CHEMICAL REACTOR DESIGN
7TH SEM, B.TECH. CHEMICAL ENGG.
Lecture-4
Subject Teacher - Dr. S.R.Mote
Combining all the resistances
We have derived the conversion-time expressions assuming
single resistance controlling throughout conversion of the
particle.
However, the relative importance of gas film, ash layer, and
reaction resistances will vary simultaneously as the particle
conversion progresses.
For ex., for a constant size particle, the gas film resistance
remains unchanged. But the resistance to reaction increases as
the surface of unreacted core decreases, while the ash layer
resistance is nonexistent at the start because no ash is present,
but ash layer progressively builds up.
In general, it may not be reasonable to consider that just one
step control throughout reaction.
To account for the simultaneous action of these
resistances, we combine them with their individual
driving forces and eliminating intermediate
concentrations, it can shown that the time to reach any
stage of conversion is the sum of the times needed if each
resistance acted alone.
Alternatively, individual resistances can be combined
directly, at any particular stage of conversion.
Determination of rate-controlling step
EX. A batch of solids of uniform size is treated by gas in a
uniform environment. Solid is converted to give a non-flaking
product according to the shrinking-core model. Conversion is
about 7/8 for a reaction time of 1 h, conversion is complete in
two hours. What mechanism is rate controlling?
SOLUTION:
Given that the reaction gives a non-flaking product. Hence, the
particle size remains unchanged.
Given data: Reaction time, t = 1 hr
Time for complete conversion, = 2 hr
Conversion, XB = 7/8 = 87.5 %
For constant size particle, t/ expressions in term of XB are
1. Gas film diffusion controls
2. Ash layer diffusion controls
3. Chemical reaction controls
Since we know all the variables, we have to check whether
LHS = RHS for all three resistances.
1. When gas film diffusion controls,
t/ = XB
½ = 0.5 0.875
Hence this mechanism is not the rate controlling.
2. When ash layer diffusion controls,
LHS = t/ = ½ = 0.5
RHS = 1 – 3(1-XB)2/3 +2 (1-XB) = 0.5
Hence this is the rate controlling step.
3. When chemical reaction controls,
LHS = t/ = ½ = 0.5
RHS = 1 – (1-XB)1/3 = 0.5
Hence this is also the rate controlling step.
Overall, both, ash layer diffusion and chemical reaction
mechanisms are the rate controlling.
Calculate the time needed to burn to completion particles of
graphite (Ro = 5mm, B = 2.2gm/cm3, k"=20cm/s) in an 8% oxygen
stream. For the high gas velocity used assume that film diffusion
does not offer any resistance to transfer and reaction. Reaction
temperature = 900°C.
SOLUTION:
Given that the solid particle is graphite, i.e. pure Carbon.
Hence, no ash layer will be formed and only two resistances due
to gas film and chemical reaction have to be considered.
Also it is given that the film diffusion does not offer any
resistance. Hence, only chemical reaction will control the rate.
If is the time required for complete conversion, when chemical
reaction controls the rate, then
Chemical reaction is
C (s) + O2 (g) CO2 (g)
From stoichiometry of the reaction, b = 1.
CAg = PAg / R T
where PAg = partial pressure of oxygen = 8% = 0.08 atm
T = temperature = 900oC = 1173 K
R = 82.06 cm3 atm/mol K
\ CAg = 0.08/(82.06 x 1173) = 8.31 x 10-7 mol/cm3
\ = 5505.4 sec = 1.53 hr = time required for complete
combustion of graphite particle.
Spherical particles of zinc blende of size R = 1 mm are roasted in an
8% oxygen stream at 900°C and 1 atm. The stoichiometry of the
reaction is 2 ZnS + 3 O2 2 ZnO + 2 SO2
Assuming that reaction proceeds by the shrinking-core model
calculate the time needed for complete conversion of a particle and
the relative resistance of ash layer diffusion during this operation.
Note that film resistance can safely be neglected as long as a
growing ash layer is present.
Data: Density of solid, B = 4.13 gm/cm3 = 0.0425 mol/cm3
Reaction rate constant, k" = 2 cm/sec
For gases in the ZnO layer, De = 0.08 cm2/sec
Solution: 2 ZnS + 3 O2 2 ZnO + 2 SO2
2/3 ZnS + O2 2/3 ZnO + 2/3 SO2
By stoichiometry of above reaction, b = 2/3.
CAg = PAg / R T
where PAg = partial pressure of oxygen = 8% = 0.08
T = temperature = 900oC = 1173 K
R = 82.06 cm3 atm/mol K
CAg = 0.08/(82.06 x 1173) = 8.31 x 10-7 mol/cm3
Given that the film resistance can be neglected. Hence, ash
layer and chemical reaction offer resistances.
Total time for complete conversion = total = ash + rxn
For ash layer resistance, ash = = 1598 sec
For chemical reaction resistance, rxn = = 3836 sec
Total time for complete conversion = total = 1598 + 3836
= 5434 sec
Resistance of ash layer = 1598 x 100/ 5434 = 29.4 %
Resistance due to chemical reaction= 3836 x 100/ 5434
= 70.6 %
Uniform-sized spherical particles UO3 are reduced to UO2 in a
uniform environment with the following results:
t, hr 0.180 0.347 0.453 0.567 0.733
XB 0.45 0.68 0.80 0.95 0.98
If reaction follows the SCM, find the controlling mechanism and a
rate equation to represent this reduction.
Solution: Assume that it is unchanging particle size.
1. Assuming diffusion through gas film is rate controlling.
Since, = t / XB
t, hr 0.180 0.347 0.453 0.567 0.733
XB 0.45 0.68 0.80 0.95 0.98
0.40 0.50 0.57 0.597 0.748
Since is not constant in above table, gas film diffusion is not the rate controlling
step.
2. Assuming diffusion through ash layer is rate controlling.
t, hr 0.180 0.347 0.453 0.567 0.733
XB 0.45 0.68 0.80 0.95 0.98
2.09 1.467 1.21 0.818 0.895
Again is not constant here also, hence ash layer diffusion is not
the rate controlling step.
3. Assuming chemical reaction is rate controlling.
t, hr 0.180 0.347 0.453 0.567 0.733
XB 0.45 0.68 0.80 0.95 0.98
0.996 1.098 1.091 0.898 1.006
The values of is almost constant in above table.
Hence, chemical reaction is the rate controlling step.
Spherical solid particles containing B are roasted isothermally in an oven with gas of
constant composition. Solids are converted to a firm non-flaking product according
to the SCM as follows:
A(g) + B(s) R(g) + S(s) CA=0.01 kmol/ m3, B = 20 kmol/ m3
From the following conversion data (by chemical analysis) or core size data (by
slicing and measuring) determine the rate controlling mechanism for the
transformation of solid.
dp , mm XB t, min
1 1 4
1.5 1 6
Solution: For constant size spherical particles,
1. When gas film diffusion controls, R/ is constant.
Also, = t / XB. Hence, = R XB/t
2. When ash layer diffusion controls, R2/ is constant.
Also,
Hence, = R2 ( )/t
3. When chemical reaction controls, R/ is constant.
Also,
Hence, = R( )/t
From above table, is constant for ash film diffusion control, it is the rate
controlling mechanism.
