Example from the book “Chemical Reaction Engineering”, by Octave Levenspiel.

At Sandy’s Rock and Gravel company, they want to shift a mountain of gravel, estimated at
about 20,000 tons, from one side of their yard to the other. For this, they intend to use a power
shovel to fill a hopper (bin), which in turn feeds a belt conveyer. The latter then transports the
gravel to the new location.

The shovel scoops up large amounts of gravel at first; however, as the gravel supply decreases,
the handling capacity of the shovel also decreases because of the increased time required to
move away from the hopper for a load and then return and dump. Roughly, then, we may
estimate that the shovel’s gravel-handling rate is proportional to the size of the pile still to be
moved, its initial rate being 10 ton/min. The conveyer, on the other hand, transports the gravel at
a uniform 5 ton/min. At first the shovel will work faster than the conveyer then slower. Hence
the storage bin / hopper will accumulate material and then empty.

Conveyer Final
Initial Bin
Location
Location Shovel

(a) What will be the largest amount of gravel in the bin?

(b) When will this occur?
(c) When will the rates of bin input and output be equal?
(d) When will the bin become empty?
 k1 k2
Consider a series reaction A  → B  →C

Initially, we have only A, some of it is converted to B and then to C. The first reaction is first
order, the second reaction is zero order.

r1 = k1C A and r2 = −k2

Initial rate = k1CA0 = 10 ton/min implies k1 = 10/20000 min-1. k2 = 5 ton/min.

Now, rA = -r1. rB = r1-r2. rC = r2.

C A = C A0e − k1t

dCB
= k1C A − k2 = k1C A0 e− k1t − k2
dt
Therefore, CB = −k2t − C A0 e− k1t + C A0

What will be the maximum concentration of B?

dCB
When will we get a maximum? When =0
dt
Find the value of CB at that time to get the maximum concentration

When will r1 be equal to r2? (when concentration of B is maximum)

When will the bin be empty? (When CB =0)

CB vs t (min)
3500
3000
2500
2000
1500
1000 Cb
500
0
-500 0 500 1000 1500 2000 2500 3000 3500 4000
-1000
-1500

Note the negative values seen at long time, this is the problem with using zero order
approximation. Also note that the first order kinetics is not a good approximation when CA is
close to zero.