Chemico/ Engineering Science, 1976, Vol. 31, pp. 1199-1205. Pergamon Press.

Printed in Great Britain

SELECTION OF MEASUREMENTS NECESSARY TO

ACHIEVE MULTICOMPONENT MASS BALANCES IN
CHEMICAL PLANT

V. VkLAVEK and M. LOU(5KA

Department of Chemical Engineering, Institute of Chemical Technology, Prague 6, Czechoslovakia

(Received 17 July 1975;accepted 25 March 1976)

Abstract-The idea of balance scheme reduction is applied to the problem of multi-component mass balance
calculations. The parameters characterizing the plant streams are the total mass Row rate and the concentrations of
individual components. Four categories of streams are distinguished according to the distribution of measured and
unmeasured parameters. Two algorithms are presented based upon this reduction. Algorithm CLASS is used to
classify, i.e. find redundant and determinable parameters, and algorithm CHOICE is used to select the necessary
measurements.

1. INTRODUCTION The aim of this paper is to present a description of both

One activity, in which the balance calculations of complex
processes have a dominant significance is in the determi-
nation of the real behaviour of a chemical plant by
extensive measurements. Due to various reasons, not all
required quantities are measurable or can be measured.
These quantities must then be evaluated indirectly from
the measurement of other variables and from exact
theoretical relationships such as balance, stoichiometric
and definition equations.
We shall focus ‘our attention on the calculation of
multi-component mass balances. The selection of neces-
sary measurements precedes any activity connected with
the balance calculations from measured data. On the other
hand, when the measurements have already been
selected, it is important to fmd out which of the
unmeasured parameters can be determined from input
information (i.e. measured data and mathematical rela-
tionships). Thus all the unmeasured parameters may be
classified either as determinable or undeterminable.
Similarly measured parameters can also be classified in
two groups. Some measured data may be obtained from
mathematical relationships using other measured parame-
ters, or may be calculated. In the former case the
measured parameters are redundant (overdetermined) and
can be reconciled. In this way the accuracy of measured
data can be improved. in the latter case the data are not
redundant, and there is no other indirect way of obtaining
their values. Hence this classification of parameters can
serve to test a given design of measuring places whether it
suits the purpose of balance calculations.
There is however a more urgent task concerning this
problem. We ought to suggest an algorithm capable of
selecting the necessary measurements directly instead of
testing the propriety of individual variants by single
classification. In this case the input information would
include the determination between measurable and
unmeasurable parameters as well as those required and
those not required. The results are obtained in the form of
three sets of parameters: the parameters which must be,
need not be, and should be measured.
algorithms, CLASS and CHOICE, developed to solve
the above-mentioned problems. A brief but necessary
theoretical background is also presented but without proof
sinceithasalreadybeenpartiallypublishedelsewhere[l, 21.
Both algorithms were programmed in FORTRAN IV and
their application is illustrated.
Z.FmLIhnNARY ASSWWllONSANDDEFlNlTlONS
(i) Let us consider a continuous balance scheme[3]
containing K nodes denoted as k = I,. . . K and J
oriented streams with indices j = 1,. . . J. A topology of
the balance scheme is expressed by an incidence matrix
{ai}. The streams connected to one node only are called
external while those incident to two nodes are internal.
Both external and internal streams comected to the same
node(s) (regardless of orientation) are called parallel. (See
Fig. 1).
(ii) The quantitative properties of the streams are
characterized by a vector.
@fj,xi,,. . .,-J&i,. . . , &I)
where Mi is the total amount of mass and X# is the
concentration mostly mass or molar fraction of the i-th
component, i=l,..., I. The parameters Mj and Xji are
mutually consistent, which means that their product-the
amount of each component-represents a conserved
quantity, i.e. term in the component balance equation. The
presence of sources and/or sinks may be represented by
fictitious streams with the same formal parameters as in
vector (1). This is particularly important if a chemical
reaction occurs in the system. In such a case the
Fig. 1. Balance scheme containing 5 nodes and 12 streams. The
streams l-7 are external, while the internal streams are g-12. The
couples (1,2), (3,4), (6.7) and (10, 11)are parallel streams.

1199
1200 V. VACLAVEKand M. LOU~KA

parameter Mi can be simply related to the amount of 3. AN ALGORITHM FOR THE CLASSIFICATION
converted mass during the reaction and the parameters Xii OF STREAM PARAMETERS

depend on stoichiometry of the reactionD]. Thus the set (i) The stream parameters may be classified as follows:
of balance equations is of the form: The measured parameters can be divided into overdeter-
mined and not overdetermined parameters with respect to
&M&=0, k=l,..., i=l,... Z (2) the system of eqns (2) and (3). Also the measured
1-1 parameters can be classitkd into determinable and
and indeterminable parameters according to the same set of
equations.
2 x, = 1 The operation of reducing the balance scheme can be
i-1
used to classify the stream parameters. In the case of
single component balance calculations [4], [5] this opera-
j=l , . . . , J except with some (3) tion is done with respect to all the streams with
fictitious streams. unmeasured parameters. When the reduction operation is
completed a “reduced balance scheme” is obtained. It
(iii) When the composition of certain streams is contains only the streams with measured overdetermined
measured, it is measured for all components. Hence each parameters, while the measured parameters in eliminated
stream can be assigned to a category as in Table 1. streams are not overdetermined.
(iv) A reduction of the balance scheme[5] with respect In such a way the classification of measured parameters
to a given stream j’ involves one of the following is easily accomplished but the classification of unmeas-
operations according to the type of the stream j’: ured parameters has still to be done. Let us imagine for
(a) The addition of the nodes connected with the this purpose, that one classified unmeasured parameter is
internal stream j’, or additionally measured. Then the above mentioned reduc-
(b) The elimination of the node comected with the tion operation is now carried out with respect to all the
external stream j’. All internal streams originally coinci- streams with unmeasured parameters except for the
dent with the eliminated node become external streams. stream with classified parameter. If the reduced scheme
The reduction can also be carried out with respect to a after this modification is the same as the original reduced
group of parallel streams. After every step the balance scheme, then the classified unmeasured stream parameter
scheme is reduced by one node. The stream with respect is indeterminable. On the other hand, if it is greater by one
to which the reduction was carried out disappears along node and the stream with classified parameter remains in
with all its parallel streams. it, then the classified parameter is determinable.
The concept of reduction can be considered as a Thus it can be seen, that the classification of measured
“natural” decomposition of the set of eqns (2) and (3) as and unmeasured parameters is bound together. The
reflected in changes of the original balance scheme. Its determinable unmeasured parameter is determinable if
usefulness can be shown, e.g. if the least square method is considered as measured and vice-versa. And moreover it
applied to reconciliation of measured values of the can be proved that if some (required) determinable
parameters Mi and X& The objective function to be unmeasured parameters are taken for additionally meas-
minimized is then a sum of weighted squares of ured, then the modified reduced scheme contains besides
corrections. As far as some of the parameters are the streams with these parameters and the streams with
unmeasured, their corrections do not occur in the overdetermined measured parameters also the measured
objective function, but still exist in the constraints. not overdetermined parameters, which are indispensable
Therefore, the set of constraints (in fact equations for determination of required determinable unmeasured
analogous to eqns (2) and (3)) can be arranged by addition parameters (see Fig. 2.).
and elimination of certain equations so that the parame- The reduction process is more complicated in multi-
ters of unmeasured streams just disappear, which component mass balance calculations. We distinguish
corresponds to the addition and elimination of nodes in here between balance scheme reduced to the 1st and to
the balance scheme. However, it can happen that during the 2nd degree.
this arrangement corrections of some measured values (ii) A reduction to the 1st degree is carried out with
disappear from the set of constraints too. These respect to the following single streams or their parallel
corrections are then identical to zero which follows from combinations:
the form of objective function. (a) Single or parallel streams of the 4th category.

Table 1. Definition of stream categories

 Measurements necessary to achieve multicomponent mass balances in chemical plant
Fig. 2. Classification of measured and unmeasured parameters in
the one-component balance. Scheme given in Fig. 1. Stream-w is
measured and + is unmeasured. The reduction with respect to
unmeasured streams: (a) After addition of the nodes cdnnected with
internal unmeasured streams, (b) After elimination of the nodes
connected with external unmeasured streams. The measured
streams 1,2,5,6,7,8,9intheRBSareoverdetermined,themeasured
stream 11 is not overdetermined. (c) The modiied RBS if the
unmeasured stream 12 denoted i), is taken for measured. The
stream parameter 12as well as 10is determinable. On the other hand
if the indeterminable unmeasured stream 3 or 4 is taken for
measured, then RBSis the same as in Fig. 2(b).(d)The modifiedRBS
if all the unmeasured determinable streams (10, 11) are taken for
measured. The measurement of not overdetermined stream
parameter 11is indispensable to determine the stream parameter 10.
(b) Parallel streams of the 2nd and 3rd categories.
(c) I-parallel streams of the 2nd category, if their
composition is different (where I is the number of
components.)
At every step during the reduction the balance scheme
is considered as original. This means that a reason for
reduction such as b- and c can arise even during this
process. When the reduction is finished and all the
streams of types a, b and c have disappeared, the
reduced balance scheme of the 1st degree is obtained
(RBS 1). This scheme need not necessarily be continuous
even when the original balance scheme was continuous.
The following main conclusion can be proved. All the
measured parameters Mi in the RBS 1 are overdetermined
except for the case when a single measured Mi occurs in
some continuous part of this scheme. Then this parameter
Mj is not overdetermined. The reason for this exception
arises because eqns (2) are homogeneous when no value
of the extensive parameter Mj or Nji = MjXji is given. It
corresponds to the well known situation in current
balance calculations when one of the extensive parame-
ters can advantageously be chosen as the so-called basis
of calculation to avoid the general or not unique solutions
of a system of homogeneous equations.
(iii) A reduction to the 2nd step is carried out with
respect to all the streams of the 3rd category remaining in
the RBS 1. In this way we obtain a reduced balance
scheme of the 2nd degree, containing the streams of the
1st and 2nd categories only.
It can be shown that all the streams in the RBS 2 have
the measured parameters Xii overdetermined, except with
some special configuration of streams of the 2nd category,
1201
which is not expected to arise in practical applications.
(To discover this case, some numerical analysis has to be
applied. Let the measured or expected values of Xii be
substituted to eqns (2) and (3) generated for RBS 2 only.
While eqns (3) disappear for streams of the 1st and 2nd
category, eqns (2) become linear. As expected the
Frobenius condition should not be satisfied, otherwise the
measured parameters Xji in the RBS 2 are not overdeter-
mined).
The algorithm CLASS was developed based on the
theory outlined above. It can be used for the classification
of the measured parameters Mj and Xji according to rules
ii and iii. The classification of unmeasured parameters is
carried out successively for individual parameters as
formulated in rule i for the case of one-component
balances (see Fig. 3). The application of this algorithm is
illustrated later in this paper.
4.ANAL.GORll%IMF’ORTERDlRR4X
SELECTION OF m
A successive use of the algorithm CLASS to test
individual variants is an indirect method of designing
measuring places. However the direct selecting necessary
measurements would be a more advantageous. Algorithm
CHOICE is presented here to solve precisely this
problem. It was published previously for single compo-
nent balance calculations[2] and is extended here to
multi-component balances. This algorithm is also based
on the idea of classification.
Input information to CHOICE:
(i) Let all the parameters be either measurable (set A)
OIunmeasurable (set B). This assignment depends on the
technical possibility of the measuring methods.
(ii) Let all the parameters be either required (set C) or
not required (set D). This assignment depends on the
purpose of balance calculations.
(iii) Let a topology of the process be defined, e.g. in the
form of balance scheme.
Now the purpose of the balance calculations is to
choose a subset R of measured parameters A so as to
determine all the required parameters C in the balance
calculations.
The algorithm CHOICE consists of the following
operations.
(i) In the 6rs.t step all the measurable parameters are
assumed measured and the classfication of parameters is
carried out. In this way the following subsets are
obtained:
Al--a set of overdetermined parameters.
A-a set of not overdetermined parameters.
&-a set of determinable parameters.
B?a set of indeterminable parameters.
The sets A1 and A2 as well as B1 and BZare disjunctive.
(ii) The problem is solvable if the disjunction BZn C is
an empty set. Let this condition be satisfied in the problem
formulation. Otherwise the problem has to be reformu-
lated.
(iii) In the 2nd step all the measurable and all the
unmeasurable required parameters (which are all deter-
minable according to ii) are assumed measured for the
 0
START

+ a) the 4th category

b) parallel streams of the
2nd and 3rd category
c) l-parallel streams of

,
7
Reduce the scheme with respect FIBS 1 is obtained
to this (these) stream(s). Mea- containing streams
sured M, and X,, of streams of the lst, 2nd and
eliminated during reduc- 3rd category only
tlon are not overdetermlned

of either the 1st or 3rd

Thls measured M, is not over- All the measured M,

determined. The measured M, - in RBS 1 are over-
in other continuous parts determined
of RBS 1 are overdetermined

Reduce the scheme wlth respect RBS 2 is obtained

to thls stream. Measured XII contalnlng streams
of streams eliminated dur- of the 1st and 2nd
ing reduction are not over- category only
determined
I

+
streams of the 2nd ca-
tegory. Is the Frobenlus

1
1

All the measured X,, In the All the measured &I

RBS 2 are not over- _ In the RBS 2 are
determined overdetermlned

)r _ I
1
-
Classiflcatlon of measured
parameters is completed. To
classify the unmeasured pa-
rameters, consider them
successively to be measured
and repeat the classification

+
f-4
Is the originally unmeasured
classified parameter found
to be overdetermined? E-l
-

I I

The unmeasured parameter is The unmeasured parame-

determinable ter is indeterminable

Fig. 3. Block scheme of the algorithm CLASS for classification of measured and unmeasured stream parameters.
1202
 Measurements necessary to achieve multicomponent mass balances in chemical plant 1203

purpose of their classiftcation. In this way a set of required but cannot be used for reconciling other
overdetermined parameters E and a set of not overdeter- measured variables or for determining the set of
mined parameters F are obtained. unmeasurable and required parameters in set E,.
(iv) The final results are derived from the expressions: The set F2 involves all the measurable but not required
parameters, which are also not used indirectly, e.g. for
F,=FnCcR reconciling the parameters in set El or for determining the
(4)
Fz=FnDcS parameters in set E,. The set EZ contains the measurable
parameters which cannot be reconciled, but which must
and
be measured to determine the parameters in set &. The
E,=A,nEcT parameters in set El can be reconciled and in this sense
Ez=AzrlEcR (5) they contribute to the improvement of the accuracy of all
E,=BrlCcS. the required parameters, except of those in the set F,.
Hence the direct design of measuring places according
Set F, is the set of measurable parameters which are to the algorithm CHOICE is completed (see Fig. 4). The

START

0
t
Read input data:
a) Topology of balance
scheme
b) Sets A and B of
parameters
c) Sets C and D of
of parameters

Consider A parameters to be measured

and classify all the parameters by
1 the algorithm CLAY -1

I Sets A,. &, B,. B2 are obtained

Consider A and 8, rl C parameters to be

measured and classify the measured
parameters only by the algorlthm CLASS

Final results are in the following form:

a) F1 = F rl C and EP = AZ rl E have to be measured
b) Fa=FnD and L=BrlC are not measured
c) El = A, fr E need not be measured In whole
extent

Fig. 4. BlockschemeofthealgorithmCHOICEfortheselectionofnecessarymeasnrements.
1204 V. VACLAVEKand M. LOUCKA

sets R and S in eqns (5) represent the groups of measured
and unmeasured parameters respectively. The parameters
in set T need not all be measured. Several of these
parameters may occur in set S, nevertheless all required
parameters must be determinable. On the other hand, the
measurement of all parameters in the set T is useful as
they can be used either directly or indirectly for
reconciling of some required parameters C.
5. EXAMPLZ
The following example is proposed to illustrate these
two algorithms. One example only is presented since the
algorithm CHOICE uses the ideas of algorithm CLASS
for the reduction of the balance scheme before it can
design the measuring places.
Figure 5 shows the balance scheme used in this
Fig. 5. Balance schemefor 4 component mass balance calcula-
tions.
example. This 4- component system contains 6 nodes and
16 streams. The coding of one form of input information
for the program CHOICE is given in Table 2.
In the first step of algorithm CEOICE the classification
of measured and unmeasured parameters is carried out,
considering all the measurable parameters to be meas-
ured. The section of this operation concerning the
classification of measured parameters by reduction of the
balance scheme is presented in more detail. In this case
the distribution of streams amongst the various categories
is given in Table 3.
The scheme is then reduced to the 1st degree with
respect to streams of the 4th category, parallel streams of
the 2nd and 3rd categories and with respect also to Z-
parallel streams of the 2nd category. The RBS 1 obtained
is shown in Fig. 6(a). Further reduction of the scheme to
the 2nd degree with respect to streams of the 3rd category
yields the RBS 2 presented in Fig. 6(b). As mentioned
earlier the set A, includes all the parameters Mi in the
RBS 1 and the parameters Xii in the RBS 2. The other
measured parameters belong to set A,.
To classify the unmeasured parameters they are
successively assumed measured parameters and classified
as explained above. The final results after the 1st step in
algorithm CHOICE are shown in Table 4.
As is evident from Tables 2 and 4, no required

Table2. Input data for direct design of measuring places. l-yes; O-no
r 1
Sl ;7.-e&?tl TOPOlOgy Xeasurable parameter Required paramete
ir 1aex _- .-
from to
MJ xJi MJ xji
node node

1 0 1 1 1 1 1

2 2 1 1 ‘0 0 0

3 1 2 1 0 0 0

4 6 1 1 1 1 1

5 2 3 0 1 0 0

6 2 6 1 0 1 1

7 3 6 0 0 1 0

8 6 0 1 1 0 0

9 5 6 1 1 0 0

10 0 5 0 1 0 0

11 4 5 0 1 0 0

12 0 4 1 1 0 0

13 0 4 0 1 0 0

14 4 0 0 1 0 0

15 0 4 0 1 0 0

16 5 0 1 0 1 0

Table 3. Stream categories for the reduction of balance scheme in the 1st and the 2nd step of algorithm CHOICE

stream stream indices

category 1
The 1st step of CHOICE : The 2nd step of CHOICE :

1 1,4,8.9,12 1.4,6,8,9,12
2 5,10,11,13,14,15 5,10,11. 13,14,15
3 2,3,6,16 2,3,7,16
 Measurementsnecessaryto achievemulticomponentmass balances in chemical plant 1205

NOTATION

ati element in incidence matrix

A set of measurable parameters
AI,& sets defined in the 1st step of CHOICE
B set of unmeasurable parameters
4, & sets defined in the 1st step of CHOICE
E, ~5,-&El sets defined in the 2nd step of CHOICE
F,F,,F, sets defined in the 2nd step of CHOICE
C set of required parameters
D set of not required parameters
i, I index and number of components
LJ index and number of streams
(b)
k K index and number of nodes
Fig. 6. Reductionof the balanceschemefrom Fig. 5: (a)to the 1st
degree.(b)to the 2nddegree. M parameter of total amount of mass
Nii parameter of amount of component
R set of measured parameters
parameter is indeterminable, therefore the problem is
S set of unmeasured parameters
solvable. T set of parameters, some of which need not
In the 2nd step of algorithm CHOICE all the
be measured
measurable required unmeasured parameters are assumed parameter of concentration
x,
measured in the process of classification. In Table 3 a
REFERENCES
modification of the stream categories for the reduction in
this step is shown, and sets E and F are presented in [l] Vaclavek V., KubIEek M. and LouEka M., Theoret. osnouy
chim. technologii (in Russian) 19759 270.
Table 5. The final results obtained using the relationships 121Vaclavek V., Bilek Z. and Karasiewicz J., Verfahrenstechnik
(5) and (6) are tabulated in Table 6. 19726 415.
131Vaclavek V., Kubfeek V., I-&v&k V. and Marek M., Colin
Acknowledgement-Authorsare very grateful to Dr. N. Peters Czech. Chem. Commun. 1968Xi 3653.
from University of Western Ontario,London, Canada for many [4] Clemenson A. T., Chemical Processing 1966S14.
valuable remarks to this paper and correction of English. [S] Vklavek V., Chem. Engng Sci. 1%9 24 947.
r
Table 4. Results of classification in the 1st step of algorithm CHOICE

Streams indices
set Paraetir uj I Param?tcr XJi

Al 1,2,3,41&V 1,&V

A2 6J2.16 4,5,10,11.12.13,14.1
5,7,10,11,13,14,15 6,7.16
El
B2 2,3

Table 5. Results of classification in the 2nd step of algorithm CHOICE

Set Stream indices

Parameter I Parameter xji

fJ

E 1,~ , 3 , 4 a6 I 8 , 9 , 9,
145689 , ,
F 5.10,~. 12,13,1.4,15,16 2,3.7,10,11,12,13,14,15,16

Table 6. Final selection of measurements according to the algorithm CHOICE

1,2,3,4,-3,9
6

7
16
5,10.11,12, 2,3,7,10,11,1~,13
13.14115 14,15,x