1.

Consider the general, balanced, reversible, and exothermic reaction

where
i) kf is the forward rate constant and kb is the reverse rate constant;
ii) both kf and kb can be expressed in the form of an Arrhenius Equation:
kf = Af exp(Ef /RT) and kb = Ab exp(Eb /RT)
iii) the stoichiometric coefficients, i.e., the νi in general; and a, b, c, and d here,
may have no factor in common; and
iv) δ = (d/a) + (c/a) – (b/a) – 1 = zero.

a) For this general reaction, what is the concentration equilibrium constant, Kc, in terms of
concentrations?
b) Provide equations that relate the concentration equilibrium constant, Kc, to the pressure
equilibrium constant, Kp, and to the “true” (dimensionless) equilibrium constant, Keq. (You can
assume the reaction occurs in the gas phase.) Under what circumstances does the concentration
equilibrium constant, Kc, equal the “true” (dimensionless) equilibrium constant, Keq? For the
rest of this question and for question 2, we will assume that these circumstances apply and that
Kc = Keq.
c) Now, let’s assume that this reversible reaction follows “power law” reaction kinetics, where
the “power”, or exponent, for each species i is equal to its stoichiometric coefficient, νi. In what
cases is this a reasonable assumption? (HINT: There are two cases, one of which we have seen
in class previously and the other you will need to arrive at on your own.)
d) Derive and equate the equations that will allow us to express
i) The relation between the enthalpy of reaction (ΔHrxn), Ef, and Eb
ii) The relation between the entropy of reaction (ΔSrxn), Af, and Ab
(HINT: Begin by relating Keq to thermodynamic variables, and assume that the thermodynamic
variables are independent of temperature.)
e) Derive an equation that will allow us to calculate the equilibrium temperature as a function of
ΔHrxn, ΔSrxn (or K0 ≡ Af/Ab), concentrations, and constants.
2. For this question, use the same information as was provided in the statement for question 1.
Recalling that the reaction is exothermic and reversible,
a) Derive an equation that will allow us to calculate the temperature at which the reaction rate is
a maximum as a function of ΔHrxn, ΔSrxn (or K0 ≡ Af/Ab), concentrations, activation barriers, and
constants. Your result should resemble closely the equation that you found in Question 1.e)
above. Compare the temperature at which the reaction rate is a maximum for a given conversion
found here with the equilibrium temperature for the same conversion found in Question 1.e), and
comment on your comparison.
b) Explain physically in one sentence why operating at the temperature at which the reaction
rate is a maximum to achieve a desired conversion of the limiting reactant is preferred.
c) Show mathematically that the net reaction rate goes through a maximum as a function of
temperature.
d) Explain physically, and in no more than five (5) complete and concise sentences, why the net
reaction rate goes through a maximum as a function of temperature.
e) On a graph of conversion of species A versus temperature, show qualitatively for the general,
balanced, reversible, and exothermic reaction in Question 1:
i) The equilibrium conversion of species A as a function of temperature. Include on the label for
this curve the value of the net reaction rate at equilibrium.
ii) Curves showing the conversion of species A as a function of temperature for several constant,
but different, reaction rates. Put a point on each of these curves where the conversion of species
A is the highest, which corresponds to the point at which the reaction rate is at a maximum.
Identify the direction in which the reaction rate is increasing for this set of curves.
iii) The loci of the temperatures at which the reaction rate is a maximum as a function of the
conversion of species A.
f) If you could be “emperor for the day”, how close would you like the curve showing the loci of
the temperatures at which the reaction rate is a maximum as a function of the conversion of
species A to the curve showing the equilibrium temperature as a function of conversion of
species A? In a few complete and concise sentences, explain physically why this may, or may
not, be desired.
3. Hydrolysis of acetyl chloride results in the production of acetic acid and hydrochloric acid
according to the following reaction:

CH3COOCl + H2O → CH3COOH + HCl

If acetone is added to the reacting mixture, this reaction is a homogeneous, liquid-phase reaction;
and for Questions 3.a) and 3.b), you can assume that the reaction is irreversible. The rate of the
forward reaction over a broad range of temperatures and solvent compositions was demonstrated
to be first order with respect to acetyl chloride and first order with respect to water.

For this project, we will simulate this reaction in a CSTR and illustrate a variety of interesting
phenomena.

Constants:
● Volume of reactor = 100 cm3
● Initial temperature = 300 K
● U*A = 38 cal/(min * K)
● Ef = 12,000 cal/mol
● Cp = 0.812 cal/(g * cm3)
● 𝜌𝜌 = 0.583 g/cm3
● Frequency factor, A = 2.02E10 cm3/(g * mol * min)
● Total volumetric flow rate of feed, νo = 91.5 cm3/min
● Let species A be acetyl chloride, species B be water, species C be acetic acid, and species
D be hydrochloric acid
● CAo (in feed) = 4.21E-3 mol/cm3, CBo (in feed) = 5.06E-3 mol/cm3, and CCo (in feed) =
CDo (in feed) = zero

a) Let’s assume that this reaction occurs in an isothermal CSTR, operating at a temperature of
300 K. Let’s further assume that the CSTR is filled initially with pure water; and that at a
residence time of tau = 0 (or at the actual time equal to zero), both acetyl chloride and additional
water are fed into the CSTR. Using MATLAB, solve the unsteady state mole balances; and plot
the concentration of each species as a function of time, for zero < time < 10.0 minutes. What is
the steady-state concentration of each species?
b) Now we want to shut down the CSTR. Assume that the acetyl chloride feed is shut off; and
pure water is fed to the CSTR. Plot the concentration of each species as a function of time, for
zero < time < 10.0 minutes. What is the steady state concentration of each species?
c) Using thermodynamics, estimate the value of the equilibrium constant for the above reaction
as a function of temperature:
CH3COOCl + H2O → CH3COOH + HCl
In this Question 3.c), you can assume that the above reaction is an elementary, reversible
reaction. You can also assume that the activity coefficients equal 1.0 (i.e., you can assume an
ideal solution, even if there may be ionic or electrostatic effects in the reacting solution).
d) Suppose that we utilized MATLAB to recalculate Questions 3.a) and 3.b) for the elementary,
reversible reaction described in Question 3.c). Explain physically in no more than 4 complete,
concise sentences how the plots of the concentration of each species as a function of time (for
zero < time < 10.0 minutes) will differ from those shown in Questions 3.a) and 3.b). An answer
with incomplete or incorrect physical justification will receive no points.
e) Repeat the MATLAB simulations for the CSTR startup and shutdown for an elementary,
reversible reaction; but in this Question 3.e), assume that ∆Grxn = 500 cal/(mol*K). Plot the
concentration of each species as a function of time, for zero < time < 10.0 minutes. What are the
new steady state concentrations of each species for the CSTR after start-up and shutdown?
Explain physically in no more than 4 complete, concise sentences why these values differ from
the values found in Questions 3.a) and 3.b). An answer with incomplete or incorrect physical
justification will receive no points.

General Tips

1) Your MATLAB code should be highly adaptable. Define the value of each constant only
once, use functions for repetitive tasks, etc. It should take only a few seconds to re-evaluate your
entire design if one of the inputs (e.g., the volumetric flow rate) needs to be changed.

2) The time you spend solving a problem is much more valuable than the cost of running a
computer for the same amount of time, especially in the future when your employer is paying
you a large salary and doesn’t want to wait a month for you to implement an elegant code.
Hence, seeking an elegant computational solution is only worthwhile when the computation time
is at least an order of magnitude larger than the time needed to implement such an elegant
solution. In other words, “brute force” approaches can be important and useful!

3) If you get stuck with something (i.e., if your ODE solver fails), try plotting the interim results
that are generated before the computer crashes to see what might be wrong. Visual debugging
can often be helpful to see if, or where, you may have made a mistake.

4) Information about heat maps in MATLAB can be found here:

https://www.mathworks.com/help/matlab/ref/imagesc.html