UNIVERSITY OF EL SALVADOR

SCHOOL OF ENGINEERING AND ARCHITECTURE

SCHOOL OF CHEMICAL ENGINEERING AND FOOD ENGINEERING
Chemical Reaction Engineering

DISCUSSION #2

Unit II: Modeling of the kinetics of chemical reactions

1. The reaction A was carried out. B + C in a batch reactor of volume

constant where the following concentration measurements were recorded in
function of time

t (min) 0 5 9 15 22 30 40 60
CA(mol/dm ) 2 1.6 1.35 1.10 0.87 0.70 0.53 0.35
3

a) Use nonlinear least squares (i.e., regression) and another method.

to determine the order of the reaction and the specific reaction rate
b) If I were to take more data, where would I place the points? Why?

2. The following data was reported for a volume decomposition

gas phase constant of methyl ether at 504°C in a batch reactor.
Initially there was only (CH3)2The gift

Tiempo (s) 390 777 1195 3155

Presión Total (mmHg) 408 488 562 799 931

a) Why do you think the total pressure measurement is missing at t=0? Can you
estimate it?
b) Assuming that the reaction (CH3)2O CH4+ O2+ CO is irreversible and
it reaches its end, determine the order of the reaction and the speed of the
specific reaction k.

3. To study the photochemical decomposition of aqueous bromine exposed to the

bright sunlight, a small amount of liquid bromine was dissolved in water
content in a battery jar placed in direct sunlight. It
they obtained the following data:

Time (min) 10 20 30 40 50 60
ppm Br22.45 1.74 1.23 0.88 0.62 0.44

a) Determine if the reaction rate is of zero, first, or second order.

to bromine and calculate the reaction rate constant in the units that
prefer
b) Assuming identical exposure conditions, calculate the speed of
bromine injection (in lb/h) required in a sun-exposed body of water

Page 1 of 8
 with a volume of 25000 gallons, in order to maintain a sterilizing level of
bromine at 1.0 ppm (Response: 0.43 Lb/h)

c) What experimental conditions would you suggest if you were to obtain more data?
(NOTE: ppm = parts per million of brominated water parts, by weight. In
diluted aqueous solutions, 1 ppm = 1 mg/l

4. The gas-phase decomposition of A is carried out. B + 2C in a

batch reactor at a constant volume. Tests 1 to 5 were carried out at
100°C, but test 6 was conducted at 110°C

Test 1 2 3 4 5 6
Initial concentration CTo 0.0250 0.0133 0.0100 0.0500 0.0750 0.0250
(g/ml)
Half-life t (min)
½ 4.1 7.7 9.8 1.96 1.3 2.0

a) Determine the order of reaction and the specific rate of reaction.

b) Calculate the activation energy of this reaction

5. The reactions of ozone in the presence of alkenes are studied. The data
The values from the table are for cis-2-butene. The reaction was carried out isothermally at 297.
K. Determine the rate law and the values of the parameters of the law of
speed
(Suggestion: ozone also decomposes upon colliding with the wall)

Test 1 2 3 4 5 6
mol
Speed of ozone x107 1.5 3.2 3.5 5.0 8.8 4.7
s*dm3
Ozone concentration (mol/dm)3) 0.010 0.020 0.015 0.005 0.001 0.018
Concentration of butane (mol/dm)310-1210-1110-1010-9 10-8 10-9

6. Calculate k and n for the following reactions under volume conditions.

constant

a) Reaction between nitric oxide and hydrogen at 826°C, starting from

equal amounts of all the components (Poit is the initial total pressure

PommHg 354 340.5 288 202

t½ seconds 81 102 140 224

b) Thermal decomposition of dimethyl ether at 540°C

P mmHg 312 408 488 562 779 931

t seconds 0 210 717 1195 3155

Page 2 of 8
7. The decomposition rates of acetaldehyde corresponding to
various percentage decompositions, expressed in millimeters of mercury per
minute, are as follows: (determine the order of the reaction)

% 0 5 10 15 20 25 30 35 40 45 50
Velocidad 8.53 7.49 6.74 5.90 5.14 4.69 4.31 3.75 3.11 2.67 2.29

8. Hexamethylenetetramine has been obtained at 0°C in a 1-liter reactor from

formaldehyde and aqueous ammonia. Find the order of the reaction with respect to
ammonia from the following data:

Weight % NH3present 0.8 0.6 0.41 0.2 0.016

Moles of NH3convertidos por minuto 0.025 0.020 0.010 0.002 0.00002

9. The condensation of formaldehyde (F) with sodium paratoluenesulfonate (M) was

carried out. The kinetic data for the formation of the monomer MA at 100°C with
pH=8.35 and starting from equal amounts of F and M are the following: (Please indicate
if the data fits better to first-order kinetics or to second-order kinetics)

F mol/litro 0.131 0.125 0.121 0.117 0.111 0.104

t minutes 0 10 20 30 40 60

dx
[Link] equation kinetics 1.5k1 ek1t  k 2x has how solution
dt
x
1.5k1
k2 k1
 ek t
1
e
 k 2t  Calculate the numerical values of k1y k2from the
following data:

t 20 30 40 50
x 0.699 0.515 0.286 0.225

[Link] following data correspond to a reaction that is considered to be

first order in reverse direction and second order in direct direction. The
the initial concentration of each of the reactants is 1.2 mol/liter, and initially
There are no products. Please calculate:

a) The specific reaction rates

b) The equilibrium constant
c) The time required for the conversion of 60% of the reactants

Moles of A
convertidos 0.00 0.05 0.10 0.15 0.20 0.30 0.40 0.50 0.60 0.70 0.80
per liter
Speed
mol 2.16 1.96 1.79 1.60 1.44 1.12 0.84 0.59 0.38 0.17 0.00
liter*minute

Page 3 of 8
 12. When studying the reaction in aqueous solution CH3COCH3+ HCN = (CH3)2C
CN
A run was taken with initial concentrations of 0.0758 normal for HCN and
OH
0.1166 for acetone. Determine a reasonable rate equation from
the data (Kc=13.87 l/mol)

t, min 4.37 73.2 172.5 265.4 346.7 434.4

CHCN, normal 0.0748 0.0710 0.0655 0.0610 0.0584 0.0557

13. The following tables show the kinetic data at 25°C for the
conversion of tert-butyl bromide to tert-butyl alcohol in a 90% solvent
acetone and 10% water

Time,
0 3.15 4.1 6.2 8.2 10.0 13.5 18.3 26.0 30.8
h
C(CH3) 3CBr
0.1039 0.0896 0.0859 0.0776 0.0701 0.0639 0.0529 0.0353 0.0270 0.0207
gmol/l

The reaction is (CH3)3CBr + H2O (CH3)3COH + HBr. Determine the equation of

speed.

14. Aqueous solutions of diazobenzene decompose

irreversibly according to the following reaction: C6H5N2Cl(aq) C6H5Cl(aq) +
N2(g)In an experiment at 50°C, the initial concentration of C6H5N2Cl was 10g/l,
and the following quantities of N were obtained2:

Time of
6 9 12 14 18 20 22 24 26 30
reaction (min)
N2produced to
50°C y 1 atm 19.3 26.0 32.6 36.0 41.3 43.3 45.0 46.5 48.4 50.3
(cm3)

The complete decomposition of the salt produced 58.3 cm3of N2. Calculate the value of
the specific reaction rate and determine the order of the reaction

15. Suppose that a kinetic study is being carried out on a gaseous reaction between A and B,
carrying out isothermal measurements of average lifespan of different
initial compositions of reactants. The results for each of four
different initial conditions are as follows:

(PA)o 500 125 250 250

(PB)o 10 15 10 20
t½B (min) 80 213 160 80

Page 4 of 8
If the reaction rate is first order with respect to A and second order
Regarding B, what is the numerical value of the specific reaction rate?

A small reaction bomb, equipped with a sensitive device for

the pressure measure is evacuated and then loaded with a mixture of 76.94%
of reactant A and the rest with inerts at a pressure of 1 atm. The operation is
takes place at 14°C, a sufficiently low temperature for the reaction not to occur
occurs over a considerable extent. The temperature rises rapidly to 100°C.
submerging the pump in boiling water, obtaining the data from the table. The
stoichiometric equation is A 2R and after a sufficient amount of time, the
the reaction is complete. Derive a kinetic equation that fits the data,
expressing the units in mol, liter and minute.

t, min 0.5 1 1.5 2 2.5 3 3.5 4 5 6 7 8

, 1.5 1.65 1.76 1.84 1.9 1.95 1.99 2.025 2.08 2.12 2.15 2.175
ATM

17. In a batch reactor of constant volume, the following data has been obtained
following using pure gas component A:

Time, min 0 2 4 6 8 10 12 14
Presión parcial de A, mmHg 760 600 475 390 320 275 240 215 150

The stoichiometry of decomposition is A 2.5R. Derive the equation

Kinetics that satisfactorily represents this decomposition.

18. For the zero-order reaction, A rR that is carried out in a pump of

constant volume, with 20% inert gases, the pressure rises from 1 to 1.3 atm
in 2 minutes. For the same reaction carried out in a batch pressure reactor
constant what is the fractional variation of the volume in 4 minutes if the feeding
Is it at 3 atm and contains 40% inerts?

[Link] the complete kinetic equation in units of moles, liters and

seconds for the thermal decomposition of tetrahydrofuran from the data
of the average period of the table

ommHg 214 204 280 130 206

t½ min 14.5 67 17.3 39 47
T °C 569 530 560 550 539

Page 5 of 8
20. In a batch reactor, 0.1 g of dimethyl ether is placed with 0.05 g of
nitrogen at 504°C and one atmosphere of pressure. At these conditions, the reactant is
pyrolysis according to the reaction:

CH 3AND 3CH H CO
4 2

As the reaction proceeds, the following time readings were taken.

and differences in volume, since the pressure in the reactor is constant, because
its piston slides freely.

Time (s) 2.5 5.3 8.5 12.2 16.6 21.8 28.8

V–Vo(l) 0.0275 0.0549 0.0824 0.1098 0.1373 0.1647 0.1922

a) Determine the order and specific rate of reaction.

b) Calculate how long it will take to have a volume equal to twice the initial one.

The production of propionic acid is carried out by acidifying a solution.

sodium salt aqueous solution at room temperature according to the following
reaction: HCl = The following data was obtained
taking a sample of 10 ml of reacting solution at various times and
neutralizing the unreacted HCl with an aqueous solution of NaOH of
0.515N, the initial concentrations of the two reactants are the same.
Determine: a) el modelo de velocidad de la reacción; b) la constante de equilibrio y
the values of the specific reaction rate; c) The time required to
achieve 73.75% conversion with an initial concentration 20% higher.

Time(min) Solution NaOH (ml)

0 52.5
12 32.1
20 23.5
30 18.9
50 14.4
∞ 10.5

22. In the following reaction, the data obtained was: A + B → C + D

CAx 103 10.0 7.4 6.34 5.5 4.64

(mol/l)
Time (min) 0 3 5 7 10

This reaction takes place at 25°C and the reactants are fed in.
equivalently. Determine:

Page 6 of 8
 a) The kinetic model for the reaction.
b) The half-life at 40°C, if the activation energy is 12.3
kcal/mol.
c) The time it takes to reach 95% conversion at 25°C, if it
uses a concentration of B that is double the concentration of A.

23. In a sealed container, the gaseous phase reaction A = R + S was carried out.
the initial partial pressures were PTo= 0.2 atm; PRo= 24.8 atm, Pso= 0 atm.
The reactor was kept in a hot oil bath at 157°C. Analyzed were
samples of the reacting mixture with the following results. Calculate the
kinetic equation, a) by the differential method; b) by the integral method.

Time 2 4 8 16 20 α
(min)
Ps (atm) 0.03142 0.05504 0.08615 0.11366 0.11927 0.12656

24. For the following liquid-phase reaction: A PRODUCTS, were obtained

the following kinetic data operating in a batch reactor operating at 30 and
50ºC, starting from an initial concentration of A of 1.5 mol/l, in both cases, a)
encuentre el orden y la velocidad específica a 30 y a 50ºC, indique dos
observations either related to the experiment or to the results; b) calculate the
temperature at which the reactor must operate to achieve 80% conversion
of the limiting reagent in 50 minutes starting from CAO= 3 mol/l.

Temperatura (ºC) Tiempo (min) Concentration of A

(mol/l)
10 1.304
20 1.154
30 40 0.937
100 0.6
10 1.003
20 0.753
50 30 0.603
40 0.503
50 0.431

Page 7 of 8
 DISCUSSION PLAN

1) Problems to be developed in teams during the discussion sessions:

PROBLEMS
1, 3, 4, 5, 8, 11, 13
14,16, 21,24

Page 8 of 8