CHE 4151 Fall, 2010

ChemE Reactor Design Y. Lin

HW # 1: Introduction and Review

(due Thursday, 1/27)

1.1) [Atkins & Jones, Problem 18-29, 18-49 modified]

From experiment (i.e. batch) you determine that dinitrogen pentoxide, N2O5,
decomposes by first order kinetics with a rate constant of 3.7 x 10-5 (units) at
298K.

a) Give proper units on the rate constant.

b) How many minutes will it take for the N2O5 concentration to decrease
from 0.0273 M to 0.0175 M?

c) You also found that the rate constant at 350K is 5.3 x 10-5 (units). Find
the activation energy of the N2O5 decomposition reaction.

ANSWER:

a) For first order reaction the rate equation is r = k CA, thus the units
for k are 1/s:
r (mol/vol*time) = k (1/s) CA (mol/vol)

b) CA indicates the concentration of N2O5,

dCA
(−rA ) = = kCA → Batch
dt
C Af t
dCA
∫ = − ∫ kdt
C Ai C A 0

CAf
ln = kt
CAi
1 C  1  0.0175M 
t = ln Af  = ln  = 12,000s = 200min
k  CAi  3.7x10−5 s−1  0.0273M 

€
 c) Let’s refer to k at T1 = 298K as k1 and k at T2 = 350K as k2,

 k  −E a  1 1 
ln 1  =  − 
 k2  R  T1 T2 
k   J   3.7x10−5 s−1 
Rln 1  8.314  ln 
 k2   mol * K   5.3x10−5 s−1 
Ea = − =− = 6000J /mol = 6.0KJ /mol
1 1  1 1 
 −   − 
T
 1 T2
 298K 350K 

€
 1.2) [Jennings 2009, modified]

A reaction, A  B, is to be carried out in a constant volume batch reactor

with an initial concentration of reactant A, CA0. The reaction follows second
order kinetics. If the conversion of A is 20% at a 25 oC and 80% conversion
at 50 oC after the same amount of time and with the same initial
concentration, calculate the activation energy of the reaction?

ANSWER:

First solve for an expression for k using the reaction rate equation
(−rA ) = kCA 2
Batch
dCA 2
(−rA ) = = kCA
dt
C Af t
dC
∫ C A2 = ∫ kdt
CA 0 A 0

 1 1 
 −  = kt
 CA 0 CAf 
For constant Volume, we know that
CAf = CA 0 (1− x A )
1  1  1  −x A 
1− =   = kt
CA 0  (1− x A )  CA 0  (1− x A ) 
−x A
k=
tCA 0 (1− x A )

Lets refer to:

€
k1 for conditions “1” 
conversion of A is 20% after “t” minutes at a temperature of 25 oC
−x A1
xA1 = 0.20, T1 = 298 K, k1 =
tCA 0 (1− x A1 )

k2 for conditions “2”  conversion of A is 80% after “t” minutes at a

temperature of 50 oC
€ −x A 2
xA2 = 0.20, T1 = 323 K, k2 =
tCA 0 (1− x A 2 )

€
  k  −E a  1 1 
ln 1  =  − 
 k2  R  T1 T2 
 −x A1   x A1 
 k1   tC (1− x )   (1− x )   x (1− x A 2 ) 
ln  = ln A 0 A1 
= ln A1 
= ln A1 
 k2   −x A 2   xA 2   x A 2 (1− x A1 ) 
   
 tCA 0 (1− x A 2 )   (1− x A 2 ) 
 x (1− x A 2 )   J   0.20(1− 0.80) 
Rln A1   8.314  ln 
 x A 2 (1− x A1 )   mol * K   0.80(1− 0.20) 
Ea = − =− = 88751J /mol = 89KJ /mol
1 1  1 1 
 −   − 
 T1 T2   298K 323K 

€
 1.3) [pg. 102 Himmelblau, 6th edition]
A common method used in manufacturing sodium hypochlorite bleach is by
the reaction:
Cl2 + 2NaOH → NaCl + NaOCl + H 2O
Chlorine gas is bubbled through an aqueous solution of sodium hydroxide,
after which the desired product is separated from the sodium chloride (a by-
product of the reaction). A water-NaOH solution that contains 1145 lb of pure
€ is reacted with 851 lb of gaseous chlorine. The NaOCl formed weighs
NaOH
618 lb.
a) What is the limiting reactant?
b) What is the degree of completion of the reaction?
c) What was the percent excess of the reactant used?

ANSWER:

MW NaOH = 40lb /lbmol

MWCl 2 = 70.9lb /lbmol
MW NaOCl = 74.5lb /lbmol

a) Calculate how much NaOCl can be formed if all of the reactant is

consumed, the reactant yielding the smaller amount of product is
€ the limiting reactant,

 lbmol 
1145lb 
N NaOH  40lb 
= = 14.3lbmol
v NaOH 2
 lbmol 
851lb 
NCl2  70.9lb 
= = 12.0lbmol
vCl2 1
N NaOH NCl2
> , therefore Cl2 is the limiting reactant
v NaOH vCl2

€
 b) Or the conversion of the limiting reactant
618lb
N NaOCl = = 8.30lbmol = NCl 2 (used)
74.5lb /lbmol

N i0 − N i  v k  NCl2 0 − NCl2 f  1 8.30lbmol

ξ=  =  = = 0.69
Nk0  vi  NCl2 0  1 12.0lbmol
69% → degree of completion

c) How much of NaOH will remain in excess if 100% of Cl2 gas is used,
€
v   2
NNaOH consumed =  NaOH  NCl2 0 =  (12.0lbmol) = 24lbmol
 vCl 2   1
NNaOH remaining =
v  2
N NaOH 0 −  NaOH  NCl2 0 = 28.6lbmol −  (12.0lbmol) = 4.6lbmol
€vCl 2  1
v 
N i0 −  i  N k 0
 vk   4.6lbmol 
% Excess = (100) =  (100) = 19% excess of NaOH
€  vi   24lbmol 
 N k 0
 vk 

€
 1.4) [Problem 3-49, pg. 239 Himmelblau, 6th edition]
A gas with the following molar flow rates (mol/s) is burned in 50% excess air
(50% more oxygen) in a furnace. What is the composition of the flue gas (mol/s)?
Assume complete combustion and air composition of 21% O2 and 79% N2 by
volume.

CH4 60
C2 H6 20
CO 5
O2 5
N2 10

ANSWER:
Draw a diagram

Write the equation for complete combustion for each entering

component (except N2 and O2):

CH 4 + 2O2 → CO2 + 2H 2O
7
C2 H 6 + O2 → 2CO2 + 3H 2O
2
1
CO + O2 → CO2
2
Find the total flow rate of water produced in the reactions (since
excess oxygen is provided we can assume that all of the carbon
€ containing compounds will completely combust, i.e. CH4, C6H6 and CO
are the limiting reactants in their respective equations):
 molCH 4 2mol H 2O molO2
60 = 120
s 1molCH 4 s
molC 2 H 6 3mol H 2O molO2
20 = 60
s 1molC 2 H 6 s
mol mol H 2O
FH 2O = (120 + 60) = 180 ⇐ FH 2O _ OUT
s s

€ Find the total flow rate of CO2 produced:

molCH 4 1molCO2 molCO2

60 = 60
s 1molCH 4 s
molC 2 H 6 2molCO2 molCO2
20 = 40
s 1molC 2 H 6 s
molCO 1molCO2 molCO2
5 =5
s 1molCO s
mol molCO2
FCO2 = (60 + 40 + 5) = 105 ⇐ FCO2 _ OUT
s s

€
 Find the total flow rate of oxygen needed for complete combustion of
the entering gas:
molCH 4 2molO2 molO2
60 = 120
s 1molCH 4 s
7
molC 2 H 6 2 molO2 molO2
20 = 70
s 1molC 2 H 6 s
1
molCO molO2 molO2
5 2 = 2.5
s 1molCO s
mol molO2
FO2 = (120 + 70 + 2.5) = 192.5
s s
for _ 50% _ excess :
molO2 molO2 _ IN
O2 _ IN :192.5 (1.5) = 288.75
s s
molO2 _ IN molO2 molO2 molO2 _ OUT
O2 _ OUT : 288.75 − (192.5) +5 = 101.25 ⇐ FO2 _ OUT
s s s s
molO2 0.79molN 2 molN 2 molN 2
N 2 _ IN & OUT : 288.75 + 10 = 1096.25 ⇐ FN 2 _ OUT
s 0.21molO2 s s