ChemE 128

Sample Long Exam

General Instructions: Write your answers clearly and legibly in the space provided below.

Part I.A. Multiple Choice: (1pt each) Encircle the letter of all correct answers.

1. Which of the following statements is INCORRECT 3. Which among the following points (labeled A, B,
about elementary reactions? C) is considered an
I. On a molecular scale the reaction should unstable steady-state
occur exactly as written. operating condition?
II. The order of reaction is not based on (Encircle your answer in the
stoichiometry but determined graph on the right)
experimentally.
III. Only applicable to simple reactions but
rarely complex reactions occur.
IV. Only applicable to irreversible reactions.
4. A typical heterogeneous
a. II, III, IV catalyst has three
b. II, III components. Which of the following is not
c. III, IV included?
d. II, IV a. Catalyst active phase
b. Support
2. In an alkaline solution, peroxydisulfate oxidizes c. Promoter/Inhibitor
sulfite to yield sulfate, d. Solvent

𝑆2 𝑂82− + 𝑆𝑂32− + 2𝑂𝐻 − → 3𝑆𝑂42− + 𝐻2 𝑂
The following mechanism has been proposed:
𝑆2 𝑂82− + 𝑆𝑂32− → 𝑆2 𝑂72− + 𝑆𝑂42− 𝑘1
2− 2− + heterogeneous catalysts.
𝑆2 𝑂7 + 𝐻2 𝑂 → 2𝑆𝑂4 + 2𝐻 𝑘2
2𝐻 + + 2𝑂𝐻 − → 2𝐻2 𝑂 𝑘3
(fast equilibrium step)
Which of the following statements is/are true about
the given overall reaction and its proposed
mechanism?
a. The rate of consuming 𝑆2 𝑂72− is equal to
𝑘1 [𝑆2 𝑂82− ][𝑆𝑂32− ] - 𝑘2 [𝑆2 𝑂72− ][ 𝐻2 𝑂]
b. The rate of consuming 𝑆2 𝑂72− is equal to 𝑘2
[𝑆2 𝑂72− ][ 𝐻2 𝑂], but [ 𝐻2 𝑂] is so large 56 M, that
its change can be neglected. Thus, the rate of
consuming is really k [𝑆2 𝑂72− ], where k =
𝑘2 [𝐻2 𝑂]
c. The rate law for this reaction derived from the
mechanism is 𝑘1 𝑘2 [𝑆2 𝑂82− ][𝑆𝑂32− ]
d. A and C
e. B and C
5. Which of the following statements is/are TRUE?
a. Homogeneous catalysts are more selective
than heterogeneous catalysts.
b. Only surface atoms are useful for
c. Heterogenous catalysts are operated at lower
temperatures than homogenous catalysts.
d. Heterogeneous reactions always involve solid
surfaces.
6. What is the effect of external mass transfer on the
point selectivity of an isothermal system with the
following reaction scheme, with B as the desired
product?
A → B (first order) k1
A → C (second order) k2
a. Selectivity is NOT affected by external mass
transport (for an isothermal case)
b. Selectivity for B increases as external mass
transfer will result in increase in the
concentration of A on the surface
c. Selectivity for B decreases as external mass
transfer will result in decrease in the
concentration of A on the surface
d. Effect of external mass transfer will depend on
the activation energies, EA1 and EA2.

1
Part I.B. Conceptual Questions: Answer the following questions concisely (within 3-7 sentences only). Write your
answers in the box provided below.

A. (10 pts.) For the reaction 𝐶𝑂 + 𝐶𝑙2 ⇌ 𝐶𝑂𝐶𝑙2 , the rate expression below can be obtained:
𝑘𝑃𝐶𝑂 𝑃𝐶𝑙2
𝑟= 2
(1 + 𝐾1 𝑃𝐶𝑙2 + 𝐾2 𝑃𝐶𝑂𝐶𝑙2 )
What does the exponent in the denominator imply and what does the lack of a P CO term in the denominator
suggest?

B. (10 pts.) For the reaction of A to form B over a solid catalyst, the reaction rate has the form
𝑘𝐾𝐴 𝑃𝐴
𝑟=
(1 + 𝐾𝐴 𝑃𝐴 + 𝐾𝐵 𝑃𝐵 )2
However, there is a large excess of inert in the reactant stream that is known to readily adsorb on the catalyst
surface. How will this affect the reaction order with respect to A?

Part II. Problem Solving: Write your solutions in the space provided below and box final answers for each question.

1. (40 pts) An elementary gas phase reaction

𝐴 → 𝐵 + 2𝐶
is carried out isothermally in a flow reactor. Pure reactant A enters the reactor at 10atm and 400 K and at a molar
flow rate of 150 mol/hr. From experimental data, it is found that the specific reaction rate constant at 323 K is
6 x 10-3 hr-1 and the activation energy is 85kJ/mol. Neglect pressure drop along the reactor.

Calculate the reactor volume and space time to achieve 90% conversion in:
(a) a PFR
(b) a CSTR.

2. Rate data for the reaction H2 + ½ O2 → H2O have been measured for single catalyst pellets (1.86-cm
diameter) of platinum on Al2O3. Catalyst properties, ke, De, and center and surface temperatures were also
evaluated. The rate was obtained in a stirred-tank reactor in which the pellet was surrounded by well-mixed
reaction gases. In one run, the data were as follows:

Gas temperature, Tg = 90°C
Average surface temperature, Ts = 101°C
Pellet center temperature, Tc = 148°C
Pellet density, ρP = 0.0602 g/cm3
Total pressure, pt = 1 atm
Oxygen mole fraction at pellet surface, yO2,s = 0.0527
Effective diffusivity inside the pellet, De = 0.166 cm2/s
Effective thermal conductivity, ke = 6.2(10-4) cal/s-cm-K
Pellet rate of reaction, rP = 2.49(10-5) mol O2/s-g cat
Heat of reaction, ΔH = -115400 cal/mol O2

Rate data were also obtained for the small (80 to 250 mesh) particles from which the pellets were prepared. The
results, expressed as the rate of oxygen consumption (mol/s-g cat), were correlated by
rpart = 0.327PO20.804exp(-5230/RgT) where PO2 is in atmospheres.

a. Determine if internal C and T gradients have a significant effect on the pellet rate.
b. Estimate the maximum temperature difference, Tc-Ts.
c. Evaluate the effectiveness factor using the experimental data for the catalyst pellet.