SCIENCE &

TECHNOLOGY
Carlo Pirola, Ilenia Rossetti,
Vittorio Ragaini*
Dipartimento di Chimica
Universit di Milano
[email protected]

Are Conversion,
Selectivity and Yield terms
unambiguously defined
in Chemical and Chemical
Engineering terminology?
This review shows and discusses the different definitions and use of conversion, selectivity and yield, with reference both to different
reactor types and reaction schemes. Books or manuscripts focusing on kinetics prefer to express selectivity as the amount of the
product desired weighted with respect to all the possible by-products. This definition, which is quite inapplicable if some
by-products are non quantitatively well defined, may come directly from the comparison of the reaction rates bringing to the different
species. By contrast, authors devoted to process or reactor design prefer a more practical definition of selectivity as amount of the
desired product formed with respect to the key-reagent that reacted. A confusing situation may arise if such expression is used
to define the yield. In such case the well known equation yield = conversion x selectivity is inapplicable.

Introduction especially if selectivity and yield are of concern. This quite confusing
In the chemical literature (in particular the one devoted to engineering situation was well commented in the past in ref. [10], p. 46, and [25],
topics) it is necessary to use the terms of conversion (X), selectivity p. 70: No universally agreed upon definitions exist for such terms-in
(S) and yield (Y) due to their relevance in kinetic studies, in order to fact quite the contrary. Rather than cite all the possible usage of these
adequately dimension reactors, to choose the best conditions to terms, many of which conflict, we shall define them as follows.
maximize the production of a given compound, limiting the amount of Such statement has been repeated in the subsequent editions of
by-products. Moreover, only if these terms are univocally defined it is this book.
possible to correctly compare different experimental results. Such confusing situation is still actual; in fact in a recent (2006) and
An inspection of a review [1] and some books [2-26] brought us to excellent book [24] it is written in chap. 6, dedicated to multiple
conclude that such terms have different meanings in many cases, reactions: As a consequence of the different definitions for selectivity

136 Marzo 13
 flow (moles or weight) of A reacted/flow (FA0-FA)
and yield, when reading literature dealing with multiple reactions, check for FR XA = = (2)

SCIENCE & TECHNOLOGY

of A introduced in the system FA0
carefully to ascertain the definition intended by the authors. From an
economic standpoint it is the overall selectivities, S-, and yields, Y-, Being n the moles or weight and F the flux, in moles or weight per unit
that are important in determining profits. However, the rate-based time; the suffix 0 indicates the initial quantity or flow of the reagent A.
selectivities give insights in choosing reactor and reaction schemes The numerators of the equations (1) and (2) are defined as conversion. If
that will help maximize the profit. However, many times there is a the system is at constant density (on molar or mass basis) the symbol n
conflict between selectivity and conversion (yield) because you want to can be changed in concentration (CA and CA0) in moles or mass per unit
make a lot of your desired product (D) and at the same time minimized volume [21, p. 351]. If there is a change, A, in the density (on molar or
the undesired product (U). However, in many instances the greater mass basis) the following definition of conversion is reported ([9], p. 59):
conversion you achieve, not only you make more D, you also form
C
more U. Among the cited textbooks the one by Fogler [24], contains, 1- A
CA0
but not exhaustively, some interesting discussions about the topics of XA = (1)
C
the present paper. 1+ A A
CA0
The most recent (2012) publication which is devoted to Chemical
Terminology (IUPAC-Gold Book [26]) contains only short definitions where, supposing a linear variation of the volume V with the conversion:
of the title terms: selectivity definition is devoted to ion exchange
(v 1 - vXA0)
chromatography, organic chemistry or analytical chemistry; the yield A = XA
(1)
vXA0
has been defined in the area of nuclear analytical chemistry and the
conversion in the one of chemical kinetics. The equations (1) and (2) hold even if the reaction scheme is complex,
Therefore it seems useful to perform a comparison among the variety of i.e. if the reactant A takes part to parallel or series reactions. However,
definitions of X, S, Y in order to rationalize the panorama of such terms. in this case, the fractional conversion parameter XA is not sufficient
A previous review titled: Yield in Chemical Reactor Engineering has to describe the course of the reaction and it is necessary to take into
been published in 1966 by Carberry [1], dealing mainly with the different account the concepts of selectivity and yield (vide infra).
regimes (isothermal, non-isothermal, diffusional) in chemical reactors. On the contrary, in [1] the following expressions are reported:
Note: The symbols X, S, Y (with different sub or/and superscripts) are Conversion or activity (as synonymous definitions), or: Conversion
used in order to standardize the different symbols used in the cited in terms of moles of reactant converted per unit time per unit volume
literature with reference to the same meaning. In few cases different of reactor, or: Conversion per se indicates the speed of reaction. In
symbols are used and explained in the text. Similarly n, F, C are used some cases [14, 17, 19] the conversion or fractional conversion are
as mole number, molar flux and molar concentration, respectively. defined without explicit mathematical expressions, like the equations
(1) and (2), but only through a word expression. In particular, in ref. [19],
1. Discussion p. 15, conversion is defined as 1 minus the fraction unreacted. In a
1.1 The definition of conversion unique case [17], p. 128, conversion is defined using an ambiguous
With respect to the three topics of this paper there is no doubt that the expression, i.e.: Conversion has several definitions and conventions.
conversion (and fractional conversion) definition is the one for which It is best to state the definition in the context of the problem being
there is an explicit, and quite agreed, definition in the majority of the solved. In ref. [22], p. 26, the following expression is reported for an
cited references [2-24]. In fact, the definition below reported is cited in irreversible reaction A to products: The quantity (CX/CA0) is a fraction
the following references: [7], p. 17; [8], p. 24; [10], p. 46; [12], p. 300; varying between zero (no conversion) and unity (complete conversion)
[13], p. 33; [14], pp. 3, 317; [15], p. 5; [16], p. 91; [18], p. 13; [20], p. for this irreversible reaction and is ordinarily called fractional conversion
47; [21], p. 351; [23], p. 152; [24], p. 38. of the reactant X. The above reported definition is correct only by
If in a reaction scheme, occurring in a closed or in a flow system in defining CX=CA0-CA. Conversion is also related to the degree of
stationary conditions, a reactant A is involved in only one irreversible completion of a reaction [10], p. 47.
reaction of known stoichiometry, then the conversion (or fractional
conversion, indicated usually as XA or in some books as f [14, p. 3;16, 1.2 The definitions of selectivity
p. 91;] or x [8], p. 24) is the unique parameter to follow the course In order to discuss conveniently this topic, it is compulsory to refer to a
of the reaction at any time (closed system) or position (flow system). scheme of irreversible reactions which include single, series or parallel
Considering a batch reactor (BR) or a flow reactor (FR) the most reactions, i.e. a multiple reaction scheme, involving a desired product
accepted definitions of XA, as fractional conversion, are: R and a reference (or limiting, or key) reagent A:

amount (moles) of A reacted/amount (nA0-nA)

for BR XA = = (1) Type 1: Single reaction
of A introduced in the system nA0
aA + bB + rR + pP +

Marzo 13 137
 SCIENCE &
TECHNOLOGY
Type 2: Parallel reactions the moles of the reference reagent A reacted:
2.1) With the same reagents
moles of R formed
aA + bB + rR + pP S
R/A
= (4)
moles of A reacted
aA + bB sS + tT
2.2) With separate reagents and products (simultaneous reactions) ([7], This definition is reported in most books: [5], p. 267; [7], p. 24; [8], p.
p. 23; [22], p. 26) 29; [10], p. 47; [12], p. 300; [13], p. 33; [16], p. 93; [18], p. 13; [21], p.
aA + bB rR + pP + 352; [22], p. 26; [23], p. 153. In some of the references above cited ([5,
cC +dD nN + mM + 8, 12, 13, 16, 23]) an explicit mathematical expression of (4) is given,
with [5, 8, 13, 16] or without [12, 23] the stoichiometric coefficients; in
Type 3: Series (or consecutive) reactions the former case it results for the different types of reactors [16]:
3.1) aA + bB + . rR + pP +
3.2) rR + bB sS + tT for BR (batch reactor) at constant or variable density:
SR/A = [(nR-nR0)/(nA0-nA)](a/r) (5)
It is useful to point out that the concept of selectivity is usefully applicable
especially to a multiple reaction scheme, but in the considered literature for FR (flow reactor) at constant or variable density:
some definitions are cited only with reference to Type 1 scheme (vide SR/A = [(FR-FR0)/(FA0-FA)](a/r) (5)
infra), where it would instead be sufficient to define the conversion and
the stoichiometric ratio among the different products to calculate the for BR or FR at constant density:
amount of desired product at the end of the reaction or at the outlet SR/A = [(CR-CR0)/(CA0-CA)](a/r) (5)
of the reactor.
Being: n the moles number, F the flux, C the concentration and the
1.2.1 General definitions suffix 0 the initial value. Eq. (5) is equivalent to the following one:
A convenient definition of selectivity to the desired product R is the
moles of A required to produce R
one that considers all (or some) the undesired product formed. Such S
R/A = (5)
moles of A reacted
definitions are prevalently given on a molar basis:
- in ref. [1], p. 41: It is noteworthy to observe that in the majority of the cited references
Selectivity, at a point, is the rate of generation of a desired product the definitions (4) and (5-5) are referred to a multiple reaction scheme,
relative to the generation of some undesired product; but in some cases [12, 18] to Type 1 (single reaction) scheme, only. In
- in ref.s. [2], p. 158; [3], p. 232; [4], p. 127: the latter case it could be observed that the selectivity has a fixed value
determined by the stoichiometric coefficients, as already observed.
moles of desired product formed
S R=
(3) Indeed, for example, if we apply Eq. (5) to a Type 1 scheme, quantity
moles of the undesired material formed
(nR-nR0) for Eq. (5), or the moles of the desired product (R) formed, for
- in ref. [23], p. 153: Eq. (3), can be evaluated from (nA0-nA) by considering the stoichiometry
of the reaction, provided that it does not change with time or position.
moles of desired product formed
SR=
(3) An example is the following one, concerning a cracking reaction:
moles of all the products formed

In ref. [24], p. 308, for flow reactors the overall selectivity is defined as: 2C3H8 1C2H2 + 2C2H6 + H2 (6)

FD Exit molar flow rate of the desired (D) product

SDU =
(3) = Considering: A=C3H8; R=C2H2, a=2; r=1, it results:
FU Exit molar flow rate of the undesired (U) product
n desired (nA0-nA)1/2 (1/2) 1
Or, for batch reactors: Eq. (3): SR/A = = = =
n undesired (nA0-nA)(1+1/2) (1+1/2) 3
n
SDU = D
(3)
nU

being n the mole number at the end of the reaction time.

Eq. (5): SR/A =
n desired (nA0-nA)1/2
n reacted
=
(nA0-nA)
=
2
1 ()
=1

Here the undesired materials formed include also, in a multiple reaction The experimental evaluation of the selectivity for Type 1 reactions
scheme, the ones coming from other reagents than the key reagent A, may not be exactly equal to the one calculated by applying the
such as M or N as defined in Type 2.2 (simultaneous reactions). Additional stoichiometry as above reported. This could happen if there are some
comments about Eq.s (3) and (3) are reported in paragraph 1.2.2. analytical errors or due to a change of the reaction scheme; this is
Another definition considers the moles of R produced with respect to more evident when the conversion of the reactant increases. It is

138 Marzo 13
reported ([18], p. 14) that the ratio (4) often changes as the reaction 1.2.2 Some ambiguous definitions

SCIENCE & TECHNOLOGY

progresses and the selectivity based on the final mixture composition In ref. [1], p. 41, a word definition equivalent to Eq. (7) is referred
should be called average selectivity. A similar terminology, overall to yield at a point within the reactor, instead of instantaneous or
or integral selectivity, is reported for Eq. (5) too ([5], p. 268; [7], p. differential selectivity.
24; [8], p. 85; [13], p. 33; [22], p. 26). This discussion justifies the In ref. [2], p. 159, the definition reported in Eq. (3) is considered a source
application of Eq.s (5, 5, 5) to Type 1 scheme. of problems if the undesired products are a goulash of undesired
In conclusion, in the absence of competing reactions (typically material. Therefore it is concluded to stay away from selectivity
Type 1 scheme), if the overall selectivity is defined and calculated and use the most clearly defined and useful fractional yield R/A (see
according to Eq.s. (5-5) its value is 100% and, moreover, the Yield paragraph 1.3). This observation can be extended to Eq. (3). It is not
(see paragraph 1.3) is the same, as observed in ref. [13], p. 33. clear in this definition if the expression: all products formed may
For some types of reaction schemes (namely catalytic reactions where include or not the desired product too.
some products can have a doping effect on the catalyst) this overall The scarce consideration of this selectivity definition may be the reason
selectivity is a degree of conversion. In such cases it is possible and why this parameter is totally ignored in the second edition of a well-
useful to define a local selectivity (for FR) or instantaneous selectivity known book [11]. In strong disagreement with the previous statement,
(for BR) ([13], p. 34), being calculated from a differential ratio. in ref. [18], p. 14, it is reported that The selectivity is a very important
For example dnR/dnA for Eq. (5), may be called istantaneous parameter for many reaction systems, being the selectivity definition
(differential) selectivity too, both for BR and FR ([5], p268; [22], p. 26): the one reported in Eq.s (5-5).
With reference to Type 1 scheme, in ref. [6], p. 98, two expressions are
SR/A =
(7)
dnR
-dnA[ ]( )
a
r
reported for the yield parameter (indicated as F and F):

(a moles of R formed)
The correlation between SR/A and the overall selectivity SR/A, as F = (10)
(r moles of A reacted)
expressed by Eq.s. (5-5), is calculated from the following equation [5],
p. 268, for BR and FR by using Eq. (5), for instance: or as:

SR/A = - [ 1
(nA0-nA) ]
nA0
n
A S
R/AdnA (8) F=
(a moles of R formed)
(r moles of A which were originally introduced in the system)
(11)

In this equation the nA value is determined as a function of the reaction Obviously these two definitions are not equivalent and, in particular, Eq.
time t (BR) or residence time t (FR) ([13], p. 35), being this last parameter (10) is equivalent to selectivity as defined in Eq.s (5-5) in the previously
determined from the ratio between the considered reaction volume, V, reported literature.
and the total volumetric flow rate vT. In ref. [10], p. 47, it is reported that selectivity, as defined by Eq. (4),
By contrast, for a CSTR (Continuously Stirred Tank Reactor) or MFR, is also called as efficiency, conversion efficiency, specificity, yield,
(Mixed Flow Reactor, according to the nomenclature of ref. [2], p. 90), ultimate yield, or recycle yield. This variety of definitions further justifies
using moles number, it results, being nR and nA constant throughout the unified discussion of the present paper.
the reactor ([15], p. 268): In ref. [14], p. 317, in defining the selectivity it is reported that Different
conventions have been used in assigning numerical values to
SR/A = SR/A =
(9)
(nR-nR0) a
(nA0-nA) r () selectivity, but one that is often useful is the ratio of the limiting reagent
that reacts to give the desired product to the amount that reacts to
Equations like (7), written without stoichiometric coefficients, and (4), give an undesired product. Such definition is too vague because
both using concentrations (C) instead of moles number (n), have been the undesired product may be P, S, T, etc. in the previously reported
used in ref. [2], p. 156, to indicate the instantaneous fractional yield schemes (paragraph 1.2).
(j) and the overall fractional yield (F), respectively, both referred to R. In the same book, the Eq. therein defined as (9.0.2), the same as Eq. (4)
It is useful to notice that equations like (8) and (9) written using of the present paper, connected with Type 1 scheme, is defined as yield,
concentrations (C) or fluxes (F) are all equivalent if the system has but previously it is reported that It is also necessary to state whether
constant molar density. the yield is computed relative to the amount of reactant introduced into
Historically, the first distinction between overall selectivity, or simply the system or relative to the amount of reactant consumed. Clearly
selectivity, and an expression like Eq. (7) appeared in the Denbighs Eq. (4) is relative to reactant (key-reagent) consumed, as Eq. 9.0.2, but
book [6], p. 112, where the Eq. there numbered (4.16), indicated with this last equation is reported in most references as selectivity not as
f at first member, is identical to the present Eq. (7) at the second yield (see paragraph 1.2.1).
member, being f called the infinitesimal yield of the product R obtained In ref. [16], p. 92, it is written: The fractional yield of a product is a
from a reagent A in a Type 1 reaction. measure of how selective a particular reactant is in forming a particular

Marzo 13 139
 SCIENCE &
TECHNOLOGY
product, and hence is sometime referred to as selectivity. Two ways selectivity from the instantaneous one. It is convenient for all the types
of representing selectivity are (1) the overall fractional yield (from the of reactors to rewrite Eq. (7) in terms of the two reaction rates rR/A and
inlet to a particular point such as the outlet);and (2) the instantaneous rS/A, which are relative to the formation of R and S from A, respectively:
fractional yield (at a point). Then the equations identical to those (5-5)
rR/A dCR/A
are reported as overall fractional yield of D (desired product) from a (12)
SR/A = =
(rR/A+rS/A) (dCR/A+dCS/A)
key reagent A, and indicated as D/A.
In our opinion, to avoid confusion, such overall fractional yield, but
rS/A dCS/A
indicated with the letter S, should be called overall selectivity as SR/A =
(13) =
(rR/A+rS/A) (dCR/A+dCS/A)
discussed in the previous paragraph.
In ref. [17], p. 128, the overall selectivity is defined as the ratio of To simplify, without a loss of a rigorous discussion, the different
the amount of one component produced to the amount of another mathematical expressions reported in the literature, it may be useful
component produced. This definition is completely new but it is to distinguish between the case in which rR/A and rS/A equations are
again too vague. Moreover, in ref. [23], p. 153, the definition (3) is different only due to the two kinetic constants kR/A and kS/A, i.e.:
not equivalent to the one reported in (3). In fact, among all the formed
products some may be desired, but they are not included in the rR/A = kR/ACaA CbB and rS/A = ks/ACAaCb
B
(14)
numerator of (3) and (3) being different from R. Besides for some
specific calculations the undesired products may be only some among where it has been supposed that the reactions orders are a=a and
all the products of a reaction, as reported in a numerical example in b=b.
ref. [4], p. 128. In this case, as outlined in ref. [13], p. 36, by substituting Eq.s (14) in
In connection with Eq.s (3) and (3), in ref. [24]), (reaction scheme at p. (12) and (13) it results:
307) only one undesired (U) product is cited. Therefore or U include all
the undesired products formed or in presence of many products (see (15) kR/A
S R/A = = const
for example Eq. (6)) one must choose which of these is the undesired kR/A+kS/A
one. But if there is a goulash (see ref. [2], p. 159) of products, may
kS/A
be that some of these are not well identified, it is difficult to include in U S S/A =
(16) = const
kR/A+kS/A
all the undesired products, or to choose some of these as undesired.
Such observations can be extended to the instantaneous selectivity It is evident that assuming SR/A and SS/A a constant value then the
(S) if this parameter is defined (ref. [24], p. 307) as: overall selectivities, also SR/A and SS/A, will have the same values as
(15) and (16), respectively. For a CSTR this derives by applying Eq. (9)
rD rate of formation of D
(7)
S DU = = and for a PFR or BR by the integration of Eq. (8), where SR/A, under
rU rate of formation of U
integral, has a constant value (15), and similarly for SS/A.
In conclusion Eq.s (3), (3) and (7) may be too limiting in the case of In conclusion, if the reaction rates are different only for the kinetic
multiple by-products. In this case, in our opinion, it is much better to constants then for every types of reactor the overall selectivities and
use Eq.s (4) and the equivalents ones (5-5) or the equivalent equations the instantaneous selectivities have the same constant values for each
for the instantaneous selectivity. desired product i:

k k
1.2.3 Parallel reactions SR/A = SR/A = R/A and SS/A = SS/A = R/A
(17)
i ki/A i ki/A
Such reaction scheme (Types 2.1 and 2.2) is considered in quite all the
books cited in the references; it is connected with both the definitions A more complex case is the one in which the rate equations have
(3) (see ref. [4], p. 128) and (4-5). Basically, the terms overall selectivity different expressions. In particular considering that a CSTR operates at
and local (or differential) selectivity are applicable to scheme 2, but it is the outlet concentration of the reactants, then instantaneous selectivity
necessary to evaluate the moles of the key reagent reacted according is always constant and equal to the overall one, but in general these
to two or more reactions. values will depend on both the kinetic constants and on the values of
Detailed discussion of this case are reported in particular, sometime CA and CB at the exit.
with numerical examples too, in ref.s. [2], pp. 159-161; [5], pp. 267- A different situation holds for a PFR or BR because in the Eq. (8) the
272; [7], pp. 23-26 and 226-228; [13], pp. 34-45. In ref. [2], pp. 155- upper limit of the integral (CA) should be evaluated at the maximum
156, the selectivity, overall and instantaneous, is called respectively residence time for a PFR (max=VR/VT) or to any other reactor volume
overall fractional yield and instantaneous fractional yield, but the VR<VR; for BR, CA can assume all the values from 0 to the final
definitions are the same as reported in Eq.s. (4) and (7). reaction time.
Now we can consider the scheme 2.2 in order to calculate the overall For instance if a=b=b=1 and a=2:

140 Marzo 13
rR/A = kR/ACACB and rS/A = ks/ACA2 CB (18) CSTR systems. Several types of calculations are presented in the

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literature concerning the two mentioned kinds of reactors; it is possible
then, by applying Eq. (12) the instantaneous or local selectivity is: to summarize such calculations in four items:
i) concentration ratios CA/CA0, CR/CA0, CS/CA0, expressed as a function
kR/ACACB kR/A
SR/A =
(19) = of the ratio between the kinetic constants k2/k1, with comparison
kR/ACACB+kS/ACA2 CB kR/A+kS/ACA
between the residence time of different reactor types;
Similarly: ii) ratio between the overall selectivity toward R (SR/A) or S at the same
kS/AC CB 2 conversion of the key reagent A (xA,max);
A kS/ACA
SS/A =
(20) = iii) optimum values of the residence time (opt) and mean residence
kR/ACACB+kS/ACACB
2
kR/A+kS/ACA
time (t-opt) to obtain the maximum concentration of R, and the
For a CSTR the CA value is the one at the exit of the reactor and the corresponding conversion of A (xA,max);
resulting overall selectivity is equal to the instantaneous one (SR/A). The iv) instantaneous selectivity towards R and S (SR/A, SS/A) for a PFR.
same holds for SS/A. Indeed, as previously indicated (Eq. (9) for a CSTR it results SR/A=SR/A.
Instead, for a PFR (or BR) the overall selectivity is evaluated by applying All the previous items can be solved by using the classical fundamental
Eq. (8) and Eq. (19): equations for a PFR and CSTR, as below reported, using the
concentrations of A, R, S (respectively CA, CR, CS), being the suffix 0
(21)
S R/A = -
1 c
A
(
kR/A
(CA0-CA) cA0 (kR/A+kS/ACA)
dCA =
) the initial value.

( ) ( )
1 kR/A (kR/A+kS/ACA0) For a PFR:
= ln
(CA0-CA) kS/A (kR/A+kS/ACA) CA
(22)
= e-k1t = 1 - XA
CA0
In the paragraph 1.3, dedicated to the yield, it is discussed how
the different equations used to calculate the instantaneous or local
selectivity strongly influence the estimation of the total production of R
C
CR

A0
=
[ k1
(k2-k1) ] (e-k1t - e-k2t) (23)

and S depending on the reactor type. or

1.2.4 Series (or consecutive) reactions

k1
The discussion for this type of reactions is limited to the case ARS. k2
CR
=
(23)
CA0 { 1
(k2/k1 - 1) }
(e-k1t - e-k2t)

[( )]
Type 3 reaction scheme is referred to different expressions found in the CS 1
literature, for example: consecutive reactions ([6], p. 25; [8], p. 108; = (1 - e-k1t ) - k
(24) (e-k1t - e-k2t)
CA0 2
-1
[9], p. 70); reaction sequential ([7], p. 27); series reactions ([2], p. 192; k 1

[3], p. 452; [13], p. 45). This topic is discussed in quite all the referred For a CSTR:
books and in particular in: [2], pp. 194-197; [3], pp. 461-464; [6], pp.
CA 1
99-104; [7], pp. 228-231; [8], pp. 109-123; [13], pp. 45-48. = = 1 - XA (25)
CA0 (1 + k1t- )
Discussing the behaviour of the different types of reactors, in connection
with series reactions, it is useful to observe that for PFR and CSTR the C
R
= k1t-
residence time distribution represents the extremes in mixing behaviour CA0 (1 + k1t- )(1 + k2t- ) (26)
([7], p. 223); besides PFR and BR can be discussed together being the
reaction time (t) in BR substituted in PFR by a residence time (t), which
CS (k1t- ) (k2t- )
is the ratio between the considered real volume, V, and the volumetric = (27)
CA0 (1 + k1t- )(1 + k2t- )
flux vT, being 0<VVmax ([13], pp. 20-22). Vmax is the volume of a CSTR
which (for a positive order reaction rate) is always greater than that of a The results of the calculations lead to the following remarks.
PFR to achieve the same reagent conversion at the same total flux. For Item i): a very useful equilateral diagram, having on the three sides CA/CA0,
a reaction order less than zero the opposite is true. For a CSTR instead CR/CA0, CS/CA0 (all three ratios varying from 0 to 1), is obtained ([8], p. 115).
it is better to use the mean residence time t-=Vmax/vT. Therefore in the Such calculation is easily performed using the following sequence, where
literature the comparison is made between PFR and CSTR. k2/k1=k is fixed: chosing a ratio CA/CA0 between 0 and 1 from Eq.s (22)
Type 3 scheme is well studied in all kinetic books where the mathematical and (25) the products k1t- and k2t- are calculated and therefore t/t-=a is
expressions show how the concentration of A continuously decreases determined. Then (k2/k1)x(t/t-)=ka=k2t/k1t- and, therefore, k2t=(ka)k1t-.
as a function of time, R reaches a maximum and S monotonously Similarly, k1t- k=k2t-. The four values k1t, k2t, and k1t-, k2t- together with
increases. This behaviour influences strongly and differently PFR and k2/k1=k allow the calculation of CA/CA0 and CR/CA0 (Eq.s (23), (26),

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respectively). Then, CS/CA0=1 - CA/CA0-CR/CA0. Therefore for a CSTR the selectivity R/A does not depend from the
Item ii): The relation between t and t- to achieve the same conversion, kinetic constant k1. This conclusion is rather surprising, but it is
xA, at the same volumetric flux, in PFR and CSTR, respectively, is easily confirmed by a simple numerical comparison between Eq.s (30) and
obtained by using Eq.s (22) and (25). It results ([7], p. 228): (34), which indeed return the same value when fixing t-, k1, k2, indeed
independent on k1. Furthermore, Eq. (34) proved much more reliable
t = [ln(1+k1t- )]/k1 (28) than Eq. (30), since it leads continuous and monotonously variable
values from 0 to 1 for SR/A(CSTR), whereas Eq. (34) is not applicable
or: t = [ln(A)]/k1 (28) for k10 and k1=k2, for which indeterminate forms are obtained. The
same situation occurs also for Eq. (29). The independence of the
being A=1+k1t-. selectivity of an intermediate from the kinetic constant for its formation,
The expression for SR/A(PFR) is obtained by using Eq. (5) in which but only for that describing its consumption rate is not very intuitive and
Eq.s (22) and (23) are included. It results ([7], pp. 29, 228): deserves a deeper investigation which goes beyond the scope of this
work. However, a first attempt to interpret such intriguing observation
SR/A(PFR) = [k1/(k2-k1)](e-k1t - e-k2t)/(1 - e-k1t) (29) is that explicit expressions to calculate selectivity for the intermediate
in consecutive reaction paths have been derived for the simplest case
Similarly, using Eq.s (25) and (26) in Eq. (5), SR/A(CSTR) is calculated only, i.e. first order reactions.
In this way an increase of k1 brings about an increase of concentration
([7], p. 228): of the intermediate R, with consequent increase of its consumption
SR/A(CSTR) = [1/(1-k)][(A/B-1)/(A-1)] (30) rate. Therefore, for instance any increase of k1 does not bring to any
net accumulation for R since its depletion is accelerated too due to an
where B=1+k2t-. increased availability of this reactant.
At last, it should be remarked that Eq.s (29) and (30) hold for CB0=0, Should the reactions exhibit different reaction orders, likely the
not explicitly indicated in the selected reference. dependence on k1 would be evident.
To calculate the ratio SR/A(PFR)/SR/A(CSTR) at the same conversion xA, Item iii): The optimum residence time opt or t-opt to obtain the maximum
it is necessary to substitute t in Eq. (29) a expressed by the Eq. (28). concentration of R is discussed in many books; we will consider some
Therefore: of them [ref.s. 2, pp. 195-196; 3, pp. 463-467; 6, pp. 101-102; 8, pp.
111-114; 13, pp. 46-47]. The starting point is to solve the equation
SR/A = [1/(k-1)][(1/A-1/Ak)/(1-1/A)] (31) dCR/dt=0 (for PFR) and dCR/dt=0 (for CSTR).
The results are:
Finally the main result for item ii) is obtained by the ratio between Eq.s
(31) and (30) ([7], p. 229): opt(PFR) = [ln(k2/k1)]/(k2-k1) (35)

R = SR/A(PFR)/SR/A(CSTR) = [1-A(1-k)]/(1-A/B) (32) t-opt(CSTR) = 1/(k1k2)1/2 (36)

A convenient diagram of the ratio R as a function of conversion xA and Eq. (36) is also reported in ref. [13], p. 47.
k is reported in the cited reference. In [7], p. 230 a sophisticated analysis is performed, which brings to
Two observations, never reported in literature, can be made concerning the equation:
Eq.s (28) and (29). The ratio
t- opt(CSTR) = [(k1k2)1/2 - 1]/[k1-k2(k1k2)1/2] (37)
t/t- = ln(1+k1t- )/k1t- (33)
After some algebraic manipulations it can be demonstrated that such
depends only on the kinetic constant k1; the second member of this equation is perfectly reducible to the simpler one (36). In [3] it seems
equation is a function only of k1t-, and it has a decreasing value lower that t-opt(CSTR) is not discussed in order to obtain an equation like (36),
than 1. This analysis brings directly to the important conclusion that a while in [2], p. 196 the following equation is reported:
PFR requires a lower residence time than a CSTR to reach the same
conversion of the key reagent. The second observation is that an easy t- opt(CSTR) = 1/(k1k2)1/2 (38)
algebra applied to Eq. (30), by substituting A=1+k1t- ; B=1+k2t- ; k=k2/k1 or:
shows that: t- opt(CSTR) = k2/(k1k2)1/2 (38)

SR/A(CSTR) = 1/B = 1/(1+k2t- ) (34) Obviously such equations do not coincide with Eq. (36). In the cited

142 Marzo 13
ref. [2] the considered reaction scheme is more complicated than: i) the majority of the definitions uses the letter Y; sometimes the suffix I

SCIENCE & TECHNOLOGY

ARS, because both A and R can react to give other 2 products and j or A and R (or similar letters) are used to indicate the key reagent
different from R and S. Eq. (36) has been written by supposing that the I or A and the desired product j or R (see: [1], [5], p. 268; [7], p. 23; [9],
reaction scheme is only as above reported. p. 70; [13], p. 33; [14], p. 317; [16], p. 92; [18], p. 13; [21], p. 353; [22],
From the values of t-opt and t-opt the corresponding values of the opti- p. 26; [23], p. 154; [24, p. 309);
mum conversion, xA,opt, is calculated by inserting such values in Eq.s ii) the Greek letter F or j ([2], p. 156; [6], p. 98) or h ([8], p. 29) are
(22), for PFR, and (25) for CSTR; this substitution is made by using used too;
Eq.s (32) and (33). The results is ([3], p. 463): iii) in all the other cited references the initial definition is given by a
suitable expression, avoiding a specific letter.
XA,opt(PFR) = 1 - (k2/k1)1/(1-k2/k1) (39) Considering the content of such definitions, the majority uses the
following expression, with Y and a molar basis [3, p. 232; 8, p. 29; 10,
or using k=k2/k1: p. 47; 12, p. 300; 21, p. 353; 23, p. 154]:

moles of desired product j formed from moles of i reacted

XA,opt(PFR) = 1 - (k)1/(1-k) (39) Yi/j =
(42)
moles of i present initially

Besides using the basic equation (25) and (35) it results: Or [7, p. 23; [13] p. 33; 16, p. 92; 22, p. 26]

moles of i reacted to form j

XA,opt(CSTR) = 1 - 1/[1+k1/(k1k2)1/2] 0 Yi/j =
(43)
moles of i present initially

or ([8], p. 114): The two definitions, above reported, are equivalent, if we consider the
reaction scheme:
XA,opt(CSTR) = 1/(1+k1/2) (40)
aA + bB rR + sS (44)
The optimum selectivity for R is easily obtained by using Eq. (5) in which
CA and CR are calculated by using Eq.s (22) and (23) at t=opt(PFR), to Considering the definition (42) it results:
give Eq. (35), or Eq.s (25) and (26) at t-=opt(CSTR), to obtain Eq. (36).
Item iv): The last subject of this discussion concerns only PFR because,
as previously discussed, the differential, SR/A, and overall selectivities,
YR/A =
(45) (
nR-nR0 a
nA0 r )
SR/A, in CSTR are the same. But: (nR-nR0)/(a/r) are the moles of A reacted to give R, as the
Few books discuss this subject for Type 3 reactions (consecutive definition (43).
reactions). The equation for SR/A(PFR) can be calculated both by It has been observed ([13], p. 33) that if there is only one product,
applying Eq. (7), written using concentration and assuming a=r: then Eq. (45) is the A conversion, xA, because (nR-nR0)/(a/r)=nA0-nA and
xA=(nA0-nA)/nA0.
SR/A = dCR/-dCA = (k1CA-k2CR)/(k1CA) (7) Some confusing situations, with respect to the definitions above given
arise if we consider [2, 6, 14, 20] where the yield is defined as:
or by using the derivative of the yield with respect to conversion (see (overall fractional) yield (F in [2], p. 156):
next paragraph). In the first case, CA and CR as described by Eq.s (22)
all R formed
and (23) respectively, are substituted in Eq. (7). The result is: Yield
(46) (F) =
all A reacted

(41)
SR/A(PFR) = 1 -
k1
(
k1-k2
k2
k1 )[ (
ek1t
1- k t
e2 )] or [6], p. 98; [14], p. 317; [20], p. 48:

or YR/A =
(47)
[
nR-nR0 a
nA0-nA r ]
SR/A(PFR) =
(41) k2
1 k2 ek1t
[ (
-1 k1 e 2
k1
k t
-1
)] (YR/A is indicated as F in ref. [6])

1.3 The definition of yield or (Instantaneous) Fractional Yield (j in [2]):

This topic is the title of a paper published in the past by Carberry [1].
dCR
Miscellaneous definitions are offered in the cited literature. Let us group (48)
j=
-dCA
such definitions in some items, starting from the letters used to identify
the yield: Such equations are the same as overall selectivity (5-5) or differential

Marzo 13 143
 SCIENCE &
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selectivity (7) discussed in the previous paragraph. Therefore:
Other definitions are:
- Yield = (moles of desired product formed)/(moles that would have iYi/A = XA (54)
been formed if there were no side reactions and the limiting reactant
had reacted completely [4], p. 127; Taking into account Eq. (49) it derives:
- Yield (Theoretical) = amount of product that would be formed if all the Y
reactant were converted to the desired product [19], p. 15; SR/A = R/A
(55) iYi/A
- Yield (Theoretical) = ratio of the rate generation of a desired product R
Y
(rR) to the rate of consumption of a key reactant A (rA) [9], p. 70; SS/A = S/A
(56)
iYi/A
- Yield = amount of desired product produced relative to the amount
that would be formed if there were no by product and the main reaction Considering now the scheme ii), where a variety of products are formed,
went to completion [18], p. 13. we may write four equations like (51) and (52) for the products R, S, D,
E with stoichiometric coefficients 1/5, 1/3, 2/1, 2/2, respectively, but it is
1.3.1 Application of Eq.s (42), (43). easy to demonstrate that the total conversion XA can be calculated from
Taking into account definitions (42), (43) and the ones of conversion Eq. (54), but using for each reaction only one product, i.e. for example:
(1) and selectivity (5) it is obvious to obtain the well-known correlation
among Y, X, S: XA = YR/A + YD/A (57)

YR/A = XASR/A (49) 1.3.1.2 Consecutive reactions

The reaction scheme is the same as reported in paragraph 1.2.
Such equation can be utilized both for parallel and series reactions in A convenient discussion for such topic, in order to correlate selectivity and
order to calculate the selectivity using the yield and viceversa. yield is presented in ref. [8], p. 108-114, both for PFR and CSTR reactors.
In the second case, the selectivity will include both the overall (SR/A) and
1.3.1.1 Parallel reactions the instantaneous one (SR/A). A general procedure for both the types of
We will consider two reaction schemes: reactors can be obtained from the derivative of Eq. (49) with respect to XA:
i) A rR
dYR/A
A sS SR/A =
(58)
dXA
Exemplified as:
AR Besides, SR/A is obtained from an equation derived from (7) and using
A 2S equation (45):
ii) aA rR + sS
Y
aA dD + eE SR/A = 1 - k R/A
(59)
1-XA
Exemplified as:
1A 5R + 3S The dependence of the conversion XA and YR/A from t and t- for PFR/
2A 1D + 2E BR or CSTR respectively are obtained from equations (22), (25) and (26)
The final results are as below reported:
For scheme i) according to Eq. (45): i) PFR/BR

Y
(
R/A =
(51)
nA0 )
nR-nR0 1
1
SR/A =
(60)
1-XA
(k-1)XA [
1-(1-XA)k-1
]
(52)
(n -n
YS/A = S S0
nA0
1
2) (61)
SR/A =
1
k-1 [
k(1-X)k-1 - 1
]
[ ]
Therefore: (62) 1-XA
YR/A = 1 - (1-XA)k-1
(nR-nR0) + (nS-nS0)/2 k-1
YR/A + YS/A =
(53)
nA0
ii) CSTR
The numerator of (50) is the number of moles of A reacted, i.e. nA-nA, Y 1-XA
SR/A = SR/A = R/A =
hence: (63) XA (k-1)XA+1
nA0-nA X (1- XA)
YR/A + YS/A = = XA YR/A = A (64)
nA0 (k-1)X +1
A

144 Marzo 13
Conclusions come directly from the comparison of the reaction rates bringing to the
The aim of the present review, probably one of the very few published different species.
about the topics reported in the title, is to show and compare the different In our opinion this definition is hardly applicable if all the by-products are

SCIENCE & TECHNOLOGY

definitions and use of conversion, selectivity and yield, with reference both not quantitatively defined.
to the reactor types and the different reaction schemes shown in paragraph By contrast, authors devoted to process or reactor design prefer a more
1.2. Some definitions appear to have more consent than others in the practical definition of selectivity as the ratio between the amount of the
analysed literature: for conversion, Eq.s (1, 2); for the (overall) selectivity, desired product formed with respect to the key-reagent reacted.
Eq.s (4, 5-5); for the local and instantaneous (differential) selectivity, Eq.s If this definition is instead applied to define the yield, as for instance in [2,
(7-9); for the yield, Eq.s (42, 43, 45). 4], then the product of this yield and the conversion as defined by Eq.s (1,
Obviously, as underlined in the sentence of [10] and [25], cited in the 2) gives the most used definition of yields (Eq. 42), i.e. the ratio between
Introduction, there are some conflicting definitions, which are discussed the amount of the desired product formed and the key-reagent fed. In
in this review. In general, the most confusing concepts seem selectivity our opinion the useful equation yield = conversion x selectivity must be
and yield. Apparently, the different definitions arise from the topic covered maintained, but this imply to define the selectivity as in Eq. (4) or (7).
by the reference considered. Indeed, books or manuscripts focusing on Anyway, the authors hope that the present review could give an help
kinetics prefer to express selectivity as the amount of the product desired to standardize the definitions and the symbology of such important
weighted with respect to all the possible by-products. This definition may parameters in the chemical engineering publications.

References
[1] J.J. Carberry, Industrial and Eng. Chem., 1966, 10, 58. and Reactor Design, Wiley & Sons, New York, 1977.
[2] O. Levenspiel, Chemical Reaction Engineering, Wiley & Sons, [15] G.F. Froment, K.B. Bischoff, Chemical Reactor Analysis
New York, 1999, 3rd Ed. and Design, Wiley & Sons, New York, 1979.
[3] H. Scott Fogler, Elements of Chemical Reaction Engineering, [16] R.W. Missen, C.A. Mims, B.A. Saville, Introduction to Chemical
Prentice-Hall, Englewood Cliffs, New Jersey, 1986, 2nd Ed. Reaction Engineering and Kinetics, Wiley & Sons, New York, 1999.
[4] R.M. Felder, R.W. Rousseau, Elementary Principles [17] J.B. Rawlings, J.G. Ekert, Chemical Reactor Analysis and Design
of Chemical Processes, Wiley & Sons, New York, 1986. Fundamentals, Nob Hill Pub., Madison, Wisconsin, 2002.
[5] H.F. Rase, Chemical Reactor Design for Process Plants, [18] P. Harriott, Chemical Reactor Design, Marcel Dekker,
Vol. 1, Wiley & Sons, New York, 1977. New York, 2003.
[6] K. Denbigh, Chemical Reactor Theory-An Introduction, [19] E.B. Naumann, Chemical Reactor Design, Optimization
Cambridge Univ. Press, Cambridge, 1966. and Scale up, McGraw-Hill, New York, 2002.
[7] J.B. Butt, Reaction Kinetics and Reactor Design, Prentice-Hall, [20] R.K. Sinnott, Chemical Engineering Design,
Enlewood Cliffs, New Jersey, 1980. Chemical Engineering, Coulson & Richardson (Eds.),
[8] K.R. Westerterp, W.P.M. Van Swaaij, A.A.C.M. Beenackers, Butterworth Heinemann, Oxford, 2003, 3rd Ed.
Chemical Reactor-Design and Operation, Wiley & Sons, [21] A. Kayode Coker, Modeling of Chemical Kinetics
New York, 1984. and Reactor Design, Butterworth-Heinemann, Oxford, 2001.
[9] M.O. Tarthan, Catalytic Reactor Design, McGraw-Hill, [22] J.B. Butt, Reaction Kinetics and Reactor Design, Marcel Dekker,
New York, 1983. New York, 2000.
[10] D.H. Himmerblau, Basic Principles and Calculation [23] L.D. Schmidt, The Engineering of Chemical Reactions,
in Chemical Engineering, Prentice-Hall, Englewood Cliffs, Oxford Univ. Press, Oxford, 1998.
New Jersey, 1974, 3rd Ed. [24] H. Scott Fogler, Elements of Chemical Reaction Engineering,
[11] O. Levenspiel, Chemical Reaction Engineering, Wiley & Sons, Prentice Hall, 2006, 4th Ed.
New York, 1972, 2nd Ed. [25] D.H. Himmerblau, Basic Principles and Calculation
[12] V. Kafarov, Cybernetic Methods in Chemistry in Chemical Engineering, Prentice Hall, Englewood Clift,
& Chemical Engineering, MIR Pub, Moscow, 1976. New Jersey, 1989, 5th Ed.
[13] I.S. Metcalfe, Chemical Reaction Engineering-A First Course, [26] IUPAC (International Union of Pure and Applied Chemistry):
Oxford Science Pub., Oxford, 1997. Compendium of Chemical Terminology - Gold Book.
[14] C.G. Hill Jr., An Introduction to Chemical Engineering Kinetics Version 2.3.2, Aug. 2012.

Conversione, selettivit, resa sono termini definiti

riassunto
in modo non ambiguo nella letteratura chimica e di ingegneria chimica?
Questa rassegna prende in considerazione e discute le differenti definizioni e usi dei termini conversione, selettivit, resa, con riferimento sia ai diversi tipi di reattori che
schemi di reazione. I libri e i lavori dedicati principalmente alla cinetica preferiscono esprimere la selettivit come rapporto tra lammontare del prodotto desiderato e quello
di tutti i possibili sottoprodotti. Questa definizione, che non applicabile se tutti i sottoprodotti non sono quantitativamente determinati, deriva direttamente dal confronto
delle velocit di formazione per le differenti specie chimiche. Gli autori che si dedicano a studi riguardanti processi o reattori chimici preferiscono invece una definizione pi
pratica di selettivit, ovvero il rapporto tra lammontare del prodotto desiderato formato con quello del reagente chiave reagito. Una situazione che pu creare confusione
nasce se questultima definizione di selettivit invece usata per definire la resa. In tal caso la ben nota equazione resa = conversione x selettivit risulta non applicabile.

Marzo 13 145