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C 01
C 01
C 01
i
v
i
A
i
= 0 (1-1)
In this equation, A
i
represents a chemical species. For instance, in Reaction (1-A), we might
choose
A
1
= Cl
2
; A
2
= C
3
H
6
; A
3
= NaOH; A
4
= C
3
H
6
O; A
5
= NaCl; A
6
= H
2
O
The stoichiometric coefcient for chemical species i is denoted v
i
: Equation (1-1)
involves a convention for writing the stoichiometric coefcients. The coefcients of the
products of a reaction are positive, and the coefcients of the reactants are negative. Thus,
for Reaction (1-A):
v
1
= v
Cl2
= 1; v
2
= v
C3H
6
= 1; v
3
= v
NaOH
= 2;
v
4
= v
C3H
6
O
= 1; v
5
= v
NaCl
= 2; v
6
= v
H2O
= 1
The sum of the stoichiometric coefcients, Dv = v
i
; shows whether the total number
of moles increases, decreases, or remains constant as the reaction proceeds. If Dv >0; the
number of moles increases; if Dv < 0; the number of moles decreases; if Dv = 0; there is
no change in the total number of moles. For Reaction (1-A), Dv = 0: As we shall see in
Chapter 4, a change in the number of moles on reaction can have an important inuence on
the design and analysis of reactions that take place in the gas phase.
You may have used this stoichiometric notation in earlier courses, such as thermody-
namics. For example, the standard Gibbs free energy change of a reaction (DG
0
R
) and the
standard enthalpy change of a reaction (DH
0
R
) can be written as
DG
0
R
=
i
v
i
DG
0
f;i
(1-2)
and
DH
0
R
=
i
v
i
DH
0
f;i
(1-3)
Intheseequations, DG
0
f;i
andDH
0
f;i
arethestandardGibbsfreeenergyofformationandstandard
enthalpy of formation of species i, respectively. For many reactions, values of DG
0
R
and DH
0
R
can be calculated from tabulated values of DG
0
f;i
and DH
0
f;i
for the reactants and products.
1.2 Stoichiometric Notation 3
1.3 EXTENT OF REACTION AND THE LAW OF DEFINITE PROPORTIONS
Consider a closed system in which one chemical reaction takes place. Let
N
i
= number of moles of species i present at time t
N
i0
= number of moles of species i present at t = 0
DN
i
= N
i
N
i0
Alternately, consider an open system at steady state, in which one reaction takes place. For
this case, let
N
i
= number of moles of species i that leave the system in the time interval Dt
N
i0
= number of moles of species i that enter the system in the same time interval Dt
DN
i
= N
i
N
i0
In both of these cases, the reaction is the only thing that causes N
i
to differ fromN
i0
; i.e., the
reaction is the only thing that causes DN
i
to be nonzero.
The extent of reaction, j is dened as
Extent of reaction for
a single reaction in
a closed system
j = DN
i
=v
i
(1-4)
The extent of reaction is a measure of howfar the reaction has progressed. Since reactants
disappear as the reaction proceeds, DN
i
for every reactant is less than 0. Conversely,
products are formed, so that DN
i
for every product is greater than 0. Therefore, the sign
convention for stoichiometric coefcients ensures that the value of j is always positive, as
long as we have identied the reactants and products correctly.
When the extent of reaction is dened by Eqn. (1-4), j has units of moles.
The maximum value of j for any reaction results when the limiting reactant has been
consumed completely, i.e.,
j
max
= N
10
=n
1
where the subscript l denotes the limiting reactant. In fact, the extent of reaction provides
a way to make sure that the limiting reactant has been identied correctly. For each reactant,
calculate j
i0
= N
i0
=v
i
: This is the value of j
max
that would result if reactant i was
consumed completely. The species with the lowest value of j
i0
is the limiting reactant. This
is the reactant that will disappear rst if the reaction goes to completion.
If the reaction is reversible, equilibrium will be reached before the limiting reactant is
consumed completely. In this case, the highest achievable value of j will be less than j
max
:
The balanced stoichiometric equation for a reaction tells us that the various chemical
species are formed or consumed in xed proportions. This idea is expressed mathematically
by the Law of Denite Proportions. For a single reaction,
Law of Definite Proportions
for a single reaction in a
closed system
DN
1
=v
1
= DN
2
=v
2
= DN
3
=v
3
=
= DN
i
=v
i
= = j
(1-5)
According to Eqn. (1-5), the value of j does not depend on the species used for the
calculation. A reaction that obeys the Law of Denite Proportions is referred to as a
4 Chapter 1 Reactions and Reaction Rates
stoichiometrically simple reaction. If the syntheses of propylene oxide (Reaction (1-A))
were stoichiometrically simple, we could write
DN
H
2
O
=1 = DN
NaCl
=2 = DN
C
3
H
6
O
=1 = DN
C
3
H
6
=1 = DN
NaOH
=2 = DN
Cl
2
=1
The extent of reaction concept can be applied to open systems at steady state in a second
way, by considering the rates at which various species are fed to and withdrawn from the
system, instead of considering the number of moles fed and withdrawn in a specied interval
of time. Let
F
i
= molar rate at which species i flows out of the system (moles i=time)
F
i0
= molar rate at which species i flows into the system (moles i=time)
DF
i0
= F
i
F
i0
The extent of reaction now can be dened as
Extent of reaction for a single
reaction in a flow system at steady state
j = DF
i
=v
i
(1-6)
When the extent of reaction is based on molar ow rates F
i
, rather than on moles N
i
; j has
units of moles/time rather than moles. For this case, the Law of Denite Proportions is
written as
Law of Definite Proportions
for a single reaction in a
flow system at steady state
DF
1
=v
1
= DF
2
=v
2
= DF
3
=v
3
=
= DF
i
=v
i
= = j
(1-7)
At rst glance, the Law of Denite Proportions and the denition of a stoichiometri-
cally simple reaction might seem trivial. However, Eqns. (1-5) and (1-7) can provide a
reality check when dealing with an actual system. Consider Example 1-1.
EXAMPLE 1-1
Hydrogenolysis of
Thiophene (C
4
H
4
S)
The thiophene hydrogenolysis reaction
C
4
H
4
S 4H
2
!C
4
H
10
H
2
S (1-B)
takes place at about 1 atmtotal pressure and about 250
i
n
ki
A
i
= 0; k = 1; 2; . . . ; R (1-8)
Here, R is the total number of independent reactions that take place and v
ki
is the
stoichiometric coefcient of species i in reaction k.
Test for stoichiometrically simple reaction
Species DN
i
v
i
j
C
4
H
4
S 70:0 1 70.0
H
2
145:9 410:9 = 265:0 4 66.25
C
4
H
10
75:1 20:1 = 55:0 1 55.0
H
2
S 95:7 25:7 = 70:0 1 70.0
6 Chapter 1 Reactions and Reaction Rates
Each of the R reactions may contribute to DN
i
; which is the change in the number of
moles of species i. If the extent of reaction k is denoted by j
k
; then the total change in the
number of moles of species i is
Total change in molesmultiple
reactions in a closed system
DN
i
= N
i
N
i0
=
R
k=1
n
ki
j
k
(1-9)
The term v
ki
j
k
is the change in the number of moles of i that is caused by reaction k.
The total change in moles of species i, DN
i
; is obtained by summing such terms over all of
reactions that take place.
When the extent of reaction is dened in terms of molar ow rates, the equivalent of
Eqn. (1-9) is
Total change in molar flow ratemultiple
reactions in a flow system at steady state
DF
i
= F
i
F
i0
=
R
k=1
n
ki
j
k
(1-10)
EXAMPLE 1-2
Thiophene
Hydrogenolysis
Multiple Reactions?
Suppose that the two reactions shown belowwere taking place in the thiophene hydrogenolysis pilot
plant of Example 1-1.
C
4
H
4
S 3H
2
!C
4
H
8
H
2
S (1-C)
C
4
H
8
H
2
!C
4
H
10
(1-D)
Are the pilot-plant data stoichiometrically consistent with these reactions?
APPROACH If Reactions (1-C) and (1-D) are sufcient to account for the behavior of the actual system, then all of
the equations for DN
i
; one equation for each species, must be satised by a single value of j
C
; the
extent of Reaction (1-C), plus a single value of j
D
; the extent of Reaction (1-D). There are ve
chemical species in Reactions (1-C) and (1-D). However, the table in Example 1-1 lacks data for
butene (C
4
H
8
), so only four equations for DN
i
can be formulated with values for DN
i
: Two of these
equations will be used to calculate values of j
C
and j
D
. The two remaining equations will be used to
check the values of j
C
and j
D
that we calculated.
SOLUTION Let v
Ci
be the stoichiometric coefcient of species i in Reaction (1-C) and let v
Di
be the
stoichiometric coefcient of species i in Reaction (1-D). For thiophene (T), from Eqn. (1-9),
DN
T
= v
CT
j
C
v
DT
j
D
= 70
Since v
CT
= 1 and v
DT
= 0; j
C
= 70:
For H
2
(H),
DN
H
= v
CH
j
C
v
DH
j
D
= 265
Since v
CH
= 3 and v
DH
= 1;
(3)(70) (1)j
D
= 265; j
D
= 55
These values of j
C
and j
D
now must satisfy the remaining two equations for DN: For H
2
S (S),
DN
S
= v
CS
j
C
v
DS
j
D
= 70
(1)(70) (0)(55) = 70 Check!
For butane (B),
DN
B
= v
CB
j
C
v
DB
j
D
= 55
1.3 Extent of Reaction and the Law of Denite Proportions 7
(0)(70) (1)(55) = 55 Check!
These calculations showthat the data, as they exist, are consistent with the hypothesis that Reactions
(1-C) and (1-D) are the only ones that take place.
This analysis does not prove that these two reactions are taking place. There are other
explanations that might account for the experimental data. First, the data may be inaccurate.
Perhaps only one reaction takes place, but the number of moles of both H
2
and C
4
H
10
was
measured incorrectly. Perhaps more than two reactions take place. Clearly, additional
data are required. The analysis of pilot-plant operations must be improved so that all the
three species balances (carbon, hydrogen, and sulfur) can be closed within reasonable
tolerances.
EXERCISE 1-1
What specic actions would you recommend to the team that is
operating the pilot plant?
EXAMPLE 1-3
Thiophene
Hydrogenolysis
Calculation of Butene
The extent of reaction concept also can be used to calculate the expected amounts of species that are
not directly measured. Consider the previous example. Suppose that Reactions (1-C) and (1-D) are,
in fact, the only independent reactions that occur in the pilot plant. What quantity of butene (C
4
H
8
)
should have been found in the efuent from the pilot plant during the third shift?
APPROACH Let the subscript E be used to denote butene. Equation (1-9) can be written for butene, as follows:
DN
E
= v
CE
j
C
v
DE
j
D
Since all of the quantities on the right-hand side of this equation are known, the value of DN
E
can be
calculated directly. The quantity of butene formed during the third shift is DN
E
: If there was no butene
in the feed to the reactor, DN
E
also is the total amount of butene that would be collected from the
efuent during the third shift.
SOLUTION From Example 1-2, j
C
= 70 and j
D
= 55: From Reactions (1-C) and (1-D), v
CE
= 1 and v
DE
=
1: Therefore,
DN
E
= (1)(70) (1)(55) = 15
If there was no butene in the feed to the reactor, we would expect to nd 15 moles in the efuent that
was collected during the third shift.
1.4 DEFINITIONS OF REACTION RATE
1.4.1 Species-Dependent Denition
In order to be useful in reactor design and analysis, the reaction rate must be an intensive
variable, i.e., one that does not depend on the size of the system. Also, it is very convenient to
dene the reaction rate so that it refers explicitly to one of the chemical species that
participates in the reaction. The reference species usually is shown as part of the symbol for
the reaction rate, and the reference species should be specied in the units of the reaction
rate.
8 Chapter 1 Reactions and Reaction Rates
Consider a systemin which one stoichiometrically simple reaction is taking place. Lets
dene a reaction rate r
i
as
r
i
=
rate of formation of product i (moles i formed=time)
unit (something)
(1-11)
The subscript i refers to the species whose rate of formation is r
i
: The denominator of the
right-hand side of Eqn. (1-11) is what makes r
i
an intensive variable. We will return to this
denominator momentarily.
Several things are obvious about this denition of r
i
: First, if i actually is being
formed, r
i
will be positive. However, we may want i to be a reactant, which is being
consumed (disappearing). In this case, the value of r
i
would be negative. An alternative,
mathematically equivalent, denition can be used when i is a reactant:
r
i
=
rate of disappearance of reactant i (moles i consumed=time)
unit (something)
(1-12)
If i actually is being consumed, then r
i
will be positive, i.e., the rate of disappearance
will be positive.
In order to properly and usefully dene unit (something), we need to knowwhere the
reaction actually takes place. Lets consider a few of the most important cases.
1.4.1.1 Single Fluid Phase
A chemical reaction may take place homogeneously throughout a single uid phase. The
reaction might result, for example, fromcollisions between molecules of the uid or it might
result from the spontaneous decomposition of a molecule of the uid. In such cases, the
overall rate at which i is generated or consumed, i.e., the number of molecules of i
converted per unit time in the whole system, will be proportional to the volume of the uid.
Fluidvolume is the appropriate variable for expressingthe rate of a homogeneous reaction as
an intensive variable. Thus,
Reaction ratehomogeneous reaction
r
i
=
rate of disappearance of reactant i (moles i consumed=time)
unit volume of fluid
(1-13)
In this case, r
i
and r
i
have the dimensions of moles i=time-volume.
1.4.1.2 Multiple Phases
Multiphase reactors are much more prevalent in industrial practice than single-phase
reactors. The behavior of multiphase systems can be very complex. It is not always
straightforward to determine whether the reaction takes place in one phase, more than
one phase, or at the interface between phases. However, there is one very important case
where the locus of reaction is well understood.
Heterogeneous Catalysis Approximately 90% of the reactions that are practiced com-
mercially in elds such as petroleumrening, chemicals and pharmaceuticals manufacture,
and pollution abatement involve solid, heterogeneous catalysts. The reaction takes place on
1.4 Denitions of Reaction Rate 9
the surface of the catalyst, not in the surrounding uid phase(s). The overall reaction rate
depends on the amount of catalyst present, and so the amount of catalyst must be used to
make r
i
and r
i
intensive.
The amount of catalyst may be expressed inseveral validways, e.g., weight, volume, and
surface area. The choice between these measures of catalyst quantity is one of convenience.
However, weight is frequently used in engineering applications. For this choice,
Reaction rateheterogeneous catalytic reaction
r
i
=
rate of formation of product i (moles i formed=time)
unit weight of catalyst
(1-14)
In fundamental catalyst research, an attempt usually is made to relate the reaction rate to
the number of atoms of the catalytic component that are in contact with the uid. For
example, if the decomposition of hydrogen peroxide (H
2
O
2
) is catalyzed by palladium
metal, the rate of disappearance of H
2
O
2
might be dened as,
r
H
2
O
2
=
rate of disappearance of H
2
O
2
(molecules reacted=time)
atoms of Pd in contact with fluid containing H
2
O
2
(1-15)
Expressed in this manner, r
H
2
O
2
has units of inverse time and is called a turnover
frequency. Physically, it is the number of molecular reaction events (i.e., H
2
O
2
decom-
positions) that occur on a single atom of the catalytic component per unit of time.
Unfortunately, except in special cases, the symbol that is used to denote reaction rate is
not constructed to tell the user what basis was used to make the rate intensive. This task
usually is left to the units of the reaction rate.
Other Cases In some cases, a reaction takes place in one of the phases in a multiphase
reactor but not in the others. Obviously, it is critical to knowthe phase in which the reaction
occurs. If the denition of the reaction rate is based on the total reactor volume, serious
troublewill result whenthe ratio of the phases changes. The ratio of the phases generally will
depend on variables such as the reactor dimensions, the intensity of mechanical agitation,
and the feed rates and compositions of the various uids. Therefore, difculty is inevitable,
especially on scaleup, if the reaction rate is misdened.
In a few industrial processes, the reaction occurs at the interface between two phases.
The interfacial area then is the appropriate parameter to use in making the reaction rate
intensive. The synthesis of poly(bisphenol A carbonate) (polycarbonate) from bisphenol A
andphosgene is anexample of a reactionthat occurs at the interface betweentwouidphases.
On occasion, a reaction takes place in more than one phase of a multiphase reactor. An
example is the so-called catalytic combustion. If the temperature is high enough, a
hydrocarbon fuel such as propane can be oxidized catalytically, on the surface of a
heterogeneous catalyst, at the same time that a homogeneous oxidation reaction takes
place in the gas phase. This situation calls for two separate denitions of the reaction rate,
one for the gas phase and the other for the heterogeneous catalyst.
1.4.1.3 Relationship Between Reaction Rates of Various Species
(Single Reaction)
For a stoichiometrically simple reaction, that obeys the Law of Denite Proportions,
the reaction rates of the various reactants and products are related through stoichiometry,
10 Chapter 1 Reactions and Reaction Rates
i.e.,
r
1
=n
1
= r
2
=n
2
= r
3
=n
3
= = r
i
=n
i
= (1-16)
For example, in the ammonia synthesis reaction
N
2
3H
2
@2NH
3
(1-E)
r
N
2
=(1) = r
H
2
=(3) = r
NH
3
=(2)
In words, the molar rate of ammonia formation is twice the molar rate of nitrogen
disappearance, and two-thirds the molar rate of hydrogen disappearance.
1.4.1.4 Multiple Reactions
If more than one reaction takes place, the rate of each reaction must be known in order to
calculate the total rate of formation or consumption of a species. Thus,
Total rate of formation of i
when multiple reactions take place
r
i
=
R
k=1
r
ki
(1-17)
where R is the number of independent reactions that take place, and k again denotes a
specic reaction. In words, the total rate of formation of species i is the sum of the rates at
which i is formed in each of the reactions taking place.
1.4.2 Species-Independent Denition
The species-dependent denitionof the reactionrate is usedina majorityof publishedarticles in
the chemical engineeringliterature. The major disadvantage of this denition is that the reaction
ratesofthevariousspeciesinonechemicalreactionaredifferentiftheirstoichiometriccoefcients
aredifferent. Therelationshipof oneratetoanother isgivenbyEqn. (1-16). Thisdisadvantagehas
led to the occasional use of an alternative, species-independent denition of reaction rate.
In the species-independent denition, the reaction rate is referenced to the reaction
itself, rather than to a species. Consider the stoichiometrically simple reaction
i
n
i
A
i
= 0
Equation (1-16) provides relationships between the various r
i
for this reaction. However, we
can dene the rate of this reaction as r =r
i
=n
i
; so that Eqn. (1-16) becomes
r = r
1
=n
1
= r
2
=n
2
= r
3
=n
3
= = r
i
=n
i
= (1-18)
With this denition, a species does not have to be specied in order to dene the reaction
rate. However, we do have to specify the exact way in which the balanced stoichiometric
equation is written. For example, the value of r is not the same for
N
2
3H
2
@2NH
3
(1-E)
as it is for
1=2N
2
3=2H
2
@NH
3
(1-F)
because the stoichiometric coefcients are not the same in these two stoichiometric
equations.
EXERCISE 1-2
If r = 0:45for Reaction (1-E) at a given set of conditions, what is
the value of r for Reaction (1-F)?
1.4 Denitions of Reaction Rate 11
Obviously, when using the species-independent denition of reaction rate, great care
must be taken to write the balanced stoichiometric equation(s) at the beginning of the
analysis, and to use the same stoichiometric equation(s) throughout the analysis.
The species-dependent denition of reaction rate will be used throughout the remainder
of this text.
SUMMARY OF IMPORTANT CONCEPTS
v
Sign convention for stoichiometric coefcients
v
products positive; reactants negative
v
Extent of reaction
v
Single reaction
Closed system j = DN
i
=v
i
v
Sign convention for stoichiometric coefcients
v
products positive; reactants negative
v
Extent of reaction
v
Single reaction
Closed system j = DN
i
=v
i
v
Sign convention for stoichiometric coefcients
v
products positive; reactants negative
v
Extent of reaction
v
Single reaction
Closed system j = DN
i
=v
i
v
Sign convention for stoichiometric coefcients
v
products positive; reactants negative
v
Extent of reaction
v
Single reaction
Closed system j = DN
i
=v
i
v
Sign convention for stoichiometric coefcients
v
products positive; reactants negative
v
Extent of reaction
v
Single reaction
Closed system j = DN
i
=v
i
Open system at steady state j = DF
i
=v
i
v
Multiple reactions
Closed system DN
i
=
R
k=1
n
ki
j
k
Open system at steady state DF
i
=
R
k=1
n
ki
j
k
v
Applications
Checking consistency of data
Single reaction?
Multiple reactions? Which ones?
Calculating unknown quantities
v
Dening the reaction rate
v
Where does the reaction occur?
PROBLEMS
Problem 1-1 (Level 1) A group of researchers is studying the
kinetics of the reaction of hydrogen with thiophene (C
4
H
4
S).
They have postulated that only one stoichiometrically simple
reaction takes place, as shown below.
C
4
H
4
S 4H
2
!H
2
S C
4
H
10
In one experiment, the feed to a continuous reactor operating at
steady state was
C
4
H
4
S0:65 gmol/min
H
2
13:53 gmol/min
H
2
S0:59 gmol/min
C
4
H
10
0:20 gmol/min
The efuent rates were
C
4
H
4
S0:29 gmol/min
H
2
12:27 gmol/min
H
2
S0:56 gmol/min
C
4
H
10
0:38 gmol/min
Are the experimental data consistent with the assumption
that only one stoichiometrically simple reaction (i.e., the above
reaction) takes place?
Problem 1-2 (Level 2) A continuous reactor operating at
steady state is being used to study the formation of methanol
(CH
3
OH) from mixtures of H
2
and CO according to the reac-
tion
CO 2H
2
@CH
3
OH
Some data from one particular run are shown below.
Does the system behave as though only one stoichiometri-
cally simple reaction, i.e., the above reaction, takes place? If not,
develop a hypothesis that quantitatively accounts for any dis-
crepancy in the data. How could your hypothesis be tested?
Problem 1-3 (Level 1) The following e-mail is in your in-box
at 8 AM on Monday:
I hope that you can help with the following:
When quinoline (C
9
H
7
N) is hydrogenated at about 350
C
over various heterogeneous catalysts, the three reactions shown
belowtake place to varying extents. In one experiment in a batch
reactor (closed system), the initial charge to the reactor was 100
mol of quinoline and 500 mol of hydrogen (H
2
). After 10 h, the
reactor contents were analyzed, with the following results:
Quinoline (C
9
H
7
N)40 mol
Hydrogen (H
2
)290 mol
Decahydroquinoline (C
9
H
17
N)20 mol
To: U. R. Loehmann
From: I. M. DeBosse
Subject: Quinoline Hydrogenation
U.R.,
Species
Rate in
(gmol/min)
Rate out
(gmol/min)
CO 100 83
H
2
72 38
CO
2
9 9
CH
4
19 19
CH
3
OH 2 13
12 Chapter 1 Reactions and Reaction Rates
If the reactions shown below are the only ones that take place,
how many moles of tetrahydroquinoline (C
9
H
11
N) and butyl-
benzylamine (C
9
H
13
N) should have been present after 10 h?
N
N
H
2
H
2
N
H
2
N
Quinoline (C
9
H
7
N)
Tetrahydroquinoline
(C
9
H
11
N)
Butylbenzylamine
(C
9
H
13
N)
Decahydroquinoline
(C
9
H
17
N)
Please write me a short memo (not more than one page)
containing the results of your calculations and explaining what
you did. Attach your calculations to the memo in case someone
wants to review the details.
Thanks, I. M.
Problem 1-4 (Level 2) The following memo is in your in-box
at 8 AM on Monday:
Hope you can help with the following:
The methanation of carbon monoxide
CO 3H
2
@CH
4
H
2
O
is an important step in the manufacture of ammonia, and in the
manufacture of synthetic natural gas (SNG) from coal or heavy
hydrocarbons. The reaction is very exothermic. Especially in the
manufacture of SNG, a large quantity of heat must be removed
from the methanation reactor in order to avoid catalyst deacti-
vation and to maintain a favorable equilibrium.
A small research company, F. A. Stone, Inc., has offered to
license us a novel methanation process. The reaction takes place
in a slurry bubble-column reactor. Small particles of the catalyst
are suspended in a hydrocarbon liquid (a mixture of heavy
parafns with an average formula of C
18
H
38
. A gas containing
carbon monoxide (CO) and hydrogen (H
2
) is sparged (bubbled)
continuously through the slurry. The gas leaving the top of the
reactor contains unreacted CO and H
2
, as well as the products,
CH
4
and H
2
O. The heat of reaction is removed by water owing
through tubes in the reactor.
Please review the following pilot-plant data provided by F.
A. Stone to be sure that the process is performing as adver-
tised. These data are from one particular continuous, steady-
state run. F. A. Stone will not release additional data until we
have made a downpayment on the license fee.
You may assume that these ow rates are accurate, at least
for now.
Specic questions
1. Does the system behave as though one stoichiometrically-
simple reaction (the methanation of carbon monoxide) is
taking place? Explain your answer.
2. If your answer is no, what explanation(s) would you
propose to account for the observed behavior?
3. Based on your hypotheses, what additional experiments or
measurements should we require from F. A. Stone before we
make a down payment?
Please write me a short memo (not more than one page)
containing the answers to these questions, and explaining how
you arrived at your conclusions. Attach your calculations to the
memo in case someone wants to review the details.
Thanks, I. M.
Problem 1-5 (Level 2) Carbon monoxide (CO) and hydrogen
(H
2
) are fed to a continuous catalytic reactor operating at steady
state. There are no other components in the feed. The outlet
streamcontains unconverted COand H
2
, along with the products
methanol (CH
3
OH), ethanol (C
2
H
5
OH), isopropanol (C
3
H
7
OH),
and carbon dioxide (CO
2
). These are the only species in the
product stream.
The reactions occurring are
CO 2H
2
!CH
3
OH
3CO 3H
2
!C
2
H
5
OH CO
2
5CO 4H
2
!C
3
H
7
OH 2CO
2
The feed rates of CO and H
2
to the reactor are 100 mol/h
(each). The rates in the streamthat leaves the reactor (in mols/h.)
To: U. R. Loehmann
From: I. M. DeBosse
Subject: Methanation
U.R.,
Species
Inlet ow rate
(lbmol/day)
Outlet ow rate
(lbmol/day)
CO 308 41
H
2
954 91
CH
4
11 327
H
2
O 2 269
CO
2
92 92
N
2
11 11
Problems 13
are H
2
-30; CO-30; C
2
H
5
OH-5. What is the mole fraction of each
species in the product stream?
Problem 1-6 (Level 1) The hydrogenation of aniline at about
50
C and 50 bar of H
2
pressure for 3 h. The
following data were obtained:
The amounts of ammonia formed and H
2
consumed were
not measured.
1. Is the experimental data consistent with the assumption that
these three reactions are the only ones that occur?
2. Estimate the amount of NH
3
formed (mols/mol A charged).
3. Estimate the amount of H
2
consumed (mol/mol A charged).
Problem 1-7 (Level 2) The gas-phase reactions
Isobutanol (B) !Isobutene (IB) H
2
O
(CH
3
)
2
CHCH
2
OH!(CH
3
)
2
C=CH
2
H
2
O
2 Methanol !Dimethyl ether (DME) H
2
O
2CH
3
OH!CH
3
OCH
3
H
2
O
Isobutanol Methanol
!Methylisobutyl ether (MIBE) H
2
O
(CH
3
)
2
CHCH
2
OH CH
3
OH!(CH
3
)
2
CHCH
2
OCH
3
H
2
O
2 Isobutanol !Diisobutyl ether (DIBE) H
2
O
2(CH
3
)
2
CHCH
2
OH
!(CH
3
)
2
CHCH
2
OCH
2
CH(CH
3
)
2
H
2
O
take place in a continuous reactor operating at steady state. The
feed to the reactor consists of N
2
10,000 mol/h, isobutanol
(B)8333 mol/h, and methanol (M)16,667 mol/h. The efu-
ent ow rates are isobutene (IB)2923 mol/h, dimethyl ether
(DME)3436 mol/h, methyl isobutyl ether (MIBE) = 5038
mol/h, and diisobutyl ether (DIBE)22 mol/h.
1. What is the fractional conversion of isobutanol?
2. What is the fractional conversion of methanol?
3. What is the mole fraction of water leaving the reactor?
Problem 1-8 (K2-1) (Level 1) Consider the reaction
C
2
H
3
Cl
3
3H
2
!C
2
H
6
3HCl
(trichloroethane) (ethane)
If the rate of formation of HCl (r
HCl
) is 25 10
6
gmol/
gcat-min
1. What is the rate of disappearance of trichloroethane?
2. What is the rate of formation of ethane?
Problem1-9(Level 1) Lookcarefully at Reaction (1-A). Refer
to the literature as necessary. Prepare brief written answers to the
following questions:
1. Is a process based on this reaction a good example of green
chemistry?
2. What can be done with the NaCl that is produced?
3. Since Cl atoms do not appear in the nal product (C
3
H
6
O),
what role does chlorine play in this reaction?
Problem 1-10 (Level 1) Calculate the standard enthalpy
change on reaction, DH
0
R
; for Reaction (1-E) at 25
C. Calculate
the standard Gibbs free energy change on reaction, DG
0
R
,
for Reaction (1E) at 25