity SD/U is the ratio of these two rates:

rD kDC A2 C B kD C A
S D /U = = =
rU kUC AC B2 kU C B

Consider a semibatch reactor that is charged with pure A and to which B is fed slowly to A as shown
in Figure 6.7. The elementary liquid-phase reaction is carried out in the reactor10:

A + B → C + D, − rA = kC ACB

Mole balance on each species yields

dC A vC dCB v0 (C B0 - CB ) dCC vC dC D vC
= rA - 0 A , = + rB , = rC - 0 C , = rD - 0 D
dt V dt V dt V dt V

-rA = -rB = rC = rD

The semibatch reactor volume can be expressed as a function of time, and the conversion of species
A is represented in terms of the reactor volume V as

C A0V0 - C AV
V = V0 + v0 t, X =
C A0V0

Example 6.10: Semibatch Reactor11

Methyl bromide is produced by the irreversible liquid-phase reaction

CNBr(A) + CH3NH2(B) → CH3Br(C) + NCNH2(D)

The reaction is carried out isothermally in a semibatch reactor. The reaction rate is given by
−rA = kCACB where k = 2.2 dm3/(sec · mol). The initial volume of liquid in the reactor is V0 = 5 dm3.
An aqueous solution of methyl amine (B) at a concentration of CB0 = 0.025 mol/dm3 is to be fed
at a volumetric ow rate of v0 = 0.05 dm3/sec to an aqueous solution of bromine cyanide (A) con-
tained in the reactor. The initial concentration of bromine cyanide is CA0 = 0.05 mol/dm3. Solve
for the concentration of each species (A and B) and the rate of reaction as a function of time. Plot
the results versus time (0 ≤ t ≤ 500 (sec)).
Chemical Reaction Engineering 287

Solution
Since −rA = − rB = rC = rD, we get the following differential equations:

dC A vC dCB v0 (CB0 - CB ) dCC vC dCD vC

= rA - 0 A , = + rA , = -rA - 0 C , = -rA - 0 D ,
dt V dt V dt V dt V
V = V0 + v0t , - rA = kC ACB

The MATLAB ® function semibrx de nes these differential equations:

function dxdt = semibrx(t,x,k,v0,V0,Cb0)

% x(1)=Ca, x(2)=Cb, x(3)=Cc, x(4)=Cd
rA = -k*x(1)*x(2); V = V0 + v0*t;
dxdt = [rA - v0*x(1)/V;
rA + (Cb0 - x(2))*v0/V;
-rA - v0*x(3)/V;
-rA - v0*x(4)/V];
end

The script usesemibrx calls the function semibrx and uses the built-in function ode45 to integrate
the system of differential equations. The script also calculates the conversion of A as a function
of time.

% usesemibrx.m
clear all;
k = 2.2; v0 = 0.05; V0 = 5; Cb0 = 0.025; Ca0 = 0.05;
x0 = [Ca0 0 0 0]; tspan = [0 500];
[t x] = ode45(@semibrx,tspan,x0,[],k,v0,V0,Cb0);
Ca = x(:,1); Cb = x(:,2); Cc = x(:,3); Cd = x(:,4);
V = V0 + v0*t; Xa = (Ca0*V0 - Ca.*V)/(Ca0*V0); rA = k*Ca.*Cb;
subplot(1, 2), plot(t,Ca, t,Cb,':', t,Cc,'.-', t,Cd,'--')
xlabel('t(s)'), ylabel('Concentration(mol/dm^3)'), legend('C_A','C_B','C_C','
C_D')
subplot(1, 2), plot(t,rA), xlabel('t(s)'), ylabel('Reaction rate(mol/dm^3s)')

The script usesemibrx generates the plots shown in Figure 6.8:

>> usesemibrx

6.4 PLUG-FLOW REACTOR

The mass balance for a plug- ow reactor can be expressed as

dX -rA dC A
= or v0 = rA
dV FA0 dV

If the reaction is carried out in isothermal isobaric conditions and the rate of reaction is taken as rst
order, FA0 = CA0v0, ε = y0δ, and

æ 1 - X ö P T0 æ 1- X ö
-rA = kC A = kC A 0 ç ÷ = kC A0 ç ÷
è 1 + εX ø P0 T è 1 + εX ø

Thus, the mass balance equation can be expressed as

dX k (1 - X )
= , X V =0 = 0
dV v0 (1 + εX )