MM 305 Autumn 2023 End semester Group projects

𝑠𝑢𝑏𝑠𝑡𝑟𝑎𝑡𝑒
1. Reversible heterogeneous reaction 𝑆𝑖𝐻4 (𝑠) ↔ 𝑆𝑖(𝑠) + 2𝐻2 (𝑔) being carried
isothermally in a tube reactor (diameter D = 10 cm and length L = 100 cm)
without pressure drop, results in the deposition of Si thin film on reactor inner
walls (or specifically substrates held in close contact with reactor inner walls). At
substrate temperature of 1000 °C, rate expression is −𝑟𝑆𝑖𝐻4 = 𝑘(𝐶𝑆𝑖𝐻4 −
𝐶𝐻22 /𝐾𝑒𝑞 ).where the forward reaction rate is k = 0.2 cm/s, and equilibrium
constant is Keq = 10 mol/cm3. Deposition rate of Si film 𝐺𝑆𝑖 (cm/s) and reaction
rate 𝑟𝑆𝑖 (mol cm-2 s-1) are related as 𝐺𝑆𝑖 = 𝑟𝑆𝑖 𝑀𝑆𝑖 /𝜌𝑆𝑖 where MSi is the molar weight
0
of Si (g/mol) and ρSi is the bulk density of Si (g/cm3). At the inlet 𝐹𝑆𝑖𝐻 4
= 10−3
mol/s, 𝐹𝐻02 = 10−2 mol/s and reactor is at a constant pressure 𝑃0 = 103 Pa.
a. Calculate variation in Si film growth rate 𝐺𝑆𝑖 along reactor length L, and
what will be the average growth rate 𝐺̂ 𝑆𝑖 .
̂
b. How does variation in 𝐺𝑆𝑖 and 𝐺𝑆𝑖 change if (i) 𝑃0 is increased to 2000 Pa
or (ii) 𝑃0 is lowered to 500 Pa
c. How does variation in 𝐺𝑆𝑖 and 𝐺̂ 0
𝑆𝑖 change if (i) 𝐹𝐻2 is increased to 0.05
mol/s or (ii) 𝐹𝐻02 is lowered to 0.005 mol/s
d. Plot 𝐺𝑆𝑖 vs reactor length L calculated in (a), (b) and (c).

2. A reversible liquid phase reaction 2𝐴 + 𝐵 ⟶ 𝐶 is carried isothermally in a PFR

reactor of length L = 1 m, at 300 °C where k = 10 s-1. For an equimolar inlet feed
𝐹𝐴0 = 𝐹𝐵0 = 10−3 𝑚𝑜𝑙/𝑠 and inlet volumetric flow 𝑣0 = 0.1 𝑑𝑚3 /𝑠. Calculate
conversion XA and CC as a function of position x along reactor length if:
a. Constant cross section diameter 𝐷0 = 0.10 𝑚.
b. Diameter D (in m) varies as 𝐷(𝑥) = 0.07 + 0.06𝑥
c. Diameter D (in m) varies as 𝐷(𝑥) = 0.13 − 0.06𝑥 m
𝜋𝑥
d. Diameter D (in m) varies as 𝐷(𝑥) = 0.10 + 0.03 sin ( 𝐿 )
𝜋𝑥
e. Diameter D (in m) varies as 𝐷(𝑥) = 0.10 + 0.03 cos ( 𝐿 )
f. Based on calculations (a) – (e), which reactor geometry allows for
maximum XA at the exit.
3. An elementary hydrogen evolution reaction 2𝐻2 𝑂(𝑔) ⟶ 2𝐻2 (𝑔) + 𝑂2 (𝑔) is
carried out isothermally with negligible pressure drop in a PBR reactor with a
total 100 kg catalyst loading. At the inlet, volumetric feed rate is 𝑣0 =
𝑑𝑚6
10 𝑑𝑚3 /𝑚𝑖𝑛 at 𝑃0 = 10 𝑎𝑡𝑚 with 𝐶𝐻02 𝑂 = 0.4 𝑚𝑜𝑙/𝑑𝑚3 , and 𝑘 = 1.37 𝑚𝑜𝑙∙𝑘𝑔−𝑐𝑎𝑡∙𝑚𝑖𝑛.
a. Calculate 𝐹𝐻2 𝑂 , 𝐹𝐻2 , 𝐹𝑂 and volumetric flow 𝑣 at the exit of PBR reactor.
b. Considering that this evolved hydrogen gas stream consists of D2 and H2
with concentration ratio FD2:FH2 = 1:100000 (D is heavy hydrogen isotope
with 1 proton and 1 neutron). With intention to isolate D2, this exiting
hydrogen stream is passed through a membrane tube reactor of diameter
d = 0.10 m and length L = 10 m at volumetric flow rate 𝑣𝑓 = 5 𝑑𝑚3 /𝑚𝑖𝑛,
where the mass transfer coefficient for H2 and D2 are 𝑘𝑐𝐻2 = 0.10 𝑠 −1 and
𝑘𝑐𝐷2 = 0.001 𝑠 −1 . Calculate the concentration ratio CD2:CH2 at the exit of
this membrane reactor
4. A liquid phase reversible reaction 𝐴 ⇄ 𝐵 + 𝐶 has a forward reaction rate constant
𝑘𝑓 = 0.2 𝑠 −1 and equilibrium constant 𝐾𝑒 = 0.2 𝑚𝑜𝑙/𝑑𝑚3 .
a. If this reaction is carried out isothermally in a plug-flow-reactor (PFR) as
show I Fig. (a) below with the inlet stream consisting of 𝐹𝐴0 = 1 𝑚𝑜𝑙/𝑚𝑖𝑛
and volumetric flow rate of 𝑣0 = 1 𝑑𝑚3 /𝑚𝑖𝑛, calculate XA as function of
reactor volume and identify reactor volume V* required to attain 95% of
equilibrium conversion (XAe).
b. If this reaction was carried out in a PFR reactor with 𝐹𝐴0 = 1 𝑚𝑜𝑙/𝑚𝑖𝑛 and
𝑣0 = 1 𝑑𝑚3 /𝑚𝑖𝑛 at the inlet. Furthermore, as shown in the Fig (b) below,
the components A and B from the outstream are separated and fed back
into the inlet at volumetric flow rate 𝑣𝑟 = 0.6 𝑑𝑚3 /𝑚𝑖𝑛. For reactor volume
0.5×V* (V* calculated in part (a)), calculate the component C
concentration (CC) in the outstream.

5. An experimental supplement S is destined to tackle a critical nutritional

deficiency. Upon ingestion, S begins to get absorbed by inner lining of small
intestine upon ingestion following rate expression 𝑅 = 𝑘𝑐 𝐶𝑆 where mass transfer
coefficient 𝑘𝑐 = 0.1 𝑠 −1. Human small intestine may be considered as a
membrane reactor of length L = 6 m and diameter d = 0.02 m, where the inner
lining acts as a membrane across which transport of S occurs. Assuming the
volumetric flow rate through intestine is 𝑣0 = 0.1 𝑑𝑚3 /𝑚𝑖𝑛.
a. For supplement concentration at the inlet 𝐶𝑆0 = 1 𝑚𝑜𝑙/𝑑𝑚3 , plot CS as a
function of reactor length, and calculate CS at the exit.
b. Calculate the total rate (in moles/s) at which supplement S gets absorbed
into human body
c. If the maximum rate at which human body can utilize S is 0.1 mol/s,
calculate the supplement concentrations CS0 required at the inlet and CS in
the exit stream.
6. A liquid phase reversible reaction 𝐴 ⇄ 𝐵 + 𝐶 has a forward reaction rate constant
𝑘𝑓 = 1 𝑠 −1 and equilibrium constant 𝐾𝑒 = 0.5 𝑚𝑜𝑙/𝑑𝑚3 is carried out in a batch
reactor (BR) of volume V1 = 100 dm3, starting with NA0 = 250 moles. Also as
shown in the figure below, this BR is connected to a CSTR through a semi-
permeable link, which allows transport of component C from BR to CSTR
(volume V2 with circulating inert medium at inlet flow rate FI0), with mass transfer
coefficient 𝑘𝑐𝐶 = 2 𝑠 −1 (𝐽𝐶 = 𝑘𝑐𝐶 (𝐶1 − 𝐶2 ), where C1 and C2 are concentrations in
BR and CSTR respectively).
a. For an isolated BR, calculate 𝑋𝐴 (𝑡) and time 𝑡0.95 required to attain 95% of
equilibrium conversion (𝑋𝐴𝑒 ).
b. For BR liked to CSTR (𝑉2 = 10 𝑑𝑚3 and 𝑣0 = 10 𝑑𝑚3 /𝑚𝑖𝑛), calculate
𝑋𝐴 (𝑡) and time 𝑡0.95 required to attain 95% of 𝑋𝐴𝑒 .
c. Comparing calculations of (a) and (b), what strategies would ensure
improved throughput (i.e. combination of process condition to minimize
𝑡_0.95).

7. Following are the elementary reactions involved in a hypothetical liquid phase

reduction process of a metalorganic MO into M using reducing agent R:
Reaction 1: 𝑀𝑂 + 𝑅 ⟶ 𝑀 + 𝑅𝑂 k1 = 0.2 dm3/mol·s
Reaction 2: 𝑀𝑂 + 𝑅𝑂 ⟶ 𝑀 + 𝑅𝑂2 k2 = 0.4 dm3/mol·s
Reaction 3: 𝑅𝑂 + 𝑅 ↔ 𝑅𝑂2 k3 = 5 dm3/mol·s, Keq = 1 dm3/mol
Overall reaction: 2𝑀𝑂 + 𝑅 ⟶ 2𝑀 + 𝑅𝑂2
As shown in the figure below, this reaction is carried out isothermally in a CSTR
reactor of volume V with volumetric flow rate 𝑣0 = 20 𝑑𝑚3 /𝑚𝑖𝑛 the inlet molar
flow rates 𝐹𝑀𝑂0 and 𝐹𝑅0 for metalorganic and reducing agent respectively.
a. Evaluate rate expression for the net reaction: 2𝑀𝑂 + 𝑅 ⟶ 2𝑀 + 𝑅𝑂2
 b. For CSTR reactor volume V = 100 dm3, what should be the required FR0 to
result in FM = 100 mol/min in the CSTR exit stream

8. A gas phase reaction 𝐴 ⟶ 2𝐵 is carried out isothermally in a PFR reactor with an

in-line IR transmittance measurement setup (where the transmitted IR intensity
can be correlated to composition) as shown in the figure below.

Above reaction can proceed only in the heated region of the PFR reactor, beyond
which the composition of reactants ad products does not change with time. If the
reaction rate expression is −𝑟𝐴 = 𝑘𝐴 𝐶𝐴𝛼 and the transmitted IR intensity scales
𝐶𝐵
with composition as 𝐼 = 𝐼0 (𝐶 )
𝐴 +𝐶𝐵
a. For V* = 5 dm3 and 𝑘𝐴 = 0.2 𝑠 −1, plot 𝐼/𝐼0 as a function of. 𝐹𝐴0
b. For V* = 10 dm3 and 𝑘𝐴 = 0.2 𝑠 −1 , plot 𝐼/𝐼0 as a function of. 𝐹𝐴0
c. For V* = 5 dm3 and 𝑘𝐴 = 0.2 𝑑𝑚3 𝑚𝑜𝑙 −1 𝑠 −1, plot 𝐼/𝐼0 as a function of. 𝐹𝐴0
d. For V* = 10 dm3 and 𝑘𝐴 = 0.2 𝑑𝑚3 𝑚𝑜𝑙 −1 𝑠 −1 , plot 𝐼/𝐼0 as a function of. 𝐹𝐴0
e. Can one identify reaction order α for an arbitrary reaction using such in-
line characterization methods?
9. Hydrogen storage in spherical media
a. For H-dissolution into solid surface 𝐻2 (𝑔) ⇄ 2𝐻(𝑠) in medium X (of
density ρ) let the equilibrium H-solubility be CHo (mole/cm3) at H2 pressure
of PH2* (Pa),
b. Consider a high-pressure tank holding M kg of media X, arranged as n
spheres of radius RS. Find n.
c. Now consider that the tank is filled with H2 gas at pressure PH2*, thereby
initiating H-absorption at surface of media X.
d. Assume: (i) spacing between the neighbouring spheres are significantly
larger than molecular mean-free path of H2 (g), and (ii) diffusion coefficient
DHX is independent of H concentration in X, determine the amount of H2
stored in media X as a function of time per unit weight of media.
e. Plot the H2 storage/charging rate (moles time-1 kg-1) as a function of
charging time for different sphere radius RS.

10. Surface oxidation (or corrosion) at the metal surface

a. Consider a metal M (density ρM) exposed to an environment (PO2) such
that it forms an oxide O (density ρO) at the metal surface.
b. Let this oxidation reaction 𝑀(𝑠) + 𝑂2 (𝑔) → 𝑀𝑂2 (𝑠) follow a mechanism
such that (i) the oxidant O2 must first adsorb at the surface 𝑟𝑎𝑑𝑠 = 𝑘𝐴 ∙ 𝑃𝑂2 ,
(ii) O2 must diffuse through the existing MO2 layer to reach M – MO2
𝑀𝑂 𝑠𝑢𝑟𝑓
interface 𝑟𝑑𝑖𝑓 = 𝐷𝑂2 2 ∙ (𝑂2 − 𝑂2𝑖𝑛𝑡𝑒𝑟 ), (iii) O2 reacts at this interface
𝑟𝑟𝑒𝑎 = 𝑘𝑟 ∙ 𝑂2𝑖𝑛𝑡𝑒𝑟 to form metal oxide MO2.
c. Formulate expression for the oxidation rate (in nm/s) in the limit of (i)
diffusion limited oxidation, and (ii) reaction limited oxidation
d. A dense metal oxide layer well-adhered to the underlying metal surface
tends to inhibit further oxidation because of slow diffusion of O 2 through
MO2 (e.g. oxidation of Si to SiO2). How would the surface
oxidation/corrosion rates change in case of metal oxide MO2 that is porous
and/or flakes off from the metal surface?