DESIGN OF SIMPLE REACTORS

BATCH REACTORS

TUBULAR REACTORS

AGITATED CONTINUOUS REACTORS

Comparison of reactors

Recirculation

Non-isothermal reactions
DISCONTINUOUS REACTORS

Phosgene is formed by the reaction of gaseous chlorine and carbon monoxide in the presence
of activated carbon:
CO (g) + Cl2(g) Cobalt dichloride2(g)

)2
v (mol/min·gC= 8.75·CCOCCl2/(1+58.6·CCl2+34.3 °CCobalt(II) chloride 30.6ºC

The charge contains 50% of each reactant in a 3-liter batch reactor, with 1 gram of
carbon and an initial pressure of 1 atm.

Calculate the time required to achieve a conversion of 75% (use the integration rule -
Simpson's integration and disregard the volume occupied by the coal.
In a batch isothermal reactor, methyl acetate is hydrolyzed. The charge consists of
8517 kg of ester, 87768 kg of water, and a catalyst, such that the density of the mixture is
0.964 g/cm3The kinetic constant is 1.5·10-4dm3mol-1min-1and the equilibrium constant K=0.22.
Calculate the required operating period to achieve a 90% conversion rate regarding
maximum possible.
Rta.: 261 min

Urea is obtained industrially, for use as fertilizer, in the form of an aqueous solution.
concentrated that later solidifies and is packaged, since when dissolved it produces the reaction of
biuret: 2 NH2CONH2(ac) NH2CONHCONH2+ NH3.
If the effluent of the process is a urea solution with a concentration of 20 mol/dm3a
80ºC, how much time can we delay its solidification if it is maintained at this temperature?
the biuret reaction constant is k= 2.38·10-5dm3mole-1h-1, in such a way that the amount
Does the transformed urea not exceed 1%?
Time: 21.2 h
In a batch isothermal reactor, methyl acetate is hydrolyzed. The feed consists of
8517 kg of ester, 87768 kg of water, and a catalyst, so that the density of the mixture is
0.964 g/cm³3The kinetic constant is 1.5·10-4direct message3mol-1min-1and the equilibrium constant K=0.22.
Calculate the required operation period to achieve a 90% conversion rate.
maximum possible.

CH3CO2CH3+ H2The CH3CO2H + CH3OH

K = (CoAxe)2/[CoA(1-xeoB-CoAxe)] xand0.91 x = 0.90 · xe= 0.82

t= CoA x/v = 116.6·{ln [(1.19·x + 16)/(1.19·x - 1.1)] - ln [16/(-1.1)]} = 261 min ([Link]&Ch A50 No. 110)

v = kdCoA(1-x)(CoB-CoAx) - ki(CoAx)2

CoA(8517/MA/V = 1.12 kmol/m3

CoB = (87768/MB)/V = 48.8 kmol/m3
V= (mA+mB)/d = 99.88 m3

kd= 1.5·104 kI= kd/K = 6.8·10-4m3kmol-1min-1

Graphically:

v = 8.20 · 10-3- 8.29·10-3x - 6.65 × 10-4x2

x/v = 23.5·10 = 235 dm·mol-1min-1

t = 235·CoA263 min

Urea is obtained industrially, for use as fertilizer, in the form of an aqueous solution.
concentrated, which is then solidified and packaged, as dissolved it produces the reaction of
biuret: 2 NH2CONH2(ac) NH2CONHCONH2+ NH3.
If the effluent from the process is a urea solution with a concentration of 20 mol/dm3a
80ºC, how long can we delay its solidification if it is maintained at this temperature?
the biuret reaction constant is k= 2.38·10-5dm3mol-1h-1, so that the amount
Does the transformed urea not exceed 1%?
TUBULAR REACTORS

It has been found that the reaction rate in homogeneous gas phase at 215ºC results
to be A 2R vA= 10-2CAmol·dm
½ -3s-1

Calculate the residence time necessary to achieve an 80% conversion rate, starting from a
A pure feed in an ideal tubular reactor operating at that temperature and 2.5 atm.

Rta.: 33 s

The decomposition of phosphamine in homogeneous gas phase occurs at 650ºC and 4.6 atm.
according to the reaction and kinetics:
4 PH3(g) P4(g) + 6 H2(g) v = k · CPH3 k=10 h-1

Approximately calculate the size of a tubular reactor for an 80% conversion and a
pure phosphine supply of 1.8 kmol/h.
Response: 6.54 m3

The rate constants of the reaction for the formation of dibromoethane in the gas phase at
600K son:
C2H4(g) + Br2(g) C2H4Br2(g) kd500 dm3mol-1h-1ki0.032 h-1

This reaction takes place in an ideal tubular reactor with a feed of 600 m.3/h of a
mixture that contains 60% Br230% of C2H4and 10% of inert materials by volume, at 600K and 1.5 atm.
Calculate the theoretically maximum possible conversion of ethylene into dibromoethane and the volume of
reactor necessary to achieve 60% of that theoretical conversion.
Response: 99.5% and 58.2 m3

The liquid phase hydrolysis of a diluted solution of acetic anhydride (10% by weight) is carried out
ends in a tubular reactor that operates with 'piston flow'. The mass flow rate through
the tube is uniform (5 kg/min), with a cross-section of 0.1 m 2the density of the fluid
it can be considered constant and equal to 950 kg/m3The speed of the hydrolysis reaction
respond to the following first-order kinetics:
v = -dCA/dt = k·CA (k = 0, 1 min-1)

Calculate the length of the reactor that would be necessary to achieve a final conversion of 90%.

Rta.: 1.21 m
It has been found that the reaction rate in homogeneous gas phase at 215ºC results
to be A 2R vA= 10-2CAmol·dm
½ -3s-1

Calculate the residence time needed to achieve an 80% conversion, starting from a
Feeding of A pure, in an ideal tubular reactor operating at that temperature and 2.5 atm.

A CoA x = 0.8
T = 488 K
2.5 atm

= CoA x/v

CoA= pA/RT = 6.25·10-2mo/dm3

v = k·CA ½ CA= CoA(1-x)/(1+ x) =1

Graphically:

= 6.25·10-2·13.25·40 = 33 s

analytically

= CoA½/k· [(1+x)/(1-x)] ½ x = CoA/k·[sen

½ -1x - (1-x2)½ (6.25·10-2)½ /10-2·(sen-10.8 - (1 - 0.64) ½+ 1 = 33 s

The decomposition of phosphine in homogeneous gas phase occurs at 650ºC and 4.6 atm.
according to the reaction and kinetics:
4 PH3(g) P4(g) + 6 H2(g) v = k · CPH3 k=10 h-1

Approximate calculation of the size of a tubular reactor for an 80% conversion and a
pure phosphine feed of 1.8 kmol/h.

= Co x/v Co= T = 0.0608 kmol/m3

v = k·Co(1-x)/(1+ x) = (7-4)/4 = 0.75

Analytically: = -1/k·[(1+ )·ln(1-x) + 0.222 h

Vr= Vo· 6.57 m3 with Vo= Fo/Co29.6 m3/h

Graphically:

V= ·Vo= 0.0608·9.1·0.4·29.6 = 6.54 m3

The rate constants of the reaction for the formation of dibromoethane in the gas phase at
600K son:
C2H4(g) + Br2(g) C2H4Br2(g) kd= 500 dm3mol-1h-1ki0.032 h-1

This reaction takes place in an ideal tubular reactor with a feed of 600 m.3of a
mixture containing 60% Br230% of C2H4and 10% of inert materials by volume, at 600K and 1.5 atm.
Calculate the theoretically possible maximum conversion of ethylene to dibromoethane and the volume of
reactor necessary to achieve 60% of that theoretical conversion.

Vo600 m3/h T= 600 K

1.5 atm xf= 0.60·xe
XC2H40,30 XBr2:0,60 XIn:0,10

Co = p/RT = 0.0305 mol/dm3 K = kdi= CC2H4Br2(CC2H4·CBr2)

Chi= CoXi(limiting reactant; C)2H4) Ci= (Chi CC2H4·x)/(1+ x)

=(0.30+0.30+0.10-1)/1 = -0.3

143.3 · x2and-430·xe+286 = 0 xe= 0.995 (2.006, invalid solution)

= CC2H4 x/v xf 0.597

v = kdCEthyleneCBr2- kiCC2H4Br2= 4,186·10-2(1-x)(2-x)/(1-0.3·x)2- 2,928·10-4x/(1-0.3·x)

x/v = 5.3 cm22 dm3mol-1h/cm2= 10.6 dm3mol-1h

= 9.15·10-3mol/dm310.6 dm3mol-1h = 0.097 h

V= ·Vo= 0.097 h · 600 m358.2 m3

The liquid-phase hydrolysis of a diluted solution of acetic anhydride (10% by mass) is carried out
at the end in a tubular reactor that operates with 'piston flow'. The mass flow rate through
the pipe is uniform (5 kg/min), with a cross section of 0.1 m2the density of the fluid
it can be considered constant and equal to 950 kg/m3The speed of the hydrolysis reaction
respond to the following first-order kinetics:
v = -dCA/dt = k·CA (k= 0,1 min-1)

Calculate the length of the reactor that would be necessary to achieve a final conversion of 90%.

L = V/S = (Fo,A· dx/v)/S = 1.21 m

Fo,A= Fo·Xo,A0.50 kgA/min v = k·Co,A(1-x), kgA/m3min Co,A= XA95 kgA/m3

23 min V = Fo/d· 0.121 m3

CONTINUOUS AGITATED TANK REACTORS

An ideal continuous stirred-tank reactor with a volume of 120 liters is used to carry out the
next reaction in the liquid phase and steady state:

A+B R+S kd= 7 ki= 3 (both in dm)3mol-1min-1)

The reactor is fed with 2 streams of equal flow: 2.8 molA1.6 molB/l, and it is desired that the
the conversion of the limiting reagent is 75%. Calculate the flow rate of the streams assuming that
the density of the system remains constant.
Rta.: 4 liters per minute

An ideal continuous stirred-tank reactor operating isothermally at 15ºC is used.

to convert a reagent A that is fed with a volumetric flow of 25 m3/day and concentration
0.005 molar. The rate equation is:
v(mol·dm-3h-1= CA/ (22.5·CA+0.02

Calculate the volume with which a simple reactor or two identical reactors should be sized in
waterfall to achieve a 90% conversion.
Rta.: 293 and 101 l

A continuous battery is to be installed consisting of 4 isothermal tanks of equal size to

carry out the esterification of ethanol with acetic acid: kd= 4.76·10-4y ki= 1.63·10-4dm3mol-1min-1.
The food is 3 m.3/h of a 6.6 molar mixture of acid and 10.8 molar of alcohol, and is
wants to obtain a 95% conversion of acetic acid regarding equilibrium.
Calculate the volume of the tanks. If one of them is taken out of service for repair and the
battery is reduced to 3 tanks What proportion of the feed flow should be reduced
to avoid modifying the composition of the output current?
Discuss the calculation of the optimal system using two or more reactors, taking into account the
sizes and the economy of the equipment.
Response: 7m3y27%

Calculate the conversion of a mixture of acetic acid (6.6 M) and ethanol (10.8 M) that is fed with
a flow of 1 m3to the following esterification teams, which in all cases have the same
total capacity of 2 m3:
a/ Maximum conversion (equilibrium).
b/ Unique continuous stirred tank (perfect mixing).
Two tanks in series of equal size.
Optimal conversion in two distinct series tanks
mathematical model and information flow diagram.

Data: kinetic constants of the forward and reverse reactions (kd= 4.76·10-4dm3mol-1min-1, k1.63
i x 10-4dm3mol-1min-1).
Density close to unity can be assumed for the mixture.
Rta.: 0.65; 0.30 and 0.34

Analyze and optimize the system of two continuous tanks in series, isothermal and well-stirred,
where the irreversible first-order reaction A takes place B, the density remains constant
dad of the dissolution and the level of the tanks, and with specified variables: flow and concentration of
the feeding, tank temperatures, kinetics and final conversion (x2=0.90).

Response:Imin= aVb(1-x1op)b+1(x2/x1op-1)b-1= [k2/k1 (1-x2)]b; for b=1y T1=T2: x1up= 0,68 (V2/V1=1)

There is a battery with tanks of 26.5 m3of unit size for the polymerization of the
styrene and butadiene, whose kinetic constant at the working temperature is 6·10-4dm3mol-1min-1. The
The feed consists of 19.6 t/h of a stream with 0.795 and 3.55 mol/l of each of the
olefins, whose density is 0.87 kg/l. Calculate the number of reactors needed to convert
85% of the styrene.
Response: N=14
An ideal continuous stirred tank reactor with a volume of 120 liters is used to carry out the
next reaction in liquid phase and stationary regime:

A+B R+S kd= 7 ki= 3 (both in dm)3mol-1min-1)

The reactor is fed with 2 streams of equal flow: 2.8 molA1.6 molesB/l, and it is desired that the
The conversion of the limiting reagent is 75%. Calculate the flow rate of the streams assuming that
the density of the system remains constant.

CoA1.4 mol/l vB= kd(CoA-CoBx)·CoB(1-x) - ki·(CoBx)20.04 mol·dm-3min-1

CoB0.8 mol/l VoA= VoB
xB= 0.75
= V/Vo= CoB-x/ v= 15 min

Vo= V/x·[kd·(CoA-CoBx)·(1-x) - kiCoBx2= 8 l/min

V = 120 dm3
Vo= VoA+ VoB Vhi4 l/min

An ideal continuous stirred-tank reactor operating isothermally at 15ºC is used

to convert a reagent A that is fed with a volumetric flow of 25 m3/day and concentration
0.005 molar. The rate equation is:
v(mol·dm-3h-1)= CA/ (22.5·CA+0.02

Calculate the volume with which a single reactor or two identical reactors should be sized.
waterfall to achieve a 90% conversion.

Vo= 1042 l/h v = CoA(1-x)/[22.5·CoA(1-x)+0.02] = 0.016 mol·dm-3h-1

CoA5 times 10-3mol/l x = 0.90

= CoA-x / v = 0.281 h
V
V = ·Vo=293 liters

Vo x1 x2

CoA

V1 V2

1= CoA·x1/ v1 2= CoA(x2-x12

x1/ CoA(1-x1)/[22.5·CoA(1-x1)+0.02] = (0.90 - x1)/0.016x10.59

1= 20.097 VI= i·V o 101 liters

A continuous battery composed of 4 isothermal tanks of the same size is to be installed for
carry out the esterification of ethanol with acetic acid: kd= 4.76·10-4y ki= 1.63·10-4dm3mol-1min-1.
The food is 3 m.3/h of a 6.6 molar mixture of acid and 10.8 molar of alcohol, and it
wants to obtain a 95% acetic acid conversion with respect to the equilibrium.
Calculate the volume of the tanks. If one of them is taken out of service for repair and the
battery is reduced to 3 tanks What proportion of the feed flow should be reduced
to avoid modifying the composition of the output current?
Discuss the calculation of the optimal system using two or more reactors, taking into account the
sizes and the economy of the equipment.

Vo= 3 m3/h CH3CO2H + C2H5OH CH3CO2C2H5+ H2O

xA= 0.95·xeA
CoA6.6 M
CoB10.8 M

V1 V2 V3 V4

2
K = kd/ki= CoAxe·(CoW+CoAxe) / CoA(1-xe)CoB-CoAxe) = 6.6·xe(1-xe)(10,8-6,6·xe= 2.92; xe0.713

The amount of water can be disregarded since the initial concentration: (6.6·60+10.8·46)/1000= 0.893 g/ml, is similar.
to the density of an ideal mixture of absolute ethanol and glacial acetic: d= [0.44/1.05 + 0.56/0.79]-1= 0.887 kg/l (CoW 0).

v = kdCoA(1-x)(CoB-CoAx) - kioAxe)2; CoA/v = [4.76·10-4-(1-x)(10.8-6.6·x) -1.68·10-46.6x2]-1

CoA(1-x) = CACoAx = CoA-CA xA0.95 · 0.713 = 0.677 CfA= 6.6·(1-xA) = 2.13 M

= 1/0.0072 = 139 min V = ·Vo=7.0 m3(with 4 reactors)

= 1/0.0052 = 192 min Vo= V/ 2.2 m3h (3 reactors) 100·(Vo-Voo26.7%

For two reactors, the graphical calculation of Vi,minit can be done based on searching for the rectangle of
maximum area that minimizes the total residence time: x1 0.50 1+ 2= 687 min

3000

T = Co·x/v

2000

1000

0
0,0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Conversion (x)

The calculation of the optimal system that minimizes equipment costs will depend on the scale coefficient:
I = n·a Vib, testing different battery configurations and graphically calculating the volumes of
the resulting reactorsI= (Co/ i)· xiVi= i·Vo(n= 1,2,3,…).
Calculate the conversion of a mixture of acetic acid (6.6 M) and ethanol (10.8 M) that is fed with
a flow of 1 m3to the following esterification teams, which in all cases have the same
total capacity of 2 m3:
a/ Maximum conversion (equilibrium).
b/ Unique stirred continuous tank (perfect mixing).
Two tanks in series of equal size.
Optimal conversion in two distinct series tanks
(mathematical model and flowchart of information).

Data: kinetic constants of the forward and reverse reactions (kd= 4.76·10-4dm3mol-1min-1, k1.63·10
i
-4dm3mol-1min-1).

Density close to one can be assumed for the mixture.

AcH + EtOH = AcEt + H2O kd= 4.76·10-4dm3mol-1min-1

ki1.63 × 10-43mol-1min-1

CoAcH6.6 mol·dm-3 Vo = 1 m3/h FoAcHVo·CoAcH0.11 kmol/min

WithEthanol10.8 mol·dm-3
CoH2O=(1000-6.6·60-10.8·46)/18= 6.0 mol·dm-3
CoAcEt= 0

CAcH=CoAcH(1-x) CAcEt=CoAcH·x
CEtOH=CoEtOH-CoAcH·x CH2O=CoH2O+CoAcH.x

a) Balance: K=kd/kI=CAcEtCH2O/CAcHCethanolxe0.65

b) Unique RCTA: V = 2 m3 = V/Vo= 120 min

v=kdCAcHCEthanol-kICAcEtCH2O
= CoAcH· x/v x = 0.303

c) RCTA cascade: VI= 1 m3 i60 min

1CoAcH·x 1/v1 x10.202

2CoAcH(x2-x1)/v2 x20.337

d) Optimal waterfall: V1+V2= 2 m3

FoAcHCoi k
V1= FoAcH·x1/v1
V2FoAcH(x2-x1) / v2

V1
(1m3)
Vo
V1x1 V2x2
V2x1x20.3371
 Calculate the conversion of a mixture of acetic acid (6.6 M) and ethanol (10.8 M) that is fed.
with a V flowo= 1 m3to the following esterification teams, which in all cases have the same
total volume (2 m3):
Maximum conversion (equilibrium).

AcH + EtOH = AcEt + H2O kd= 4.76·10-4dm3mol-1min-1

d 1 ki= 1.63·10-4dm3mol-1min-1 10

CAcH= CoAcH(1-x) CoAcH6.6 mol·dm-3 FoAcHVo·CoAcH = 8

CEthanol= CoEthanol-CoAcH·x CoEtOH10.8 mol·dm-3 0.11 kmol/min 7

CAcEtCoAcH·x CoAcEt= 0 6
CH2O= CoH2O+CoAcH·x CoH2O=(1000-6.6·60-10.8·46)/18= 6.0 mol·dm-3
5

a) Balance: K= kd/ki= CAcEtCH2O/CAcHCEtOH xe0.65 4

b) Unique RCTA: V = 2 m3 V/Vo = 120 min 2

v= kdCAcHCEthanol-kiCAcEtCH2O 1

CoAcH· x/v x = 0.303 0

0,0 0,1 0.2 0.3 0.4

c) Optimal cascade: V1+V2= 2 m3
V1= FoAcH·x1/v1 Conversion (x)
0.04

V2= FoAcH(x2-x12 FoAchCoi k

0.03

V1
(1m3) 0.02

Vo 0.01

V1x1 V2x2
V2x1 x20.3371 0.00

0,0 0.1 0.2 0.3 0.4 0.5 0.6

Conversion (x)

Analyze and optimize the system of two continuous tanks in series, isothermal and well stirred,
where the irreversible first-order reaction A takes place B, the density remains constant
from the dissolution and the level of the tanks, and with specified variables: flow and concentration of
the feed, tank temperatures, kinetics, and final conversion (x2=0.90).

VoCok1k2x2
Design relationships:
1. V1/Vo= Co x1/v1= x11(1-x1) V1
2. V2/Vo= Co x2/v2= (x2-x1) / k2(1-x2) x1
1 2 V2
Design criterion: (I1+I2)min(I=aVb)
I1+I2= a Vob{[x1/k1(1-x1)]b+[ (x2-x1) / k2(1-x2)]b}; (I1+I2)/ x1=0: (1-x1op)b+1(x2/x1up-1)b-1nicorecnitput2/k1 (1-x2)]bin the case b=1
the criterion is equivalent to minimizing the global volume V1+V2, and the optimal result is: x1up= 1-[k2/k1 (1-x2] ; if the tempe-
½
½
The readings of the tanks match; the optimum is reduced to: x1 = 1-(1-x20.68 (V)2/V1=1)
up

It is desired to find the best arrangement to carry out the hydrolysis reaction of the diazoacetate ester.
tico2CHCO2C2H5+H2The HIGH2CO2C2H5+N2in a continuous system of stirred tanks in
series of equal size. The system operates at room temperature with a supply of 10 m3/h
of an aqueous solution 4 M in ester and 0.001 M in protons (1.10 kg/dm)3The reaction is catalyzed
subjected to acids and the following kinetic data has been found at 25ºC:

CH/10-3mol dm-3: 0,46 0,87 1,57 3,230

k/10-2dm3mol-1-1: 1,68 3,20 5,78 12,18

The price of the reactors as a function of the volume of the tanks is given by I=a V0.69Find yourself the
optimal number and size of units to achieve a 90% conversion. Rta: 3 x 2.6 dm3
A battery with tanks of 26.5 m is available.3unit size
for the polymerization of styrene and butadiene, whose kinetics is second order
order and its constant at the working temperature 6·10-4dm3mol-1min-1.
The feed consists of 19.6 t/h of a stream with 0.795 and 3.55
mol/l of each of the olefins, whose density is 0.87 kg/l.
Calculate the number of reactors needed to convert 85% of
styrene.

v = k·CACB= k·CAoB-(CoA-CA)] = 6·10-4·CA(2,755+CA)

= V/Vo 70.6 min Vo = m/d = 0.375 m3/min

-1= v/(CoA-CA0.014 min-1

CfA= CoA(1-xf0.12 mol/l

Number of reactors: 14

Develop a program to calculate the number of tanks needed for the saponification reaction.
Establishment of ethyl acetate, with the following operational data:

AcEt + NaOH NaAc + EtOH k (20ºC) = 92.4 dm3mol-1min-1

CoA= 5 g/l CoB= 0.1 M Vo= 430 l/min V = 200 l x 0.95

(1) = V/Vo= CoAΔx / v = 1/k· (xI–xi-1)/{(1-xioB-CoAxi)}

(2) k ·C oAxi2- {1+k oA+CoB)})xi(CoB+xi-1= 0

xi= {1+k ·(CoA+CoB) {{1+k (C oA+CoB)}2-4· k ·C oA·(CoB+xi-1)}½ }/{2·k ·C oA}

INPUT k, CoA, CoB, Vo, V, x, n

CALCULATE (1)

FOR i=1 TO n

CALCULATE xI(2)

IF xI x THEN PRINT i, xiEND

xi-1= xI

NEXT i
Comparison of reactors

A diluted aqueous solution of acetic anhydride is planned to be hydrolyzed continuously at 25ºC.

the reaction is first order and the rate constant at that temperature is 0.158 min-1. The
The feed flow rate is 0.5 l/min, the concentration of anhydride is 0.15 molar and is available
several models of reactors whose behavior can be assumed to be ideal, the density of the
the dissolution remains constant, the operation is isothermal and the steady state.
Determine which of the following options (with the same overall volume) is more advisable.
taking into account only the performance of the process: a) 5 liters RCTA; b) 2 RCTA of
2.5 liters in cascade; c) a 5 liters pure RFP and another with a recirculation ratio R=1.
d) Calculate the length of an RFP with a diameter of 4 cm that should be mounted at the outlet of a
waterfall of three identical tanks of 2.5 l volume, to achieve a conversion of 90%.

Rta.: 61, 69, 79, 71% and 1.34 m

In an ideal continuous stirred tank reactor, the conversion of a reactant is 50%.

in homogeneous liquid phase. The kinetics is second order with respect to the concentration of the reactant.
and the extension of the reverse reaction can be considered negligible. Calculate the conversion that
it would be achieved if we made each of the following modifications to the system while
we always kept the flow, composition of the feed, and temperature constant
process, assuming that all systems are stationary and operate ideally: a) RCTA
six times greater; b) two identical RCTA in cascade to the original; c) one RFP of the same size or a
Discontinuous RTA with identical residence time.
Response: 75, 69 and 67%

The reaction of sulfuric acid with diethyl sulfate is a bidirectional process whose rate constant...
direct temperature at 22.9ºC:
H2SO4+2H5)2SO4 2 C2H5SO4H kd= 1.45·10-3dm3mol-1min-1

In a laboratory reactor, 58.3 g of acid and 92.0 g of diethyl sulfate are mixed to form a solution.
with a total volume of 109 ml; at equilibrium, the concentration of the product ethyl sulfate resulted
It is 5.8 mol·dm-3.

To carry out the process on an industrial scale, two systems are available:

a) A `continuous stirred-tank reactor` with a diameter of 2 m and a height of 1 m

up to the overflow.
b) A tubular reactor with an interior diameter of 10 cm and a total length of 100 m.

It can be assumed that both systems are ideal, operating isothermally at 23ºC and that the
the fluid density barely changes during the reaction.

The composition of the feed to be used is the same as that of the experimental reactor.
previous, and it is desired to achieve a conversion of 90% of the maximum corresponding to equilibrium.
Determine the volumetric flow rate with which each of the two systems should be supplied to
achieve the desired conversion.
Rta.: 5.05 5.13 l/min

The pyrolytic polymerization of acetylene in the gas phase fits a second-order kinetic equation.
order whose rate constant at 550ºC is: 4 C2H2(g) (C2H2)4g) k=0.153 dm3mol-1s-1. The
The feed consists of 80% by volume of acetylene and the rest inert, with a flow
of 1000 m3measured at 550ºC and 20atm. There are two continuous systems available to take to
the reaction ends: one formed by five identical tubular furnaces, each with 47 tubes
3.5 m in length and 5 cm in internal diameter; the other is a complete mix reactor, whose
global volume is equal to the previous one; both systems operate in an isothermal manner and it can
assuming a negligible drop in pressure, that the ideal gas law is fulfilled, that
The reactors are ideal and stationary. Calculate the conversion and production of the complex.
tetramer (kg/day) in both facilities.
Rta.: 19.2 17.8%
A diluted aqueous solution of acetic anhydride is planned to be hydrolyzed continuously at 25ºC. The
the reaction is first order and the rate constant at that temperature is 0.158 min-1The
The feed flow rate is 0.5 l/min, the anhydride concentration is 0.15 molar, and it is available
various models of reactors whose behavior can be assumed to be ideal, the density of the
the dissolution remains constant, the operation is isothermal and the steady state.
Determine which of the following options (with the same overall volume) is more advisable.
taking into account only the performance of the process: a) 5 liters RCTA; b) 2 RCTA of
2.5 liters in cascade; c) an RFP of 5 liters pure and another with a recirculation ratio R=1.
d) Calculate the length of an RFP with a diameter of 4 cm that should be mounted at the outlet of a
waterfall of three identical tanks of 2.5 l volume, to achieve a conversion of 90%.

a) Vo0.5l/min
v = k·CA0.158min-1·CoA(1-x)
CoA0.15 mol/l = V/Vo 10 minutes
x
= CoAx / v

V = 5 liters
x / (1-x) = k· x = 0.61

b)
Vo x1 x2
1= 2= Vi/Vo5min
CoA
x1/ (1-x1) = k· 1x10.44

V12.5 l V22.5 l (x2-1/(1-x2= k· 2 x20.69

1= CoA·x1/ v1 2= CoA(x2-x1) / v2

c)
Vo R V/Vo= 10min
V=5l x
CoA = CoA x/v = -1/k·ln(1-x) x = 0.79

(R+1)·CoA x/v = 2/k·ln[(1-½x)/(1-x)] x = 0.71

d) Vo
x2=0.69 x3
CoA
x4=0.90
D44 cm
V1 V2 V3= 2.5 l

(x3-x2/(1-x3) = k· 3 V4= Vo·1/k·ln[(1-x3/(1-x4)] = 1.68 dm3

x30.83 L4=V4/( ·¼·D4=1.342 m
In an ideal continuous stirred-tank reactor, the conversion of a reactant is 50%
in homogeneous liquid phase. The kinetics are second order with respect to the concentration of the reactant
and the extent of the reverse reaction can be considered negligible. Calculate the conversion that
it would be achieved if we made each of the following modifications to the system while
we always maintained constant the flow, composition of the food and the temperature of the
process, assuming that all systems are stationary and operate ideally: a) RCTA
six times greater; b) two identical RCTAs in cascade to the original; c) an RFP of equal size or a
Discontinuous RTA with identical residence time.

a) Vo
2
v = k·CA
CoA 1= V1/Vo= CoAx1/ v1
x1= 0.50
V1= Vo·x1/ k·CoA(1-x1)2
V1

V2= 6·V1
V2/V1= 6= [x2(1-x2)2] / [ x1/(1-x1)2]x2= 0.75

b) Vo x1 x3
3= Vi/Vo
CoA
(x3-x1)/(1-x3)2= k·CoA·V1/Vo= 2

V1 V1 x3= 0.69

1= CoA·x1/ v1 3= CoA(x31) / v3

c) VoCoA x4 4= V1/Vo= CoA x/v = - 1/CoAk·[(1-x4)-1-1]

V1
x4/(1-x4) = x1(1-x1)2= 2 x40.67
1=1
The reaction of sulfuric acid with diethyl sulfate is a bidirectional process whose rate constant...
direct temperature 22.9ºC:
H2SO4+ (C2H5)2SO4 2 C2H5SO4H kd= 1.45·10-3dm3mol-1min-1

In a laboratory reactor, 58.3 g of acid and 92.0 g of diethyl sulfate are mixed to form a solution.
with a total volume of 109 ml; at equilibrium the concentration of the product ethyl sulfate resulted
to be 5.8 mol·dm-3.

To carry out the process on an industrial scale, there are two systems available:

c) A continuous stirred tank reactor with a diameter of 2 m and a height of 1 m.

up to the overflow.
d) A tubular reactor with an inner diameter of 10 cm and a total length of 100 m.

It can be assumed that both systems are ideal, operating isothermally at 23ºC and that the
the fluid density barely varies during the reaction.

The composition of the feed that will be used is the same as that of the experimental reactor.
previous, and a conversion of 90% of the maximum corresponding to equilibrium is desired.
Determine the volumetric flow rate with which each of the two systems must be supplied to
achieve the desired conversion.

CTo(58.3 / 98) / 0.109 = 5.5 mol/l CPe5.8 mol/l

CBo=(92,0/154)/0.109 = 5.5 mol/l xand= CPe/2Co= 0.53 x = 0.90 · xand0.475

K = kd/ki= CPe2CAe·CBe) = CPe2/(Co-½CPe)2= 5.0

v = kdCACB- kICP= k2dCTo(1-x)]2- kd/K·[2·CTox]2

Voh, a Vo,b

d, L
D, h

a= Cox / v = 6 2 2 m i n b= Co x/v = 153 min

Va= (D/2)23.14 m3 Vb= (d/2)2L = 0.785 m3

Vor, a= Va/ a5.05 l/min Vo,b= Vb/ b5.13 l/min

The pyrolytic polymerization of acetylene in the gas phase fits a second-order kinetic equation.
Order whose rate constant at 550ºC is: 4 C2H2(g) (C2H2)40.153 dm3mol-1s-1. The
The feed consists of 80% by volume of acetylene and the rest inert, with a flow
of 1000 m3Measured at 550ºC and 20atm. There are two continuous systems available to carry to
The reaction is completed: one formed by five identical tubular furnaces, each with 47 tubes.
3.5 m in length and 5 cm in internal diameter; the other is a complete mix reactor, whose
The global volume is equal to the previous one; both systems operate isothermally and can
assuming a negligible pressure drop, that the ideal gas law is fulfilled, that
the reactors are ideal and stationary.

Calculate the conversion and production of the tetramer complex (kg/day) in both facilities.

Vo= 1000 m3/h 5 47 tubes

550°C 3.5 m
5 cm
XoA= 0.80

v = k·CA 2 CA= CoA(1-x)/(1+ ·x)

V = 5.47 (5·10-2/2)2-3.5 = 1.61 m3
CoA= XoA·p/RT = 0.237 mol/dm3

= (0.20 + 0.20 - 1) / 1 = -0.60

1= CoA x/v x/v = V/VoCoA24.46 dm3mol-1s (A=9.78 cm2) x10.19

2= CoAx / v x·1/v = V/VoCoA24.46 dm3mol-1s (A=9.78 cm2) x2= 0.18

= 1= 2= V/Vo5.80 s

Analytically:

1= 1/kCoA (1-0.6·x)/(1-x)2 x = 1/kCoA[0,16/(1-xone-0.48·ln(1-x)1-0.36·(1-x)1) + 0.20]

by substitution: x=1-t x1= 0.192

2= CoAx / v = 1 / k C oA·x2(1-0.6·x2/(1-x2)]2 x20.178

A tubular reactor with 'recirculation' is fed with 0.5 m3at least a 2 molar solution of
a reagent that shows the following kinetic behavior, studied under the same conditions
operational processes that the productive system where the conversion into liquid phase is desired to be planned:

C (mol/l) 2.0 1.3 1.0 0.8 0.7 0.6 0,5 0,4 0,3 0,2 0,1
v 0,042 0,045 0,05 0,06 0,10 0,25 0,5 0,6 0,5 0,3 0,1
(mol/min·l)

The reactive system seems to show an initial long induction period, with a progressive increase.
from the speed and a slow decrease in concentration at the end of the process.

Graphically estimate the optimal recirculation ratio to be used and the size of the reactor for
achieve a 95% conversion. Compare it with the volume of a continuous stirred tank reactor and
of an ideal tubular reactor without recirculation.
Rta.: 3.0 9.5 and 14.25 m3

The biological oxidation of an urban waste leachate shows a kinetic behavior.

according to Haldane's inhibitory model with the following parameters:

60
v = KC/(Ks+C+C2/Ki)

Km = 70mg/l·h
50
Ks = 20mg/l
KI = 1000mg/l
40

30

20

10

0 500 1000 1500 2000

Concentration of substrate, C (mg/l)

The initial concentration of the contaminant substrate is 1000 mg/l and a rate is desired.
98% removal in an aerobic digester; calculate the size and the recirculation ratio
optimal in a plug flow reactor for a flow rate of contaminated water to be treated of 1 m3/h.

Rta.: 19.1 m3y R=2.5

A tubular reactor with 'recirculation' is fed with 0.5 m3at least one 2 molar solution of
a reactant that shows the following kinetic behavior, studied under the same conditions
operational procedures of the production system where the conversion into liquid phase is to be planned:

C (mol/l) 2.0 1.3 1.0 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1
v 0,042 0,045 0,05 0,06 0,10 0,25 0,5 0,6 0,5 0,3 0,1
(mol/min·l)

The reactive system seems to exhibit a long initial induction period, with a gradual increase.
from the speed and a slow drop in concentration at the end of the process.

Graphically estimate the optimal recirculation ratio to be used and the size of the reactor for
achieve a conversion of 95%. Compare it with the volume of a continuous tank reactor and
of an ideal tubular reactor without recirculation.

R·Vo

VoCoA
xo xf

25
Reactorrecirculation:R=x/(x-x) o f o

20

15

10

5
V/F
r oA= x
f /mv

xo xf
0
0,0 0,1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Conversion ( x )

Combined feeding: xo 0.72 Recirculation: R = 3.13

Reactor volume: Vr = FoA·xf /vm 1·0,95·3,2 =3,04m3

Volume of the mixing tank: Vt1·0.95·10 = 9.50m3

Volume of the piston flow: Vp 1·0,95·15 = 14.25m3

The biological oxidation of an urban waste leachate shows a kinetic behavior
according to Haldane's inhibitory model with the following parameters:

60
v = KmC/(Ks+C+C2/Ki)

Km = 70mg/l·h
50
Ks = 20mg/l
KI = 1000 mg/l
40

30

20

10

0 500 1000 1500 2000

Substrate concentration, C (mg/l)

The initial concentration of the contaminant substrate is 1000 mg/l and it is desired to achieve a rate
of 98% elimination in an aerobic digester; calculate the size and the recirculation ratio
optimal in a plug flow reactor for a flow of contaminated water to be treated of 1 m3/h.

2
1/v = [Ks+ Co (1-x) + Co(1-x)2/Kim·C o(1-x)

0.05

0.04

0.03

0.02
(v)m

0.01

xo xf

0.00
0,0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Substrate deacetylation, x

R = xoInvalid inputf-xo= 0.70 / (0.98-0.70) = 2.50

 Vr=FoA·xf/vm= 1 (m3/h)·1000 (g/m3)·0.98·0.0195 (m3h·g) = 19.1 m3

Non-isothermal reactions

R that adjusts to a bidirectional first-order kinetics

The process A is desired to be carried out.
The feed consists of 250 l/min of an aqueous solution of 4 mol.A/l, y
an 80% conversion is desired. The thermodynamic data of the process and the measurements
Kinetics obtained from two experiments in a batch reactor are:

temperature time conversion

Grº= -3375 cal/mol 25°C 10 min 60.0%
Hrº= -18000 cal/mol 65°C 1 min 58.1%

It can be assumed that the solution is ideal and that the heat capacities and density of the
Fluid currents are constant and equal to that of water.

Build the equilibrium conversion vs temperature graph (0-100ºC), and on it the

isokinetic curves v(x,T) for CA= 1 and Co R= 0, with the reaction rate as a parameter.
Deduce the necessary time with a reactor that operates with optimal temperature progression and
represent the temperature and conversion profile along the differential reactor (temperature
maximum allowable 95ºC). Calculate the optimal size of a continuous stirred-tank reactor and the
thermal exchange needs in the reactor and the effluent, if the feed enters at 25ºC and
the product must be collected at the same temperature in the collectors. Finally, estimate the
necessary size of an adiabatic tubular reactor and compare it with that of a stirred tank, with
a recirculation reactor, a combination of RCTA+RFP in series, and with the minimum volume
corresponding to the optimal operating line (maximum speeds).

The following expressions allow the calculation of the equilibrium constant at any temperature, from
Hrº and the variation of Cpiwith the temperature:

Ln K = - Gr/RT Gr= Hr-T Sr ( ln K/ T)P= Hr/RT2-1/RT·( Hr/ T)P+ 1/R·( Sir T)P

Hr = Hrº + iCpi T

As the specific heats are equal ( iCpi=0), the reaction enthalpy does not vary with temperature:

Ln K/Kº = 1/R. Hr/T2 T =- Hrº/R·(1/T-1/Tº) Ln Kº = - Grº/RTº = 5.69

Ln K = 5.69 + 18000/1.99·(1/T - 1/298) = 9045/T - 24.7 K = CeR/CeA= xand(1-xe)

xe = K/(1+K)

v = - CA/ t = k1CA- k2CR x/ t = k1(1-x)-k1/K·x

t= x / k 1(1-x/xe) k1= -xe/t·ln(1-x/xe) k2= k1/K

k = A·eEa/RT Ea= R·ln k/k'/(1/T' - 1/T)

25ºC k1= 0.092 k2= 3.2·10-4

xe0.997 K = 285

65ºC k10.94 k20.12

xe0.89

E1= 11650 E2= 29650 cal/mol

A1= 3.1·107 A21.7·1018min-1

v = CoAk1(1-x) - k2x]

k1= 3.1 · 107·e-5850/T k2= 1.7·1018.e-14900/T

 v/ t = 0 ; Topt=1-E2)/R ln [E1A1/E2A2(1-x)/x

a)
Optimal temperature progression:

= CoA x/v= x / v max

b) Vo250 liters per minute

To 25ºC CoAvmax0.4 mol/l·min
CoA4 mol/l T = 62ºC = CoAx / v = 8 min
q x = 0.80
Tf25°C V = Vo =2000 l

V
Operation line: T = To+r- Hrx)/CpMr.

qr-5.15 kcal/molA-5150kcal/min
qr
q =(Vod·Cp)·(Tf -T) = -9250kcal/min

c) Adiabatic operation line:

pend = -Cpmrl/ Hr(1kcal/l·K/4mol)A18 kcal/molA= 1/72 K-1
The procedure consists of testing different lines of
operation with this slope (at various temperatures)
as input), so that it is minimized: x/v

Thus, the optimal operating line would be the one that starts from
a temperature of 16ºC and reaches a temperature of
output of 74ºC:

= CoA x/v = 6.9 min V = 1720 l

This volume is somewhat smaller than that of the reactor.

of complete mixture, but it is still 4 times higher than
the minimum of section a) 1.62 min (405 l).

The graph represents the v-x-T diagram for a first-order bidirectional reaction of
transformation of A into R. The feed is 250 l/min of a 1 molar solution of pure A in
water, and an 80% conversion is desired. The heat of the reaction is Hr-18 kcal/mol y
It can be assumed that the properties of the solution are the same as those of water.

Represent the progression of optimal temperature and calculate the necessary volume of a
complete mixing reactor operating at the maximum velocity point.

Draw the corresponding operating line if the feed enters the reactor at 25ºC.
and calculate the necessary heat exchange in the jacket to maintain the optimal temperature.

2000 dm3y 5650 kcal/min

The graph represents the v-x-T diagram for a first-order bidirectional reaction.
transformation of A into R. The feed is a 1 M solution of pure A in water, at 15ºC, and
the process takes place under adiabatic conditions (the heat of reaction is Hr-72 kcal/mol and can
assuming that the properties of the solution are the same as those of water).

Estimate the conversion above which the piston flow reactor becomes better
regarding the complete mixture, and estimate the optimal volume approximately of two
series reactors, tank and tubular type, to achieve a total conversion of 80%.

Response: 2.5 + 1.9 min

Laboratory tests on the hydrolysis of acetic anhydride, with an initial concentration of
Co= 0.2150 mol/l, have yielded the following results:

t/min 1 2 3 4 5 6 7 8 10 15 20
C,10ºC 0,2037 0,1930 0,1830 0,1719 0,1633 0,1527 0,1473 0,1385 0,1228 0,0942 0,0716
20°C 0,1920 0,1712 0,1536 0,1374 0,1222 0,1085 0,1385 0,0878 0,0695 0,0401 0,0224
C,60ºC 0,0619 0,0178 0,0051 0,0015 0,0001 0 0 0 0 0 0

A batch reactor is charged with 250 kg of the anhydride solution in water with the same
concentration and a density of 1.050 kg/l at 15ºC. The heat capacity can be considered
constant (0.9 kcal/kgºC) and the reaction heat is -50 kcal/mol.

Calculate the precise time to reach an 80% conversion under the following conditions:
a) Operación isotérmica a 15ºC; b) Operación adiabática con una temperatura inicial de 15ºC; c)
Non-isothermal operation with water heating at 50ºC, in a 0.5 m coil2of
surface (heat transmission coefficient, U = 250 kcal/m2°C), with an initial temperature of
15ºC
Rta.: 20.6 13.5 minyadvanced program

The second stage of ammonia oxidation to obtain nitric acid consists of cooling the
nitrous gases coming from the converter, in such a way that the transformation is produced to
nitric oxide in the same tubes of the exchangers, which are taken to absorption towers.

2 NO (g) + O2(g) 2 NO2(g) v = k·CNOC2O2

This reaction is one of the few known trimolecular elementary processes, with the
additional peculiarity of not obeying the Arrhenius law, since the function is controlled by the
Pre-exponential factor: k(T) = 1590 + 4.33·1010/T3dm6mol-2-1thus cooling favors the
see the formation of NO2and its absorption with water). The process operates at about 900 K (they cannot
exceeding 700ºC) and 4 atm (to increase absorption and the rate of oxidation, thus
how to reduce the installation size); the feed to the changers is a mixture
soft drink of NO (9%), O2(10%) and N2(81%), and the conditions at the exit of the exchangers are
at approximately 300 K and 4 atm, it can be assumed that heat is removed in a way that
proportional to the progress of the reaction in such a way that the temperature pattern is not
adiabatic results in a straight-line operating line: T = T o+ (Tf-ToEstimate the time of
residence in the changers if the achieved conversion turns out to be 98%.

Response: 7.6 s

The saponification of ethyl acetate in alkaline aqueous medium is essentially a reaction

unidirectional and second order, with kinetic constants of 4.17 and 5.15 dm3mol-1min-1
(at 25 and 30ºC respectively).
AcEt + NaOH NaAc + EtOH

The initial concentration of the reactants is 25 g/l of acetate and 0.5 N of soda, at a temperature
at 25ºC, and a conversion of 95% is desired.

Determine the required operating time in a batch reactor and the volume of a reactor.
continuous stirred tank reactor (of perfect mixing) for a flow rate of 1 m3/h, supposed regimes
isothermal or adiabatic.
Rta.: 2.5 y 2.2 min; 320 y 260 l

The decomposition of phosphine occurs according to the endothermic, unidirectional reaction.

first order:
4 PH3 P4+ 6 H2 lg k(s-1) 12.3 + 2·log T - 18960/T(K)

It is about producing phosphorus in a tubular reactor of 2832 dm.3, which operates at atmospheric pressure
with a feeding flow of phosphine of 45.36 kg/h, and whose maximum allowable temperature
due to the construction material used is 680ºC. Please note that under the conditions
during operation, all components remain in gaseous state, that the heat of reaction
normal is 5.66 kcal/molPH3and that can be taken as average values of the capacities
caloric:CPH3= 12.6; CP414.9 and CH2= 7.2 cal/mol°C.

Calculate the conversion achieved: a) in isothermal conditions at 680ºC;

with an inlet temperature of 680ºC.
Response: 69% and 13%

The following kinetic data is available for the trimolecular elementary reaction for the
formation of nitrosyl chloride:
2 NO + Cl2 2 NOCl T/K k/dm6mol-2s-1
273 5.5
355 27.2
451 182
566 1130
To carry out the process, there is a tubular reactor of 80 m in length and 20 cm of
diameter, and of two supply currents of NO and Cl2pure at atmospheric pressure and with a
flow of 200 and 100 mol/min respectively. Estimate the inlet temperature under conditions
adiabatic and isobaric, to achieve a conversion of 95%.

If the reactants are introduced at normal pressure and temperature, determine what will be in this.
case of conversion in adiabatic and isobaric regime at 1 atm.

Calculate the conversion and space time of the reactor if the reactants are introduced in proportion.
stoichiometric at 300K, and the products exit at 900K (q = 0; 1 atm).

Response: solutions by iteration, trial and direct calculation

In a continuous stirred tank reactor, a solution of an ester of an acid is hydrolyzed.

monobasic organic with alkaline solution. The volume of the tank is 6 m3and inside it
There is a submerged cooling coil that maintains the reaction temperature at 25ºC.
Use the following data to estimate the heat transfer area under conditions
such that the water enters at 15ºC and exits at 20ºC, disregarding the heat losses from the reactor.
1.0 M
5.0 M, 20ºC and 10 l/s, respectively; velocity constant at 25ºC: k = 0.11 dm3mole-1s-1;
-3500 cal/mol2hºC.

Rta.: 7.8 m2

The graph represents the v-x-T diagram for a first-order bidirectional reaction of
transformation of A into R. The feed is 250 l/min of a 1 molar solution of pure A in
water, and it is desired to achieve an 80% conversion. The heat of the reaction is Hr-18 kcal/mol y
It can be assumed that the properties of the solution are the same as those of water.
 Represent the optimal temperature progression and calculate the necessary volume of a
full mixing reactor that operates at the maximum speed point.

x = 0.80 vmax0.1 mol/dm3min V= Vo·Cox / v = 2000 dm3

Draw the corresponding operating line if the feed enters the reactor at 25ºC,
and calculate the necessary heat exchange in the jacket to maintain the optimal temperature.

q = Cp· T + Hr·x = (1 kcal·l-1K-11 molA·l-162-25-18 kcal/molA-0.8 = 22.6 kcal/molA= 5650 kcal/min

The graph represents the v-x-T diagram for a first-order bidirectional reaction.
transformation of A into R. The feed is a 1 M solution of pure A in water, at 15ºC, and
the process takes place under adiabatic conditions (the heat of reaction is Hr-72 kcal/mol and can
assuming that the properties of the solution are the same as those of water).
Estimate the conversion above which the piston flow reactor begins to be better.
regarding the complete mixture, and approximately calculate the optimal volume ( of two
series reactors, tank and tubular type, to achieve a total conversion of 80%.

T = To + Hr·x /Cmrl pend = Cpmrl/ Hr(1 kcal/l·K/1molA/l)/72 kcal/molA1/72 K-1

v = CoA[k1(1-x) - k2x] (graphically)

50 CoA/vvsx

40

30

20

10

0
0,0 0.2 0.4 0.6 0.8
Conversion,x

1=CoA-x/v 2.5 min (RCTA) 2=CoA· dx/v 1.9 min (RT)

V2
V1

Laboratory tests on the hydrolysis of acetic anhydride, with an initial concentration of

Co= 0.2150 mol/l, have provided the following results:

t/min 1 2 3 4 5 6 7 8 10 15 20
 C,10ºC 0,2037 0,1930 0,1830 0,1719 0,1633 0,1527 0,1473 0,1385 0,1228 0,0942 0,0716
C,20ºC 0,1920 0,1712 0,1536 0,1374 0,1222 0,1085 0,1385 0,0878 0,0695 0,0401 0,0224
C,60ºC 0,0619 0,0178 0,0051 0,0015 0,0001 0 0 0 0 0 0

A discontinuous reactor is loaded with 250 kg of the solution of anhydride in water with the same
concentration and a density of 1.050 kg/l at 15ºC. The heat capacity can be considered
constant (0.9 kcal/kgºC) and the heat of reaction is -50 kcal/mol.

Calculate the precise time to reach an 80% conversion under the following conditions:
Isothermal operation at 15ºC;
Non-isothermal operation with water heating at 50ºC, in a 0.5 m coil.2of
surface (heat transmission coefficient, U = 250 kcal/m2hºC), with an initial temperature of
15ºC

Determination of the kinetic model:

- C/ t = k·Cn

As can be seen in the figure, the correlation ln CoCvs.t is

excellent for all studied temperatures, so it can
deduce a first order for the reaction and some kinetic constants.
of the slopes of the corresponding lines (k, min-1).

The Arrhenius correlation is also good (ln k = ln A - Ea/R·1/T)

Where the frequency factor (ordinate) and coefficient are deduced from
of temperature (slope):
v = k·C k=5.54·107.e-5870/T

a) t = CoA x/v = -1/k·ln(1-x) = 20.6 min

0.078 min-1
mo To

q
b) t = x/kT(1-x) = 13.5 min
ts= 323K
T = To - Hr/Cx = 288 + 11.63 · x
Cmrl= Cp·do/CoA4.28 kcal/molAK

c) x/ t = 5.54 × 107·e -5879/T(1-x)

T= ( Hr x)/Cmrl q(kcal/mol)A)=U·S·(Ts t/noA

noA= moA/do·CoA51.2 mol

to=0, xo=0, To=288( t ) t= to+ t ; x = xo+ ( x/ t)· t

T = To+( T/ t)· t
(Euler) tf(xf= 0.98)

In a batch reactor, 250 kg of aqueous acetic anhydride solution is charged at 15ºC.

with a concentration of 0.215 mol/dm3and density 1.05 g/cm3Its specific heat and enthalpy
reaction can be considered constant and equal to 0.9 cal/gmix°Canhydride .
The hydrolysis reaction is first order and its kinetic parameters are: A= 5.54·107min-1y
Ea/ = 5870 K. Estimate the time required to achieve an 80% conversion, if the reactor
operates in an adiabatic manner.

t = Co x/v = x/A·eEa/ T(1-x) = 13.5 min (graphically)

T = To + (- Hr)·x /Cpmrl= 288 + 11.63·x Cpmrl= Cp/(Cod) = 4.28 kcal/molaK

The second stage of the oxidation of ammonia to obtain nitric acid consists of cooling the
nitrous gases coming from the converter, so that the transformation occurs to
nitric oxide in the same tubes of the exchangers, which are taken to absorption towers.
 2 NO (g) + O2(g) 2 NO2(g) v = k·CNOC2O2

This reaction is one of the few known trimolecular elementary processes, with the
additional peculiarity of not complying with the Arrhenius law, as the function is controlled by the
pre-exponential factor: k(T) = 1590 + 4.33·1010/T3dm6mol-2s-1thus the cooling favors the
look at the formation of NO2and its absorption with water). The process operates at about 900 K (they cannot
exceeding 700ºC) and 4 atm (to increase absorption and oxidation rate, thus
how to reduce the size of the installation); the supply to the changers is a mixture
soda of NO (9%), O2(10%) and N2(81%), and the conditions at the exit of the exchangers are
at approximately 300 K and 4 atm, assuming that heat is removed in a way that
proportional to the progress of the reaction in such a way that the temperature profile in the steady state
Adiabatic results in a straight operation line: T = To+ (Tf-ToEstimate the time of
residence in the changers if the conversion achieved turns out to be 98%.
x=0.98
The saponification of ethyl acetate in an alkaline aqueous medium is essentially a reaction
unidirectional and second order, with kinetic constants of 4.17 and 5.15 dm3mol-1min-1
(at 25 and 30ºC respectively).
AcEt + NaOH NaAc + EtOH

The initial concentration of the reagents is 25 g/l of acetate and 0.5 N of soda, at a temperature
at 25ºC, and a conversion of 95% is desired.

Determine the required operating time in a batch reactor and the volume of a reactor
continuous stirred tank reactor (of perfect mixing) for a flow rate of 1 m3/h, supposed regimes
isothermal or adiabatic.

Design equations: t= CoA· dx/v (batch)

= V/Vo= CoA· x/v (CSTR)

x0=0 xf=0.95 Vo=16.7dm3/min

Reaction kinetics: v = k · CACB

k = A · e-Ea/RTEaR·ln(k´/k)/(1/T-1/T´)= 31700 J/mol

A = k/e-Ea/RT1.5 x 106dm3mol-1min-1
CA= CoA(1-x) WhatA25 g/l = 0.284 mol/dm3
CB= CoB-CoAx CoB= 0.5 N = 0.5 mol/dm3

Temperature guidelines: T = To = 25ºC (isothermal)

T= To - Hr·x/CmA (adiabatic)

Species Hfº Hcº Hsº Hfº(kcal/mol)

AcNa -169.8 (c) -4.3 -174.1 (ac)
Sodium hydroxide
-102.0 (c) -10,2 -112.2 (ac)
AcEt -538,8 -110.8 (l)
EtOH -326,7 -66.4 (l)
CO2 -94.1 (g) Hr -17.5 kcal/molA
H2O -68.3 (l) CmA 1/CoA= 3.5 kcal/molA°C

Tf29.75°C
 tisotm.2.5 min
tadiab.2.2 min

Visotm.= 320 l. 19 min

Vadiab.= 260 l. (15.6 min)

The saponification of ethyl acetate in alkaline aqueous medium is essentially a reaction

unidirectional and second order, with kinetic constants of 4.17 and 5.15 dm3mol-1min-1
(at 25 and 30ºC respectively).
AcEt + NaOH NaAc + EtOH -17.5 kcal/molA

The initial concentration of the reactants is 25 g/l of acetate and 0.5 N of soda, with a temperature
at 25ºC, and the heat capacity of the mixture can be considered similar to that of water.

Determine the volume of a continuous stirred-tank reactor (perfect mixing) for a flow rate.
of 1 m3in the case of supposed isothermal or adiabatic regimes, if a conversion of 95% is desired.

Design equation: = V/Vo= CoA· x/v (RCTA)

x0=0 xf=0.95 16.7dm3/min

Reaction kinetics: v = k · CACB

k = A·eEa/RTEa= R·ln(k´/k)/(1/T-1/T´)= 31700 J/mol

A = k/e-Ea/RT= 1.5·106dm3mol-1min-1
CACoA(1-x) CoA= 25 g/l = 0.284 mol/dm3
CB= CoB-CoAx CoB= 0.5 N = 0.5 mol/dm3

Temperature guidelines: T = To = 25ºC isothermal

To - Hr·x/CmA (adiabatic)

CmA 1/CoA3.5 kcal/molA°C Tf29.75ºC

Visotm.= 320 l. ( 19 min

Vadiab.= 260 l. (15.6 min)
The decomposition of phosphine occurs according to the endothermic, unidirectional reaction.
of first order:
4 PH3 P4+ 6 H2 lg k(s-1) 12.3 + 2·lg T - 18960/T(K)

It is about producing phosphorus in a tubular reactor of 2832 dm3that operates at atmospheric pressure
with a phosphine feed rate of 45.36 kg/h, and whose maximum permissible temperature
due to the construction material used is 680ºC. Be aware that under the conditions
in operation all components remain in gaseous state, that the heat of reaction
Normal is 5.66 kcal/molPH3and can be taken as average values of the capacities
caloric:CPH3= 12.6; CP4= 14.9 and CH2= 7.2 cal/molºC.

Calculate the conversion achieved: a) in isothermal conditions at 680ºC;

with an inlet temperature of 680ºC.

45.36 kgPH3/h
V = 2832 dm3
To= 953K x
p = 1 atm

V = Fo dx/v V/Fo7642 dm3s / mol

v = k·CPH3k(T)·Co (1-x)/(1+ x)T/To Co= p/ To0.0128 mol/dm3 = 3/4

x = Cp(T-To) / (- Hr) Cp12.6 kcal/kmol·K Hr= Hrº + ¼ (14.9 + 6·7.2 - 4·12.6)(T - 298)

a)
953K v = 2·10-4(1-x)/(1+0.75x) mol·dm 3 x = 0,69

b)
T = f(x) v = 12.2 · k(T) / T · (1 - x) / (1 + 0.75x) x = 0.13

T/K x=f(T) k(T) v(x,T), mol/dm3s

953 0 0.0156 2.00·10-4
900 0.0989,37·10-4 1.07·10-5
875 0.1452,22·10-4 2.38 times 10-6
850 0.1934,82·10-5 4.88 x 10-7
825 0.2429,57·10-6 9.09·10-8
800 0.2911,72·10-6 1.53 × 10-8
The following kinetic data is available for the elementary trimolecular reaction for the
formation of nitrosyl chloride:
2 NO + Cl2 2 NOCl T/K k/dm6mol-2s-1
273 5.5
355 27.2
451 182
567 1130

To carry out the process, there is a tubular reactor 80 m long and 20 cm

diameter, and of two feeding currents of NO and Cl2cigars at atmospheric pressure and with a
flow of 200 and 100 mol/min respectively. Estimate the inlet temperature under conditions
adiabatic and isobaric, to achieve a 95% conversion.

If the reactants are introduced at normal pressure and temperature, determine what will be in this.
in the case of conversion in an adiabatic and isobaric process at 1 atm.

Calculate the conversion and space time of the reactor if the reactants are fed in proportion.
stoichiometric at 300K, and the products exit at 900K (q= 0; 1 atm).

Foh, NO= 200 mol/min po= 1 atm 2 NO (g) + Cl2(g) 2 NOCl (g)
Fo,Cl2= 100 mol/min
80m Xf= 0.95 v = k(T)·CNO2·CCl2 -1/3

k = 1.09 x 106e-2787/T(r=0.98)
Vr= r22,512m3

Vr= Fo,Cl2 x/v

v = k·nNOCl22 /V3= k(T)·4·[Co,Cl2(1-x)/(1+ x)T/To]3= 4·k(T)[Xo,Cl2po/ (1-x)/T(1-1/3·x)3

Cafter T / (- Hr) = [a(T-To)+b/2·(T2-To) +2 c/3·(T3-To)+d/4·(T

3 4-To] / (a'T
4 + b'T2+c´T3+dT4+e´)

Cafter= 2·Cp,NO+ Cp,Cl2(cal/molCl2K) Hr= i( Hfi+ Cpi T)cal/molCl2

Cpi= aI + bTi + ciT2 + dT

i
3

i Xoh, I Hfi, cal/mol ai, cal/mol-K bi/10-3ciNo text provided for translation.-6di/10-10
NO 2/3 21600 6.46 2.4 -0.77
 Cl2 1/3 0 6.82 5.7 -5.1 15.5
NOCl - 12600

calculation algorithm (a):

To x (T) v (x,T) Vr(xf) (per iteration)

Unidirectional reaction
xf v(x,T) Fo, Cl2/v

x(T)

Vr
0
To Tf 0 xf

(b): x (Ti) v (x,T) Vr xf (by trial)

(c): x (Tf) xf 0.82 v (x,T) 6.5s (for direct calculation)

In a continuous stirred tank reactor, a solution of an acid ester is hydrolyzed.

monobasic organic with alkaline solution. The volume of the tank is 6 m3and inside it
There is a submerged cooling coil that maintains the reaction temperature at 25ºC.
Use the following data to estimate the heat transfer surface under conditions
such that the water enters at 15ºC and leaves at 20ºC, ignoring the heat losses of the reactor.
1.0 M
5.0 M, 20ºC and 10 l/s, respectively; velocity constant at 25ºC: k = 0.11 dm3mol-1s-1;
-3500 cal/mol2h°C.

AB + OH- A- + BOH
25 l/s, 1M, 25ºC
OH-10 l/s, 5M, 20C k = 0.11 dm3/mol·s

-3500 cal/mol
V= 6000 dm3

25°C
Vo= VAB+ VOH= 35 dm3/s

15°C 20°C Co= VAB·CAB/Vo 0.715 mol/dm3

Co´ = VOHCOH/Vo1,429 mol/dm3
U = 1950 kcal/m2h°C
= V/Vo= 171.4 s
= Cox / v

2
v = k·Co (1-x)·(Co-Cox) = k·Co(1-x) (2-x) x2-3.0743·x + 2 = 0 x = 0,935

q = nAB Hr·x + moCpo (T-To= (25 mol/s)(-3.5 kcal/mol)·0.935 + (10 kg/s)(1 kcal/kgºC)(25-20)ºC= -41.8 kcal/s

A = q / U. Tm = (114480 kcal/h) / (1950 kcal/m2hºC)[25-½(15+20)] =7.83 m2