Exercise 5.7: Two candidate reduced models.

Consider the simple series reaction mechanism taking place in a constant volume hatch reactor:

(a) Write down the mole balance differential equations for species A, B and C. We call this set of
differential equations the full model.
(b) For what range of rate constants would you think it is reasonable to assume the second reaction
is at equilibrium compared to the first reaction?
(c) We write down two candidate simplified models to try to describe this situation. In the first
one, set 𝑟2 = 0 and solve for 𝐶𝐶 .Then set 𝑟2 = 0 in the remaining ODEs for 𝐶𝐴 and 𝐶𝐵 .
(d) in the second one, solve for 𝐶𝐶 as above, but now eliminate 𝑟2 , from the differential equations,
rather than setting it to zero, and write down differential equations for 𝐶𝐴 and 𝐶𝐵
(e) Solve the three models for the following values (choose any time and concentration units you
like), Feel free to solve it analytically or numerically. Plot the concentrations versus time for each
model.

Which Simplified model correctly describes the full model in the limit of a fast second reaction?
What went wrong in the approach that didn't work?

Solution:
𝑑𝐶𝐴 𝑑𝐶𝐶
(a) = 𝑟𝐴 = −𝑘1 𝐶𝐴 + 𝑘−1 𝐶𝐵 = 𝑟𝐶 = 𝑘2 𝐶𝐵 − 𝑘−2 𝐶𝐶
𝑑𝑡 𝑑𝑡

Where: 𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋1 ); 𝐶𝐵 = 𝐶𝐵0 (1 − 𝑋2 ) + 𝐶𝐴0 𝑋1;

𝐶𝐶 = 𝐶𝐶0 + 𝐶𝐵0 𝑋2

(b) It becomes reasonable to assume that the second reaction is at equilibrium compared to the
first reaction when 𝑘2 ≫ 𝑘1 and 𝑘−2 ≫ 𝑘−1 . Based on the rate equations given above,
when rate constants of the second reaction are much greater relative to that of first reaction,
the 𝑟𝐶 becomes greater in magnitude compared to 𝑟𝐴 , meaning the second reaches
equilibrium faster than first reaction.
(c) −𝑟𝐴 = 𝑟𝐵 = 𝑟1 −𝑟𝐵 = 𝑟𝐶 = 𝑟2
𝑑𝐶
𝐶 𝑑𝑋2
If 𝑟2 = 0; then: 0 = 𝑘2 𝐶𝐵 − 𝑘−2 𝐶𝐵 𝑘2 𝐶𝐵 = 𝑘−2 𝐶𝐶 ; = 𝐶𝐶0 =0
𝑑𝑡 𝑑𝑡
𝑑𝑋2 𝑑𝑋2
=0→∫ = 0 → 𝑋2 = 𝐶1 (𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡)
𝑑𝑡 𝑑𝑡

𝑑𝐶𝐴 𝑑𝑋1
= 𝐶𝐴0 = −𝑘1 (𝐶𝐴0 − 𝐶𝐴0 𝑋1 ) + 𝑘−1 (𝐶𝐵0 − 𝐶𝐵0 𝑋2 + 𝐶𝐴0 𝑋1 )
𝑑𝑡 𝑑𝑡

𝑑𝑋1 𝐶𝐵0 𝐶1 𝐶𝐵0

= 𝑘1 𝑋1 − 𝑘1 + 𝑘−1 − 𝑘−1 + 𝑘−1 𝑋1
𝑑𝑡 𝐶𝐴0 𝐶𝐴0

𝑑𝑋1 𝐶𝐵0 𝐶1 𝐶𝐵0

= 𝑋1 (𝑘1 + 𝑘−1 ) + (−𝑘1 + 𝑘−1 − 𝑘−1 )
𝑑𝑡 𝐶𝐴0 𝐶𝐴0
𝐶 𝐶1 𝐶𝐵0
where: −𝑘1 + 𝑘−1 𝐶𝐵0 − 𝑘−1 = 𝐶2 (𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡)
𝐴0 𝐶𝐴0

𝑑𝑋1
= 𝑋1 (𝑘1 + 𝑘−1 ) + 𝐶2
𝑑𝑡
Using 1st order differential equation:
𝑘−1 𝐶1
𝑋1 = + 𝐶2 𝑒 −(𝑘1+𝑘−1)𝑡
𝑘1 + 𝑘−1

(d) If 𝑟2 is eliminated: 𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋) 𝐶𝐵 = 𝐶𝐴0 𝑋

𝑑𝑋
𝐶𝐴0 = −𝑘1 (𝐶𝐴0 − 𝐶𝐴0 𝑋) + 𝑘−1 (𝐶𝐴0 𝑋)
𝑑𝑡

𝑑𝑋
= (𝑘1 + 𝑘−1 )𝑋 − 𝑘−1
𝑑𝑡
Using 1st order differential equation:
𝑋 = −𝑘1 𝑒 −(𝑘1+𝑘−1 )𝑡

(e)