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# Fall 2010

ChE 471
Homework No. 8 (FINAL VERSION)

(due Friday, November 12)

1. The reaction between sodium thiosulfate and hydrogen peroxide in dilute aqueous
solution is irreversible and second order in thiosulfate. The rate constant is the following
function of temperature:

 18300 
k  6.85 x 1014 exp  , cm 3 /(mol)(s)
 Rg T 

Reaction stoichiometry indicates that 2 moles of H2O2 react with one mol of Na2S2O3.
The heat of reaction at 25˚C is  HR = -131,000 (cal/mol). The universal gas
constant is Rg = 1.987 (cal/mol  ˚C). Kearns and Manning's (AIChE J., 15, 660
(1969)) experimental studies in a continuous flow stirred-tank reactor (CSTR or MFR)
included the following conditions:

Reactor volume = 2790 cm3
Feed temperature = 25˚C
Feed rate = 14.2 cm3/s

Consider adiabatic operation and feed concentrations of 2.04 x 10-4 (mol/cm3) and
4.08 x 10-4 (mol/cm3) of thiosulfate and hydrogen peroxide, respectively. What is
the conversion and temperature in the reactor effluent?

2. A tubular-flow reactor (assume plug flow) is to be designed for the production of
butadiene from butene by the following reaction in the gas phase:

C4H8  C4H6 + H2
The composition of the feed is 10 moles of steam per mole butene and no butadiene or
hydrogen. The reactor operated at 2 atmospheres pressure with an inlet (feed)
temperature of 1200˚ F. The reaction rate follows a first-order, irreversible equation for
which the rate constant k as a function of temperature is:

T(K) 922 (1200 ˚F)
900

877

855

832
k 11.0 4.90 2.04 0.85 0.32

(k = mol butene reacted/(h) (liter) (atm)).

The heat of reaction may be taken as constant and equal to   HR = 26,360 (cal/mol).
Similarly the specific heat of the system may be regarded as constant and equal
to 0.5 Btu/lb ˚R.

1

First prepare curves of net rate vs. 2 . What would be the volume required for a conversion (of butene) of 20% if the reactor were operated isothermally at 1200˚F with a butene-plus-steam feed rate of 22 lb mol/h? B. (a) Assuming that  H˚ is constant. (b) If the forward-rate constant is k = 5 x 108 e-12. at 298 K. reversible reactions increasing the temperature reduces the maximum (equilibrium) conversion but increases the forward rate. temperature from 0 to 100˚C. conversion and then as temperature vs. d) Plot the heat to be removed (added) from each 10th of the rector volume for part c). Calculate the conversion for a series of temperatures from 0 to 100˚C and plot the results on the figure prepared for part (a). feed rate.987 (cal/mol ˚C) determine the conversion in the effluent from an isothermal tubular-flow reactor for which the volumetric feed rate is 100 liters/min and the volume is 1500 liters. each with a volume of 750 liters. To obtain the maximum conversion a high temperature is needed at low conversions (where the reverse reaction is unimportant) and a lower temperature at higher conversions. temperature at constant conversion for several conversion levels. first as temperature vs. As noted in class for exothermic. Rg = 1. and composition as in Problem 3. It is desired to determine the conversion as a function of reactor volume (ft3) for adiabatic operation if the feed rate is 2. What should be the temperature (within the range 0 to 100˚C) in each reactor in order to obtain the maximum conversion in the effluent from the second reactor? The graphical method for multi-stirred tank reactors may be helpful. Consider a reversible first-order reaction A  B for which.0 lb mol of butene per hour and 20 lb mol of steam per hour.000 cal/mol (heat of reaction) The reaction mixture is an ideal liquid solution (constant density) at all temperatures. rate equation. plot a curve of the equilibrium conversion vs. 4. (c) Suppose that the maximum permissible temperature is 100˚C and the concentration of A in the feed stream is 2 (mol/liter) (the feed contains no B). Then plot the optimum temperature profile.500/RgT min-1 . A.20. The reaction is to be carried out in two-stirred tank reactors. Determine the maximum conversion obtainable in the reactor of part (b) if the temperature can be varied along the length of the reactor. Demonstrate your ability to solve this type of problem by calculating the reactor volume for conversions (of butane) of 10% and 20%. Consider the same reaction system. What changes in operating conditions could be employed to reduce the volume required for a given conversion? 3.  G˚298 = . V/Q.2500 cal/mol  H˚298 = .

7.. How long a time do you have to bring the fire under control and cool the cylinders before the point of no return is reached? Hint: Use the data that you need for this reaction system from problem 1.5.000 cal/mol and the heat capacity of the mixture is Cp = 300 cal/m3˚K We run this reaction in a wall cooled tubular (plug flow) reactor of diameter of 2. The reactant often was kept for years at such conditions in the storage area.RA = 4. The following irreversible second order gas phase reaction 2A = R + S is to be conducted in a wall cooled tubular (plug flow) reactor.5 x 1015e 25.e the time to the point of no return at To = 25 + 273 = 298˚ K for this reactant? Is storage for up to 5 years at 25˚C safe? b) A fire broke out and heated our storage area with the cylinders with A to 200˚C (473˚K). The inlet and wall temperature are To = Tc = 640˚K. What is the maximum reactant feed concentration that we can use and still avoid hot spots in the reactor? 6.000/RT CA m3 s with the activation energy given in calories per mol. The overall heat transfer coefficient is estimated to be U = 25 (cal/mol2 s˚K).5 cm. Consider a first order reaction (A  P) with the rate mol  . Reactant A that undergoes the reaction considered in problem 1 has been routinely stored in cylinders at concentration of 20 mol/m3 and stocked in a storage area with temperature at 25˚C.2 x 108 e-30.000/ RT CA2 ms 3 . Recall the analogy between adiabatic plug flow and adiabatic batch reactor and therefore the analogy between safe  * and safe t*. The heat of this highly exothermic reaction is H R = -150. a) What is the time to explosion i. Reaction rate is given by:  RA  mol3 A   1.

m K s  a) Would 2" diameter (dt = 0. coolant and feed temperature To = Tc = 300˚K. 000 cal/mol A: volumetric heat capacity of the reaction mixture  C p = 600 (cal/m3 ˚K). Other pertinent data include the heat of reaction H RA   20.e is    * ? 4 . mol A  where E = 25. feed reactant concentration CAo = 20 (mol A/m3).000 cal/mol is the activation energy and CA  m3  is reactant concentration.0508 m) tubes be safe to use? b) If the coolant failed what is the potential maximum temperature rise in this reactor? Is it dangerous? If the reactor became adiabatic and the gas velocity is 20 (m/s) and the reactor length is 5 meters would the resulting  avoid the maximum rate of the temperature rise to occur on the reactor i. overall wall heat transfer coefficient  cal  U = 50  2 o .