Exercise 3.

4
The flashing frequency of fireflies and the chirping of crickets in function
of the temperature, are:
For the fireflies
T(°C) 21.0 25.00 30.0
Flash/min 9.0 12.16 16.2
For the crickets
T(°C) 12.2 20.3 27.0
Squeaks/min 80 126 200

The speed at which ants run and the speed at which bees fly
of the temperature are:
For the ants
T(°C) 10 20 30.0 38
V(cm/s) 0.5 2 3.4 6.5
For the bees
T(°C) 25 30 35 40
V(cm/s) 0.7 1.8 3 ¿?

(a) What do fireflies and crickets have in common? What are the differences?
they present?

Fireflies
T(°C) 1/T (K-1) Flash / min Ln(Glare / min)
294.1
21 0.00340 9 2.19722458
5
298.1
25 0.00335 12.16 2.49815188
5
303.1
30 0.00330 16.2 2.78501124
5
Crickets
T(°C) 1/T (K-1) Chirps / min Ln(Chirps / min)
285.3
12.2 0.00350 80 4.38202663
5
293.4
20.3 0.00341 126 4.83628191
5
300.1
27 0.00333 200 5.29831737
5
 2.9 5.3
2.8 f(x) = -5275.64 x + 22.85 5.2
f(x) = -5801.39 x + 21.93 5.1
2.7
5
2.6 4.9
2.5 4.8
2.4 4.7
4.6
2.3
4.5
2.2 4.4
2.1 4.3
0.003295 0.003300.00334 0.00335 0.00033.090340 0.00.03043544 0.003500.00349 0.00355
1/T

Fireflies Linear (Fireflies)

Crickets Linear (Grillos)

When graphing the behavior of crickets (Ln(Crickets/min) vs 1/T) and fireflies

(Ln(Flashes/min) vs 1/T) both exhibit behavior according to
Arrhenius model Ln(y) = Ea/(R*T) + Ln(A) and performing a linear regression on the
In the semi-logarithmic graph, we can notice that both have a slope
similar therefore to an activation energy very similar.

(b) ¿Qué velocidad tiene la abeja a 40°C? ¿A - 5° C?

The graph of the data Ln(V) vs 1/T allows us to determine if these fit the
Arrhenius model Ln(y)=A+B/T

Bees
1.20000
1.00000
0.80000
0.60000
0.40000
0.20000
0.00000
-0.20000
-0.40000
0.00324 0.00326 0.00328 0.00330 0.00332 0.00334 0.00336
1/T
By behaving according to the Arrhenius law, we proceed to use the spreadsheet of
Excel to obtain the values of A and B in the equation Ln(y)=A+B/T and from this
how to calculate the speeds at the required temperatures.

Bees
V
T(°C) 1/T (K-1) Ln(V) Ln(CalculatedV) (LnV-LnVcal)^2
(cm/min)
25 298.15 0.00335 0.70000 -0.35667 -0.28953 0.00451
30 303.15 0.00330 180000 0.58779 0.45125 0.01864
35 308.15 0.00325 3.00000 1.09861 1.16800 0.00482
40 313.15 0.00319 6.43571 1.86186 1.86186
-5 268.15 0.00373 0.00492 -5.31441 -5.31441
A 44.6244 Sum 0.02796
B 13391.1

Do bees, ants, crickets, and fireflies have anything in common?

If so, what is it? It can also make a pairwise comparison.
To compare, we graph the behavior of the ant data Ln(V) vs
1/T.

Ants
2

1.5

0.5

-0.5

-1
0.00320 0.00325 0.00330 0.00335 0.00340 0.00345 0.00350
1/T

Therefore, the activity of bees, ants, crickets, and fireflies follows the
Arrhenius model, activity increases with an increase in temperature. The
The activation energies of fireflies and crickets are almost the same.
Would more data help clarify the relationship between frequency, speed, and
temperature? If so, at what temperature should such data be obtained?
Choose an insect and explain how you would conduct the experiment to obtain more.
data.
There is a temperature limit for which the data can be extrapolated from
any of the insects. The data that would be useful are the maximum temperature
and the minimum that these insects can reach before dying.
Therefore, even if the extrapolation gives us a value that seems reasonable, to
a certain temperature could be useful.
Exercise 3.11
Prepare a stoichiometric table for each of the following reactions and
express the concentration of each species in the reaction as a function of the
conversion, evaluating all the constants (for example, ε, θ). Then, assume
that the reaction follows an elementary rate law and write the speed of
reaction solely as a function of conversion, that is, - r A = f(X).
(a) For the liquid phase reaction
A+B→C
the initial concentrations of ethylene oxide and water are 1-lb-mol/feet 3y 3.47
lb-mol/feet362.41 lb/feet3÷18), respectively. If k = 0.1 dm3/mol . s at 300 K
With E = 12,500 cal/mol, calculate the space-time in a CSTR for a
conversion of 90% to 300 K and 350 K.
Hypothesis:
Steady state.
Elemental reaction.
Irreversible reaction
P and V constants
Limiting reagent 'A'
CSTR Reactor
Stoichiometry:
Oxidized styrene: C=C1−X
A A0 ( A )
3.47 lbmol
Water:C=C
B θ−
A0( BX=C A) A0
( − X=C3.47−
1 pound moleA A0( X
) A )

Glycol:C=C
C A0 θ+
( X=C
C A) X A0 A

Speed law:
2
−r=k
A C C=k
A C
B 1− XA 0 (C θ−X=k
A) A0 C
( B A ) A0 ( 1−X A ) (θ−X
B A )
Design equation for CSTR:
F A 0−F Aυ 0 (C A0−C A ) (CA 0−CA ) (C−C1−X)
A0 A0( A )
V= = →τ= = 2
−r A −r A −r A CKA01−( X θ−A) ( XB A )
XA
τ=
k CA0
1−( X A −X
theta)(
B A )
Evaluating for T1=300K
 dm3
∗1m 3
mol∗s ft 3
∗35.315
1000 DM3 lbmol∗s ft 3
k =0.1 =0.0035
m3 lbmol∗s
1
mol∗s
XA 0.9
τ= =
k CA0
1−X( θ−
A) ( XB ) 3

( )(
ft lbmol
)
A
0.0035 1 ( 1−0.9) ( 3.47−0.9)
lbmol∗s ft 3

τ =1000.55595s
Evaluating for T2=350K Using the Arrhenius equation.
Ea
[
1 1
] R
Ea
[
1 1
]
2 1∗e
K2 R
→K=K
∗ − ∗ −
T 1T2 T1T2
=e
K1

∗e 1.987 [
300 350 ]
12500 1 1
ft 3 ∗ − ft 3
K 2=0.0035 =0.0699
lbmol∗s lbmol∗s
XA 0.9
τ= =
k CA0
1−X( θ−
A) ( XB ) 3

( 0.0699 lbmol∗s)(1
ft lbmol
)
A
( 1−0.9) ( 3.47−0.9)
ft 3

τ =500335s

(b) For isothermal, isobaric pyrolysis in the gaseous phase.

A→B+C

Pure ethane enters the flow reactor at 6 atm and 1100 K. How would it change its
equation for concentration and reaction rate if it were to occur
in a constant volume intermittent reactor?
Hypothesis:
Steady state.
Irreversible reaction
P and V constants
Limiting reactant 'A'
CSTR Reactor

Stoichiometry:
A : F A =F A 0 (1− X A )

B:F Aθ+X=F
0( B A) X A0 A

C:F θ+
A 0X=F
( C X)
A A0 A

T:FA 0 (1−X A )

ε = y A 0∗δ=1∗ ( 1+1−1 )=1

V =V1+e
0( X=V1+
A) X0 ( A )
P0 6atm mol
CA 0 = = =0.067
RT 0 3
m ∗atm dm3
( 1100K ) 0.082
( kmol∗K )
1−X A
A : C A =CA 0
1+ X A
C A0X A
B:C Aθ+X=
0( B A ) 1+ X A
C A 0X A
C:C θ+X=
A0( C A ) 1+X A
1−X A
−A =kCA=0.0664
1+ X A

For a constant volume reactor:

V =V1+e
0( X ;e=0
A) ; V =V 0

A : C A =CA 0 (1−X A )

B:C Aθ+X=C
0( B A) X A0 A

C:C θ+
A 0 (X=C
C A X
) A0 A

−r A =kCA=0.0664(1−X A )

(c) For catalytic oxidation, isobaric, isothermal in gas phase.

A plus 0.5B leads to C
The feed enters a PBR at 6 atm and 260°C, and it is a stoichiometric mixture.
only of oxygen and ethylene.
Stoichiometry:
A : F A =F A 0 (1− X A )

B:F Aθ+X=0.5F
0( B A) X A0 A

C:F θ+
A 0X
( C=F A X
) A0 A

0.5
−A =kCAC B
2
ε = y A 0∗δ= ∗( 1−0.5−1 )=−0.33
3
V =V1+
0( X A )
P0 6atm mole
CA 0= = =0.092
RT 0 3
m ∗atm dm3
( 533K ) 0.082
( kmol∗K )
1−X A
A : C A =CA 0
1+ X A
0.092XA
B: 0.5CAθ+
0 ( X=
B A ) 1−0.33X
A

0.046XA
C:C θ+
A 0 (X=
C A ) 1−0.33X
A

0.5

( )(
0.092 ( 1− X A) 0.046XA
−r A =k
1−0.33XA 1−0.33XA )
(d) For the isothermal, isobaric, catalytic reaction in the gas phase conducted in a
Fluidized CSTR
A→C
The feed enters at 6 atm and 170°C and is a stoichiometric mixture. What?
catalyst weight required to achieve an 80% conversion in a
CSTR fluidized at 70°C and 270°C? The rate constant is defined with
regarding benzene and V o = 50 dm3/min.
53 mol kJ
k B= a 3 0 0 K c o n E a =80
kgcat∗min∗atm 3 mol
Exercise 3.16
Calculate the equilibrium conversion and the concentrations for each of the
following reactions.
the reaction in the liquid phase.
A+B↔C
with CA0= CS0= 2 mol/dm3y Kc = 10 dm3/mol.
Hypothesis:
Liquid phase reaction
Constant volume.
Reversible reaction
Speed law.
CC
−r A =kCAC B−C C =k[CAC B− ]
k eq

Stoichiometry:
C=C1−
A AX;C=C
0( A) θ−B X;C=C
A 0 ( B θ+ AX
) C A0 ( C A )
In balance:

[ ]
CC
−r A =0=k CAC B− → C AC Bk eq =CC
k eq

C 2A 0 (1− X eq )2k eq =C A0X eq

Developing the equation:

1
0=X 2q − 2+
( C A 0k eq )
X eq +1

Solving for CA02 mol/dm3y Kc=10 dm3/mol:

X eq=0.80

mol mol
C=C1−
A AX=2
0( A ) 3
∗(1−0.8)=0.4
dm dm3
mole mol
C=C
B A0θ−
( X=2
B A) 3
∗(1−0.8 )=0.4
dm dm3
mol mol
C=C
C A0θ+
( X=2
C A) 3
∗(0+ 0.8 )=1.6
dm dm3
(b) The reaction in the gas phase.

A↔3C
it takes place in a flow reactor without pressure drop. Pure A enters to
400 K2.
Hypothesis:
Gas phase reaction
Variable volume
Reversible reaction
Speed law.
CC
−r A =kCAC B−C C =k[CAC B− ]
k

Stoichiometry:
ε = y A 0∗δ=1∗( 3−1
) =2
N A N1−
A 0 (X A) ( 1−X A ) ;C = N C c N A0θ (+ CX A) 3X
( A)
CA =
V
=
V1+e
( X A) =C A0 ( 1+ 2X A)
C
V
=
aV1+ ( e X A) =C A0 ( 1+2X A)
In equilibrium:

[ ]
CC
−r A =0=k CA− → C Ak eq=C C
k eq
3
( 1− X eq ) k = C
[ ]
3X
( eq )
CA 0 eq A0
( 1+2X eq ) ( 1+2X eq )
2 22
k1−X1+2X=27C
eq ( eq ) ( X
eq ) A0eq

3 27C2A 0X 3eq
0=−4Xeq + +3Xeq + 1
k
X eq=0.58

P0 10atm mol
CA 0= = =0.305
RT 0 3
dm ∗atm dm3
( 400K ) 0.082
( mol∗K )
 mole
∗( 1−0.58 )
( 1−X A) dm3 mole
CA=CA 0
( 1+2 X A) =0.305 ( 1+2∗0.58)
=0.059
dm3
mole
∗3( 0.58 )
3X
( A) dm3 mol
C C =CA 0
( 1+2X A )
=0.305 ( 1+2∗0.58)
=0.246
dm3

The gas-phase reaction from section (b) takes place in a reactor.

constant volume intermittent.
Hypothesis:
Gas phase reaction
Constant volume
Reversible reaction
Speed law.
CC
−r A =kCAC B−C C =k[CAC B− ]
k eq

Stoichiometry:
ε = y A 0∗δ=1∗( 3−1 )
=2
N A N1−
A0(X ) =C ( 1− X A) ;C = N C c N Aθ0 (+X ) 3X
( A)
=C A0
A C A
CA = = A0 C =
V V1+e
A0( X A) ( 1+2X A ) V aV1+ A0e( X A) ( 1+2X A)

In equilibrium:

[ ]
CC
−r A =0=k CA− → C Ak eq=C C
k eq
3
C1−X
A0( k=
eq ) C3X
eq [ A0 ( eq )]
X eq=0.39

P0 10atm mol
CA 0= = =0.305
RT 0 dm ∗ATM dm3 3

(
( 400K ) 0.082
mol∗K )
mol mol
C=C1−
A AX=0.305
0( A) 3
∗(1−0.39)=0.19
dm dm3
 mol mol
C=C3X=0.305
C A0 ( A) 3
∗3( 0.39=0.36
)
dm dm3
(d) The gas phase reaction from subsection (b) takes place as a reaction
discontinuous at constant pressure.
Hypothesis:
Gas phase reaction
Constant volume.
Reversible reaction
Speed law.
CC
−r A =kCAC B−C C =k[CAC B− ]
k eq

Stoichiometry:
ε = y A 0∗δ=1∗( 3−1 )=2

N A N1−
A 0 (X ) NC c N Aθ0 (+ CX )
=C1− X;C= =C3X
A A
CA= = A0 ( A ) C = A0 ( A )
V VA0 V AVA 0

In balance:
3
( 1− X eq ) k = C
[ ]
3X
( eq )
CA 0 eq A0
( 1+2X eq ) ( 1+2X eq )
2 2 2
k1−X1+2X=27C
eq ( eq ) ( X
eq ) A0eq

3 27C2A 0X 3eq
0=−4Xeq + +3Xeq + 1
k eq
X eq=0.58

P0 10atm mol
CA 0= = =0.305
RT 0 dm ∗atm 3 dm3
(
( 400K ) 0.082
mole∗K )
mol
∗( 1−0.58 )
( 1−X A) dm3 mole
CA=CA 0
( 1+2 X A) =0.305 ( 1+2∗0.58 )
=0.059
dm3
mol
∗3( 0.58 )
3X
( A) dm3 mol
C C =CA 0
( 1+2X A )
=0.305 ( 1+2∗0.58)
=0.246
dm3
Exercise 3.17
Consider a cylindrical batch reactor at whose end a has been installed a
frictionless piston connected to a spring. The reaction
A + B → 8C
whose expression of speed
2
−r A =kCAC B
it will be carried out in this type of reactor.

Hypothesis:
Gas phase reaction
Constant volume.
Irreversible reaction
Stationary state
Isothermal system
Cylindrical reactor
(a) Write the rate law solely as a function of conversion, evaluating
numerically all possible symbols. (Answer: - r A = 5.03 X 10-9[(1 -
X)3/(1 +3X)3/2] lb mol/ft3 . s).
2
P0
( )
V0 2
V =V0 (1+ ε X)A P=10V;V= ( 1+ eXA ) → V 2=V0(1+ εXA )
P V

Determining the molar flows for the rate law.

N=N1−
A AX
0( ; N
=
A) N(θA− X)A 0 B A

2
2
k NA N B
K ( N A1−
0( X ) ) ( N A 0 ( θ−X
A B A))
−r A = =k 3
V3 3 2
V1+e
0 ( X A )
3 3 3
NA 01−( X y A 0∗P 0 ( 1− X A)
−r A =k
3
V1+e
0 ( X A
A)

)
3
2
=k
( RT ) V1+ε( X
0
3
A )
3
2

ε = y A 0∗δ=( 0.5)∗( 8−1−1 )=3

P0=10V0 =10∗0.15=1.5
3
ft 3
3
( 1− X A)
( )(
1.5∗0.5
−r A = 1
lbmol0.73∗600R ) V1+( ε X 0
3
A)
2
3

−r A =5.0207∗10−9 ( 1−X A )
3
3 2
V1+X
0 ( A )

What is the conversion and the reaction rate when V = 0.2 ft³?
(Response: X = 0.259, -r A = 8.63 X 10-10 lb mol/ft3 . s).