1) In order to determine the effect of temperature rise on rate contants k

1
, k
2
, and k
3
,
Arrhenius equation must be rearranged.

Arrhenius equation relates k to arrhenius constant A, activation energy E
a
, gas
constant R and temperature T.
k = A exp (-E
a
/ RT)
by rearranging,
ln k = ln A E
a
/RT
ln k = -E
a
/RT + ln A
To investigate effect of T rise on k, a graph of ln k vs 1/T is plotted.
Three plot was contructed:
Reaction 1: ln k
1
= -25000/RT + ln 4300
Reaction 2: ln k2 = -30000/Rt + ln 70100
Reaction 3 : ln k
3
= -21000/RT + ln 26

The results was shown in figure 1 below



From the figure 1, it was shown that when T increases, k also increases. Besides that, the
higher the E
a
of the reaction, the steeper is the slope, in other words, the rate of increment
of k per unit temperature increase.
y = -1E+07x + 8.3664
y = -2E+07x + 11.158
y = -1E+07x + 3.2581
-6.00E+04
-5.00E+04
-4.00E+04
-3.00E+04
-2.00E+04
-1.00E+04
0.00E+00
0 0.001 0.002 0.003 0.004
l
n

k

1/T
ln k1 vs 1/T
ln k2 vs 1/T
ln k3 vs 1/T
Linear (ln k1 vs 1/T)
Linear (ln k2 vs 1/T)
Linear (ln k3 vs 1/T)
From these three equations, the k
2
is most sensitive to T change as it has the largest E
a
,
followed by k
1
and k
3
.

The significance of these observations are:
i) For reaction rate constant k, it always increases with increasing temperature
T. Hence, with higher T, reaction rate will be higher.

ii) The larger the activation energy E
a
is, the larger the change in k per unit
change in T. (the larger the E
a
, the higher the sensitivity of k toward T
change.)

iii) For this MA synthesis processes, an intermediate temperature range is
desired
because the main reaction 1s rate constant k
1
has an intermediate sensitivity ,
which is lower than the side reaction 2 and higher than side reaction 3. Only with
intermediate operating temperature range, the main reaction 1 can be dominant.



2) In these three reactions, main reaction 1 and side reaction 2 are reactions in series,
whereby main reaction 1 and side reaction 3 are reactions in parallel.
For series reactions, a PFR always achieve higher selectivity of the main product.
r
1
= k
1
C
benzene

r
2
= k
2
C
MA

For maximize the selectivity , this ratio must be minimized. C
MA
must be keep low while
C
benzene
must be kept high.
To achieve this, a PFR is preferred as at a given reaction volume, once benzene entered
and reacted to produce MA, the MA will leave the reaction volume immediately (keep
Low concentration of MA). In other words, the MA molecule will have less time to
undergo side reaction 2, hence selectivity of MA will be higher.
In CSTR, the different molecule of MA produced will have different residence time, there
is more time for these MA molecule to react through side reaction 2, hence selectivity is
always lower than in PFR.
For parallel reaction reactions involve main reaction 1 r
1
and side reaction 3 r
3
, the effect
of using CSTR and PFR is the same.
R
1
= k
1
C
benzene

R
3
= k
3
C
benzene

Since the ratio is independent on C
benzene
, the effect of using PFR and CSTR on the
selectivity will be the same. In addition to this, the ratio is only dependent on k values,
so selectivity should be controlled by temperature only.

In a nutshell, PFR is chosen to model the reactions.


In this MA synthesis process, excess air is an essential tools to control selectivity. By
having large amount of excess air, all three reactions kinetic can be approximated using
first-order rate laws. With this approximation,
r
1
= k
1
C
benzene

r
2
= k
2
C
MA

R
3
= k
3
C
benzene


All reactions are only depend on one concentration of reactant, namely C
benzene
or C
MA
.
By controlling concentration of one reactant, the reaction rate for that particular
reaction can be manipulated, and next, selectivity. Hence, this simplification to reduce
the reactions kinetics to first-order reactions eases the analysis on enhancement of
selectivity.

Excess nitrogen acts as coolant to maintain the temperature of reactions in this region,
hence increases the selectivity.