Cinética Questões

dos Materiais e Metalurgia
Departamento de Ciência
Cinética e Engenharia de Reatores

Lista 6
Professor: Francisco Moura

Bibliografia: Fogler, H. S., Elementos de Engenharia das Reações
Químicas, 3a edição, Editora LTC, 2002.
1
Sexta Lista de
Exercício P5-2 Exercí
Exercícios
P5-2A The irreversible isomerization

A→B
was carried out in a batch reactor and the following
concentration-time data were obtained:
t (min) 0 5 8 10 12 15 17.5 20
CA (mol/L) 4.0 2.25 1.45 1.0 0.65 0.25 0.06 0.008
Determine the reaction order and specific reaction rate.
2
Sexta Lista de
Exercícios
P5-3B GaInAs films are important materials in fiber optic communication

and in high-speed microelectronic devices. A preliminary reaction
between triethylindium and arisine is carried out to form an
intermediate, which is then used in the deposition to form GaInAs.
The reaction is
Et3In(g) + AsH3(g) ↔ Adduct (g)
The following data were obtained in a plug-flow reactor. [JECS
135 No.6 p.1530 (1988)]. Total pressure (including inerts) = 152.0
Torr.
Distance Down Reactor (cm) 0 1.5 2.5 4.0 6.5 9.0
For AsH3 = 1.5 Torr Inlet
Et3In (Torr) 0.129 0.075 0.05 0.03 0.018 0.016
Et3In (Torr) 0.129 0.095 0.085 0.08 0.042 0.04
3 Et3In (Torr) 0.129 0.045 0.022 0.01 0.01 0.01
Sexta Lista de
Exercícios
P5-4B The following data were reported [C. N. Hinshelwood and P. J.

Ackey, Proc. R. Soc. (Lond)., A115, 215 (1927).] for a gas-
phase constant-volume decomposition of dimethyl ether at
504°C in a batch reactor. Initially, only (CH3)2O was present.
Time (s) 390 777 1195 3155 ∞

Total Pressure (mmHg) 408 488 562 799 931
Assuming that the reaction

(CH3)2O → CH4 + H2 + CO
is irreversible and goes to completion, determine the reaction
order and specific reaction rate k.
4
Sexta Lista de
Exercícios
P5-5B In order to study the photochemical decay of aqueous bromine in

bright sunlight, a small quantity of liquid bromine was dissolved in
water contained in a glass battery jar and placed in direct sunlight.
The following data were obtained:
Time (min) 10 20 30 40 50 60
ppm Br2 2.45 1.74 1.23 0.88 0.62 0.44
temperature = 25oC
(a) Determine whether the reaction rate is zero-, first-, or second-order in
bromine, and calculate the reaction rate constant in units of your
choice.
(b) Assuming identical exposure conditions, calculate the required hourly
of rate of injection of bromine (in pounds) into a sunlit body of water,
25,000 gal in volume, in order to maintain a sterilizing level of
bromine of 1.0 ppm.
(Note: ppm = parts of bromine per million parts of brominated water by
weight. In dilute aqueous solutions, 1 ppm = 1 milligram per liter.)
5 (California Professional Engineers Exam)
Sexta Lista de
Exercícios
P5-6C Triaminoguanidine (TAGN) is an important propellent ingredient

which is used as an oxidizer. It can be produced from guanidine
(GN) and hydrazine in an aqueous solution [Ind. Eng. Chem. Res.
28 p.431 (1989)].
The reaction is
GN + 3N2H4 → TAGN + 3NH3 ↑

The following data give the cumulative ammonia evolved as a

function of time. The initial concentrations of GN and hydrazine
were 0.5 molar and 2.575 molar, respectively, in a 200 ml batch
reactor. Neglect any volume change in the liquid with reaction
for this aqueous reaction.
At 371K
Time (min) 0 5 10 20 30 40 50 60 80 100 150
NH3 (milimoles) 0 38 69 95 116 151 177 213 237 264 279
At 351K
Time (min) 0 5 10 20 30 40 50 60 80 100 150
NH3 (milimoles) 0 30 55 97 130 154 174 190 216 234 263
6 Determine as many rate law parameters as possible.

Sexta Lista de
Exercícios
P5-7C The reactions of ozone were studied in the presence of alkenes

[R. Atkinson et al., Int. J. Chem. Kinet. 15(8), 721 (1983)]. The
data below are for one of the alkenes studied, cis-2-butene. The
reaction was carried out isothermally at 297 K. Determine the rate
law and the values of the rate-law parameters.

Ozone Butene
Ozone Rate
Run Concentration Concentration
(mol/s.dm3 x 107)
(mol/dm3) (mol/dm3)
1 1.5 0.01 10-12
2 3.2 0.02 10-11
3 3.5 0.015 10-10
4 5.0 0.005 10-9
5 8.8 0.001 10-8
6 4.7 0.018 10-9
7
Sexta Lista de
Exercícios
P5-8c Examples of autocatalytic reactions can be found in methanol

conversion [Ind. Eng. Chem. Res. 27 p.942 (1988)], the
preparation of Raney Nickel Catalysts [Ind. Eng. Chem. Res. 28,
p. 33 (1989)], the disproportionation of potassium benzoate, [Ind.
Eng. Chem. Res. 27 p.947 (1988)], and in bioreactors. Consider
the following elementary reaction sequence as a model system for

autocatalytic reactions: k
1
A →B
k2
A + B → 2B
The conversion of A as a function of space time in a packed-bed
reactor for conversion methanol is
τ, seconds 0 0.042 0.062 0.1
χ 0 0.06 0.13 0.38
Pure A enters at a concentration of 0.05 mol/dm3.
(a) Estimate k1 and k2.
(b) At what conversion and space time is the rate of
disappearance of A a maximum.
8
(c) Plot the concentrations of A and B as a function of space time.
Sexta Lista de
Exercícios
P5-9A Tests were run on a small experimental reactor used for

decomposing nitrogen oxides in an automobile exhaust stream. In
one series of tests, a nitrogen stream containing various
concentrations of NO2 was fed to a reactor and the kinetic data
obtained are shown in Figure P5-9. Each point represents one

complete run. The reactor operates essentially as an isothermal

backmix reactor (CSTR). What can you deduce about the
apparent order of the reaction over the temperature range
studied?
The plot gives the fractional decomposition of NO2 fed versus the
ratio of reactor volume V (in cm3) to the NO2 feed rate, FNO2,0 (g-
mol/h), at different feed concentrations of N02 (in parts per million
by weight).
9
Sexta Lista de
dos Materiais e Metalurgia Exercício P5-9 (continuação) Exercí
Exercícios
10
Sexta Lista de
Exercícios
P5-10B Penicillin G reacts with hydroxylamine (NH2OH) to form

hydroxamic acid, which produces a colored complex with iron (III).
To determine the overall reaction order, equal concentrations of
penicillin and NH2OH were mixed together in a 250-ml flask [J.
Chem. Educ., 49, 539 (1972)]. Samples were withdrawn every 10

minutes and added to a solution containing iron (III) chloride. With

the aid of a colorimeter, the concentration of the colored complex,
and hence the concentration of hydroxamic acid, was obtained as
a function of time. The absorbance shown in the table below is
directly proportional to the hydroxamic acid concentration.
Time (min) 0 10 20 30 40 50 ∞
Absorbance 0.00 0.337 0.433 0.495 0.539 0.561 0.685
Determine the overall order of reaction assuming that the

reaction is irreversible. (Ans.: Second-order.)
11

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What reaction is being studied in exercise P5-10B and what is its overall order?

What reaction is being studied in exercise P5-10B and what is its overall order?

What information can be deduced from the plot shown in exercise P5-9?

What information can be deduced from the plot shown in exercise P5-9?

dos Materiais e Metalurgia

Cinética e Engenharia de Reatores

Professor: Francisco Moura

P5-2A The irreversible isomerization

Determine the reaction order and specific reaction rate.

P5-3B GaInAs films are important materials in fiber optic communication

P5-4B The following data were reported [C. N. Hinshelwood and P. J.

Time (s) 390 777 1195 3155 ∞

Assuming that the reaction

P5-5B In order to study the photochemical decay of aqueous bromine in

P5-6C Triaminoguanidine (TAGN) is an important propellent ingredient

GN + 3N2H4 → TAGN + 3NH3 ↑

The following data give the cumulative ammonia evolved as a

6 Determine as many rate law parameters as possible.

P5-7C The reactions of ozone were studied in the presence of alkenes

law and the values of the rate-law parameters.

P5-8c Examples of autocatalytic reactions can be found in methanol

the following elementary reaction sequence as a model system for

P5-9A Tests were run on a small experimental reactor used for

obtained are shown in Figure P5-9. Each point represents one

complete run. The reactor operates essentially as an isothermal

P5-10B Penicillin G reacts with hydroxylamine (NH2OH) to form

Chem. Educ., 49, 539 (1972)]. Samples were withdrawn every 10

minutes and added to a solution containing iron (III) chloride. With

Determine the overall order of reaction assuming that the

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