Solved Example
By
Wasi ur Rahman
Department of Chemistry
AMU Aligarh
PROBLEM 1
A batch of solids of uniform size is treated by gas in a uniform
environment. Solid is converted to give a nonflaking 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
For constant size Spherical Particle, the time conversion expression
for different mechanisms are
• t/τ = XB Film Diffusion Control
• t/τ = 1 - 3(1-XB )2/3- 2(1-XB ) Ash Diffusion Control
• t/τ = 1 - (1-XB )1/3 Chemical Reaction Control
For any mechanism to be rate controlling the corresponding expression
should be satisfied, i.e. data should fit the expression. Now let us check
which of these mechanisms controls the rate.
Given
τ =2 hr
t =1 hr,
XB=0.875
When Film Diffusion controls the rate
t/τ = XB the data should satisfy this expression
LHS
t/τ = ½ = 0.5
RHS
XB=0.875
t/τ ≠ XB
So this mechanism is not rate controlling.
When Ash Diffusion controls the rate
t/τ = 1 - 3(1-XB )2/3- 2(1-XB )
LHS
t/τ =1/2 = 0.5
RHS
1 - 3(1-XB )2/3- 2(1-XB )
1 – 3(1-0.875)2/3 – 2 (1-0.875) =0.5
LHS =RHS
i.e. Ash diffusion is rate controlling.
When Chemical Reaction controls the rate
t/τ = 1 - (1-XB )1/3
LHS
t/τ = 0.5
RHS
1 - (1-XB )1/3
1 – (1-0.875) 1/3 = 0.5
LHS = RHS
Ans. Hence Ash diffusion and Chemical reaction are rate
controlling.
Problem 2
Calculate the time needed to burn to completion particles of graphite
(R, = 5 mm, , = 2.2 gm/cm3 , k" = 20 cm/sec) 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
In burning of particles of graphite (pure C) there is no ash formation. The
reacting particle shrinks in size as reaction progresses and finally
disappears (on complete combustion).
As the ash layer is absent there are only two possible resistances :
(i) Resistance offered by film diffusion.
(ii) Resistance offered by chemical reaction.
But we are provided with: film diffusion does not offer any resistance. So
in our case we have only one resistance : resistance offered by
chemical reaction, i.e., in our present case chemical reaction controls the
rate. For small spherical particles when chemical reaction controls the
rate, the time required for complete conversion (i.e., the time required for
complete burning of particle of graphite) is given by
1
Combustion Reaction :
C(s) + O2 (g) → CO2(g)
A(g) + bB(s)→fluid product.
Comparing the above two equations, we get b = 1 and A = O2
Ro= 5 mm = 0.5 cm
density of graphite = ρB = 2.2 g/cm3
rate constant = k'' = 20 cm/s
Evaluate CAg: bulk gas phase concentration of A.
Here A is O2. CAg = pAg / RT
A in the gas stream is 8% by volume, total pressure= 1 atm.
For an ideal gas : volume % A = mole % A
We know that
pAg= xA.P = 8/100 x 1 = 0.08 atm
T = 900 oC = 1173 K , R = 82.06 (cm3·atm)/mol.K
The concentration of O2 is calculated using the relation
CAg = pAg / RT
CAg = 0.08 / ( 82.06 × 1173) = 8.31 × 10–7 mol/cm3
ρB = 2.2 g/cm3 convert this mass density of carbon into molar density
mol/cm3
Molar density ρB = 2.2/12= 0.183 mol/cm3, (At. M. Wt. C = 12)
Substituting the values in Equation (1), we get
τ = (0.183 X 0.5) / (1 X 20 X 8.31 X 10-7 ) = 5505.4 sec
Ans. Time required for the complete burning of particles of graphite
=5505.4 s
For any clarification, You may contact me at my email id
azmiwasi@gmail.com
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