The Role of Water in Iron Trichloride-Catalyzed

Chlorination of Benzene
Henk van den Berg*1 and Ríen M. Westerink
Chemical Engineering Laboratory, State University, Groningen, The Netherlands

The influence of small amounts of water on the reaction rate of the chlorination of benzene catalyzed by iron tri-
chloride has been determined. The reaction rate was calculated from the temperature rise caused by the chlorin-
ation carried out in a small, well isolated flow reactor. This reactor contained a homogeneous liquid mixture of
benzene, chlorine and catalyst. Comparatively small values of the reaction rates are obtained for ratios of the
concentrations FeCÍ3/H20 between 3 and 6. When this ratio is reduced below 2, a sharp increase of the catalytic
activity is observed. The catalytic active component is a monocomplex of iron trichloride and water, FeCI3-H20.
For the first time the influence of small amounts of water on the reaction rate of this reaction has been deter-
mined quantitatively.
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Introduction stants themselves. In contrast with the authors just men-

In industry most of the chlorobenzenes are produced in
continuous operation by liquid-phase chlorination. Usually
liquid benzene and gaseous chlorine dispersed in it flow co-
currently upward through a column packed with iron rings.
The reaction is catalyzed by iron trichloride, which is formed
in the reactor from chlorine and the iron rings. It is generally
known (see e.g. Braendlin and McBee, 1965) that in these
reactions no water should be present. In industrial processes,
therefore, the raw materials benzene and chlorine are dried.
In his extensive review “Friedel-Crafts and related reactions”,
Olah (1963) states, however, that “in general H20 and small
quantities of other contaminants enlarge the reaction rate in
nonaqueous solvents”. These statements seem contradictory
and could only be reconciled if, with respect to the catalytic
activity, an optimum would exist somewhere in the range of
very small traces of water.
Concerning the industrially applied continuous chlorination
of benzene, it is not clear in which process'step water exerts
its influence. Is it in the formation of the catalyst, i.e. in the
reaction 2Fe + 3C12 —
2FeCl3 which reaction is either ham-
pered or induced by water, or is it in the rate of the chlorina-
tion of benzene itself?
The main aim of the work described in this contribution was
to determine the influence of small amounts of water on the
reaction rate of the chlorination of benzene carried out in a
homogeneous reaction medium and catalyzed by dissolved
iron trichloride.
Kinetics. A Review of Literature
In Table I a survey is given of measurements of the rate of
the chlorination of benzene. A generalized rate expression for
the first step runs
r =
ka+b+c [Cl2]a[FeCl3]b[B]c
The subscripts of k indicate the order of the reaction rate
constant. For the second step [B] is replaced by [MCB] and
the reaction rate constant is provided with an accent. For the
third step we use k"a+b+c and [DCB],
Bourion (1920 a,b) was the first to publish about the ratio
of the reaction rate constants of the second and first steps,
fc2Vfc2. It was McMullin (1948) who added the ratio of the
third and second steps, fc2"/&2'. Lebedev and Baltadzhi (1961,
1963) first provided reliable values of the reaction rate con-
1
Address correspondence to this author at Dow Chemical (Ned-
erland) B.V., P.O. Box 48, Terneuzen, The Netherlands.
tioned, they carried out their experiments in homogeneous
media.
Lebedev and Baltadzhi measured the reaction rate in
mixtures of nitrobenzene (PhN02), CCI4, benzene, and FeCl3.
They found that the first-order reaction rate constant, k\, at
a given iron trichloride concentration, depends strongly upon
the quantity of nitrobenzene (a polar solvent) in the reaction
mixture (see Figure la). Cf. Table I.
The values for ki published by Schmidt (1968) are of the
same order of magnitude, but they were measured at catalyst
concentrations which were about 1% of the concentrations
used by the Russian authors and in reaction mixtures con-
taining B, MCB, DCB, but no PhN02. Schmidt, unlike Le-
bedev and Baltadzhi, mentions problems regarding the re-
producibility of the measurements. The reaction rate con-
stants in his experiments varied, occasionally by as much a
factor of 2. Considering the techniques used, his analysis was
accurate. It may be inferred, therefore, that these variations
were caused by other factors. Schmidt reports that in his ex-
periments the catalyst was easily poisoned, due to traces of
water, for example.
Donohoe (1968) discontinued measuring the reaction rate
of the chlorination catalyzed by FeCl3, because he was faced
with problems such as turbidity and decomposition of the
catalyst solution, which he ascribed to the influence of H20
on the catalyst.
The results of the last two authors point to the major part
which small quantities of water play in the activity of the
FeCl3 catalyst. For his reaction mixture, Schmidt found a
first-order dependence of the catalyst concentration in the
reaction rate expression. Lebedev and Baltadzhi, on the other
hand, found a decrease of this order starting with 3.5-4 in 12
vol % PhN02 + 80 vol % CCI4 to 1-1.5 in 92 vol % PhN02 (see
(1)
Figure lc).
In the literature no adequate description is given of the
reaction rate of the chlorination of benzene catalyzed by FeCl3
and carried out in a homogeneous mixture of the reaction
components. Two of the main problems were evidently the
solubility and the preservation of the FeCl3 catalyst. We de-
voted a separate study to this problem (Berg, 1973; Berg and
Gerritsen, 1976). The results are summarized as follows.
Dry iron trichloride is practically insoluble in dry benzene.
FeCl3 is only reasonably well soluble in B, if both FeCl3 and
FeCl3-2H20 are present in the solid phase. When this condi-
tion is fulfilled a monocomplex FeCl3-H20 will be formed in
the solution. If the solution is not in equilibrium with the two

164 Ind. Eng. Chem., Fundam., Vol. 15, No. 3, 1976

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Ind. Eng. Chem., Fundam., Vol. 15, No. 3, 1976 165

 — %vol PhN02

Figure 2. Experimental layout: 1, reactor; 2, measuring bridge; 3,

thermostat; 4, stock FeClg-HaO in B; 5, metering pump; 6, sedimen-
tation vessel; 7, magnetic stirrer; 8, washing bottle, B + CL; 9, Mar-
iotte’s vessel, B + Cl2; 10, capillary; 11, flowmeter; 12, mixer; T, To,
thermistors.
b. Schmidt
9x10"s<[FeCy<1,5x10"4
T. 20'C heat of hydration (-AH^lQFeCl^]
heat of reaction: r(-AH )V heat loss: Q(T-T )

heat contents of heat of stirring: h

^
entering flows: y
^ heat content of
d ,pc T exit flow:
'vi p 0
6 8 T
rvtot .pc p
,

d T
v2 pc 0
p
^ heat capacity of
reactor and contents
H + Vc p
P

Figure 3. Heat balance over the flow reactor.

Rate by Means of the Heat of the Reaction. The reaction

Figure 1. Literature data for (a) and (b) reaction rate constants; (c)
order of [FeCL],
solids mentioned, but with FeCls^FUO and FeCl3-%H20 or
with two higher hydrates, the solubility decreases sharply. At
all values of the ratio FeCls/B (kmol/kmol) in the mixture a
good solubility is guaranteed if the overall ratio H20/FeCl3
is 1.
The presence of HC1 increases the solubility of iron tri-
chloride. Generally, the percentage increase of the solubility
is larger if the overall ratio H20/FeCl3 in the system is larger.
The setup and interpretation of the kinetic investigation re-
ported now are based on this monocomplex concept.
Experimental Section
Apparatus Used for the Determination of the Reaction
rate of the first step has been calculated from the temperature
rise caused by the chlorination carried out in a small well
isolated flow reactor.
The continuously operated flow reactor was chosen because
the activity of the catalyst is preserved better under flow
conditions than in a batchwise operated reactor. Both by
measurement of the rise in temperature, and by chemical
analysis, the reaction rate can be determined for small con-
versions of the B feed. The first method, however, gives im-
mediate information of the reaction rate occurring and enables
us to determine the reaction rate under unsteady-state con-
ditions. The principle of the determination of the reaction rate
by measurement of the rise in temperature has been known
for many years; see, e.g., Rand and Hammett (1950).
The reactor consists of a small flow reactor placed in a
thermostat, accuracy: ±0.002 °C. Two streams of benzene
enter the reactor: the one containing B + FeCls, the other B
+ Cl2. Long spiral glass tubes guarantee that the B-feeds into
the reactor reach the temperature of the thermostat within
0.002 °C. The conversion is determined by the difference in
temperature between the reactor and the thermostat, mea-
sured by two thermistors (Philips E 205CE P 100k). The signal
obtained from these thermistors is fed to a modified Wheat-
stone bridge constructed by Knauer (Berlin). In order to apply
this principle of measuring accurately, the reactions that occur
and the heat effects of the reactions must be known.

166 Ind. Eng. Chem., Fundam., Vol. 15, No. 3, 1976

 Figure 2 shows the experimental layout. Provisions are
made for the possibility of varying the concentrations of cat-
alyst, CI2, HC1, and H2O. To minimize loss of heat the reactor
itself has a double evacuated wall which is covered with a thin
layer of metallic silver.
The relation between the reaction rate and the difference
in temperature measured is described in a heat balance over
the reactor; cf. Figure 3. The resulting expression for the re-
action rate is
(T —
ToXtfvtotCpP + Q) +
As the concentrations of CI2, HC1, and catalyst are small,
variations in cp, p, and heats of mixing can be neglected. The
temperature rise which is used in the following sections, in-
dicated by T To, has been corrected for the small temper-
—
ature rise caused by stirring, hst.
Due to construction details, e.g., fixed glass inlet and outlet
tubes, the reactor volume had to be calculated from the resi-
dence time distribution of the liquid in the reactor. We found
V 7.0 X 10-6 m3 for this perfectly mixed system.
=
The heat-loss factor, Q 4.5 X 10-2 Js-1 °C~1 has been
=
determined by dilution of sulfuric acid in the reactor under
steady-state conditions. Then, the terms for the reaction heat
of the chlorination and the heat of hydration of FeCls in eq 2
are substituted by the heat from mixing H2SO4 and H2O. The
latter and cpp are known, /dt is zero, so Q can be calculated.
The heat capacity, 16.8 J °C_1, was determined by
= 4- H2O + 01( 2). HC1 is added to simulate the conditions
measuring the cooling curve of the reactor. In that case tot
and the heat of hydration are zero.
Provided that the reactor is fed with B and not with MCB,
only the first chlorination step takes place since the conversion
in the reactor is small, 0.5 mol % or less. The heat of reaction
for the first step, / , amounts to —134.106 J kmol-1
(Groggins, 1958; Kirkbride, 1956). The product cpp amounts
to 1.55 X 106 J m-3 °C_1 for pure benzene. Using these con-
stants eq 2 becomes
r =
(T -
To')(0vtot 1.55 X 106 + 4.5 X 10~* 2) + ^dt
940
tot (—AHh)[FeCl3]
A relation to calculate the heat of hydration is given in the
next section. To calculate the reaction rate we measure: T
T0' (0.15 3.5 °C), plus dT/dT if experiments are carried out
—
under unsteady conditions; 0vtot> which is determined by
measuring the total exit flow from the reactor or by summing
i and 2\ 0vi(B + FeCl3), which is determined by an accu-
rate, calibrated metering pump (Telab BF 411/250); and </>v2ÍB
+ CI2), determined by reading a calibrated flowmeter.
The catalyst solution is prepared as follows. To a 1-1. vessel
are successively added 11 of B, 16 g of FeCls, and 0.9 g of H2O.
After having been sufficiently stirred, the catalyst solution
is pumped into the reactor. The catalyst solution gave initially
the same problems as described by Donohoe (1968) and
Schmidt (1968). We found that the catalyst solution prepared
in this way contains a monocomplex of iron trichloride and
water. In contrast with the higher hydrates of FeCls and H2O,
only this monocomplex, FeCls-E^O, is fairly well soluble in
benzene (cf. Berg, 1973; Berg and Gerritsen, 1976).
The CI2 fed into B to prepare the B + CI2 solution is purified
by CUSO4 and P2O5 to remove traces of iron and H2O, re-
spectively. The concentration of CI2 is found by mixing a 2-ml
sample of the organic phase with a 70 ml of 0.1 N KI solution.
This mixture is titrated with a thiosulfate solution. To de-
termine the acid concentration, the mixture is further titrated
with 0.1 N NaOH. The concentration of the organic compo-
nents is determined by GC analysis. Iron is determined by
atomic absorption analysis. Concerning the H2O analysis, a
GC technique has recently been published by Berg and Olst
(1973).
The concentrations in the reactor are found by means of (a)
—
(Vcpp + H)
—
0vtot( -
Affh) [FeCls] —
hst
at
(-AHr)V
chemical analysis of the exit stream from the reactor and (b)
determination of the concentrations in the entering flows and
by multiplying them with a factor / or 2/ · To
obtain the concentrations of the components which are formed
or used by reaction, these concentrations should be increased
or reduced by a term r6.
The Hydration of FeCls-HsO. Further hydration of
FeCls-H20 will be accompanied by a heat effect. The for-
*,
mation of higher hydrates might take place during the chlo-
rination reaction: the B 4- FeCls feed contains FeCls-HsO
which might be further hydrated by the H2O present in the
B 4- CI2 feed. The occurrence of this phenomenon was estab-
lished by measuring this heat effect in the flow reactor by
applying a feed of B + FeCls-HsO^vi) and a second flow B
of the chlorination reactions and to prevent precipitation of
the higher hydrates. The experiments are carried out under
steady-state conditions. Then (2) is reduced to
0
=
ATh(</>vtotCpp 4- Q)
—
0vtot(~A/ih)[FeCls]
or
ATh(cpp 4- Q/cftytot)
-Affh =
(3)
[FeCls]
The dots in Figure 4 represent the values for — H^, cal-
culated from the differences in temperature. The experiments
(10.9 + 16.8) were carried out at 25 °C, while [HC1]/[H20] varied from 0.4
to 3. The line in the figure is obtained by connecting the values
of the heats of dilution given by Perry (1963); see Table II.
Since the monocomplex FeCls-HsO enters the reactor, we
shifted the ordinate in such a way that the heat of dilution of
FeCls-HsO (complex) was taken as a standard, or AHh = 0 —
for FeCls-HsO. The results of the chlorinations, which are
described in the following sections, show that the rise in
—
temperature (given by Berg and Gerritsen, 1976) caused by
hydration is small, usually about 5% of thd rise caused by the
chlorination.
(-Affh)[FeCls] ,
h
(cpp + Q/ tot)
For the sake of simplicity, we use the straight line, formu-
lated by eq 4; only a minor error in the determination of the
reaction rate of the chlorination is introduced.
for 1 < [H20]/[FeCl3] < 6 (4)
The heat effect due to the hydration has also to be taken
into account in the chlorination reactions carried out. The
dependence of the temperature of the reaction rates measured
is caused by activation energies of the chlorination and the
hydration reaction.
Check of the Measuring Procedure. The reaction
rates measured by employing the method of difference in
Ind. Eng. Chem., Fundam., Vol. 15, No. 3, 1976 167
 Figure 5. Apparatus for mixing the organic phase with an aqueous
KI solution (reaction quencher).

Figure 4. Heat of hydration of FeCls-^O.

Table II. Heats of Dilution and Hydration of FeCl3 Hydrates

-AHdil, 106 J -AHh, 106
kmol"‘a (10"3 kg J kmol'1 (ref.
in 1 kmol of H20) FeCl3-H20 O) =

FeCl3 133
FeCl3—H20 0
FeCl3’5/2 H20 88.2 26.8
FeCl3-6H20 23.5 91.5
a
Perry (1963).

temperature are indicated by rAr and are calculated according

to eq 2.
A reliable calculation of the reaction rate is of vital impor-
tance for our experiments. We verified the measurement of
r at by calculating the reaction rate from the decrease of the
chlorine concentration over the reactor. This check was carried
out by application of a special device shown in Figure 5.
A thorough mixing of the organic phase with a 0.1 N KI
solution stopped the reaction. This “reaction-quencher” was
connected with the reactor exit. As the reaction proceeds in
the exit tube until it is stopped by KI, the volume and conse-
quently the residence time, , increase by a factor 1.04. The
reaction rate is calculated from
[C^lin ~
in the alternative feed was filled with benzene without CI2,
having the same [H2O] as the B + CI2 stock in the Mariotte’s
flask, so the concentration of CI2, fed into the reactor, in-
creased steadily. In accordance with the conception of ideal
mixing, we found an exponential curve for [612)2 vs. time.
From this curve the mean residence time in the mixer, ', and
the volume of the mixer, V' =
'/ 2, were calculated. We
measured [C^jout by application of the reaction-quencher. A

[Clalout small correction on [CI2] out, for the reaction in the exit tube,
7aC12
=
(5) gives the chlorine concentration in the reactor. The above
1.046
method enabled us to determine the influence of [CI2] keeping
[Cldin = ~
2
[Cldz (6) all other variables at a constant level.
tot In runs A-6 and A-7 we aimed at the introduction of varia-
In accordance with tions in [H2O]. In A-6 we started with “dry” B in the mixer and
(subscript 2 refers to the (B + CI2 feed).
Schmidt (1968) we formulate with “wet” B in the Mariotte’s flask, so
[H20]2 =
[ 2 ]2, =0 + ([H20]Mariotte ~

k2*
[Cl2] [FeCls]
Figure 6 shows that a close accordance exists between k*2at
and k*2ACi2· We conclude that the measurement of the reac-
tion rate by the method of differences in temperature is a re-
liable experimental procedure.
The Influence of Variations of the Concentrations of
FeCls, CI2, H2O, HC1, and the Temperature on the Reac-
tion Rate, a survey of the experiments carried out is given in
Table III. In runs A-2 and A-3 additional variations in the
catalyst concentration were induced by changing the B +
catalyst flow, , to the reactor. The B + CI2 feed in the A-4
run contained a fixed concentration of HC1.
In order to vary the chlorine concentration we used the al-
ternative B + CI2 feed, given in Figure 2 (run A-5). The mixer
[H20]2,t = o) e~t/e
(7) (8)
In run A-7 we provided the Mariotte’s flask with “dry” B
and the mixer with “wet” B.
Results
Determination of the Reaction Rate by the Proce-
dure. In runs A we measured the reaction rate as a function
of a number of variables at 28 °C. To interpret the reaction
rates measured, we use eq 7 in which a first-order dependence
of [Cl2] and [FeClg] on the reaction rate is assumed. From A-5
it appeared that r at varied linearly with [CI2] and that k 2* was
independent of [CI2]. Runs A-6 and A-7 showed that k2* de-
creased steadily by increasing [H2O]. Taking into consider-
ation the presence of the hydrates of FeCla in the reaction

168 Ind. Eng. Chem., Fundam., Vol. 15, No. 3, 1976

Table III. Experimental Scheme for the Determination of
the Reaction Rate Constant, Catalyst FeCl3
Run Aim of experiment Experimental layout used
A-l | check of -measuring See Figures 2 and 5
(method
A-2 (effect of variations in See Figure 2
A-3 J[FeCl3]
A-4 effect of surplus HC1 See Figure 2
A-5 effect of variations See Figure 2 (alternative
in [C1J Cl2 feed) and Figure 5
A-6 1effect of variations See Figure 2 (alternative
A-7 Jin [H20] Cl2 feed)
B-l )
B-2
J- determination of Ea See Figure 2

mixture, we plotted the values calculated for k2* as a function

of [H20]/[FeCls]; see Figure 7.
The measurements can be represented by the following
correlation, calculated by regression analysis
k2* = 72.8e-L57([H20]/[FeCi3J) + 0.46 (9)
We observe that the value for k2* increases if the ratio
[H20]/[FeCl3] is reduced. Seeing that [H20]/[FeCl3] = 1 in the
catalyst feed to the reactor, and some water is always intro-
duced into the reactor by the (B + Cl2) feed, we can only de-
termine k2* for [H20]/[FeCl3] > 1. We assume that the highest
value for k2* is obtained at [H20]/[FeCl3] = 1. Moreover, the
accuracy of the determination of k2* for 1 < [H20]/[FeCl3] <
2 is less than for the higher values of [H20]/[FeCl3]. The es-
timated accuracy of k2* = 15.6 for [H20]/[FeCl3] = 1 amounts
to 50%. The estimated accuracies of the measured values of
k2* and of [H20]/[FeCl3] for four experiments arbitrarily
chosen are marked in Figure 7. Variations in [HC1] had no
significant effect on k2*, so far as we could detect.
Discussion
Considering the equilibria of the hydrates of FeCl3, we have
worked out how the fraction of iron trichloride present as the Figure 8. The fraction catalytically active FeCl3 vs. [H20]/[FeCl3].
monohydrate decreases if the ratio [H20]/[FeCl3] increases;
see Appendix. The results are given by triangle marks in
method to determine this active fraction, and that some as-
Figure 8.
The line in Figure 8 is obtained from the measured reaction sumptions have been made in the calculation based on esti-
rates on the assumption that the monocomplex FeCl3-H20 mated values of the free enthalpies of the hydrates, the results
is also the active catalyst in the chlorination reaction. In this of these two methods agree fairly well.
way we can write the reaction rate equation as follows Finally we shall give the fraction of the active catalyst based
on eq 9
k2[Cl2][FeCl3-H20] [FeCl3] (10)
gf^C]
=
r =
k2[C\2]
[ [^3^]2°] = 4_66e-l.B7([H20]/[FeCl3]) + 0.03 (13)
Thus [FeCl3J
and
[FeCl3-H20]
,
Ro----:- k2* (ID k2 =
15.6 s'1 kmol"1 m3 (T = 28 °C) (14)
[FeCl3]
The values for k2* contain the fraction FeCl3 present as mo- The ranges of concentrations in which our experiments have
nocomplex and the true reaction rate constant k2. been conducted are: 0.07 X 10-2 < [Cl2] < 6.0 X 10-2; 0.1 X
In view of the relation given by Figure 8, we assume that this 10~2 < [HC1] < 7.0 X ”2; 0.2 X 10"2 < [FeCls] < 10"2; 0.5 X
active fraction of iron trichloride is at its maximum when '2 < [H20] < 2.7 X 10-2. The concentration ranges applied
[H20]/[FeCl3] 1. In this way the decrease of k2* with
=
for Cl2 and HC1 are limited by the fact that the reactors’
[H20]/[FeCl3] is explained as a reduction of the catalytic ac- contents must remain homogeneous, which means that gas
tivity of iron trichloride generation must be avoided.
/ [H2Q] \
To obtain the activation energy we carried out the chlo-
[FeCl3-H20] k2* _

_
rination of benzene at 28, 39, and 51.5 °C. For the measure-
[FeCls] 15.6 V [FeCls]/ ments at 39 and 51.5 °C, runs B-l and B-2, the experimental
Comparing the triangle marks with the line given in Figure layout given in Figure 2 was used. The fraction of the catalyst
8, we have evidence that the complex FeCl3-H20 is actually which is active can be calculated with eq 13.
the active catalyst in the chlorination reaction. This active We obtained as mean values, at 39 °C
fraction was obtained from reaction rate measurements and
k2 = 27 s-1 kmol-1 m3 (15)
from estimates of free enthalpies of FeCl3 hydrates. In spite
of the fact the measurement of the reaction rate is not a direct for T = 51.5 °C

Ind. Eng. Chem., Fundam., Vol. 15, No. 3, 1976 169

 F.CI3nH20 Table IV. The Fraction of Active Catalyst3
MgCI2nH20
[H20 ] /[FeCl3 ] [FeCl3—H20] /[FeCl3 ]
1.2 0.8
1.5 0.6
1.75 0.35
2.0 0.25
2.0 0.18
3.0 0.11
4.0 0.04
3Landolt, . H., Bdrnstein, R., “Zahlenwerte and
Funktionen aus Physik .”, Band II, 4. Teil, s.209,
. .

Springer-Verlag, Berlin, 1961. Perry, J. H., Ed., “Chemical

Engineers’ Handbook”, 4th ed, Vol. 3, p 137 McGraw-
Hill, New York, N.Y., 1963. Lange, N. A., Ed., “Hand-
book of Chemistry”, 5th ed, p 1594, McGraw-Hill, New
York, N.Y., 1967.

with a reproducible activity and can now fairly accurately

Figure 9. Enthalpies of formation and free enthalpies of formation predict the chlorination rate.
of MgClz and FeCls hydrates.

Appendix
Calculation of the Fraction [FeCls-HaO]/ [FeCls]. The
&2 = 56 s-1 kmol 1
m3 (16) fraction of active catalyst [FeCl3-H20]/[FeCl3] was calculated
on the assumption that an equilibrium exists in benzene be-
Thus for the first step we compute: Ea = 43.106 J kmol-1.
tween the hydrates of ferrichloride. For 1 < < 2, [H20]/ =

Conclusion [FeCl3], the following reaction occurs

We measured reaction rates of the chlorination of benzene FeCl3.nH20 —
(2 -

n)FeCl3-H20 + (n -

l)FeCl3-2H20
and found that the monocomplex FeCl3-H20 is the active (Al)
catalyst in this reaction. When we compare the data given in
the literature, cf. Figure 1, we are first of all struck by the fact This means that for a ratio 1 < [H20]/[FeCl3] < 2, FeCl3-H20
that there is a discrepancy between the values of the first- and FeCl3-2H20 are formed. Further, an equilibrium exists
order reaction rate constants found by Lebedev and Baltadzhi 3FeCl3-2H20 ^ FeCl3-H20 + 2FeCl3-%H20 (A2)
and those found by Schmidt.
Secondly, for the catalyst concentration used by Lebedev and
and Baltadzhi, [FeCls] = 0.0113, we calculated from our ex- [FeCl3-H2Q][FeCl3-%H2Q]2
perimental results: k\ = r/[Cl2] < 1.5 X 10-2 s-1 (because ki (A3)
= 1.5 X 10-2 for [H20]/[FeCl3] = 1 and k\ < 1.5 X 10-2 for
[FeCl3.2H20]3
[H20]/[FeCl3] > 1). A great number of our experiments were Due to the equilibrium given in (A2), the concentration
carried out at 1.7 < [H20]/[FeCls] < 3. For [H20]/[FeCl3] = monocomplex is increased at the cost of the concentration of
2.2, e.g., the active fraction of the catalyst is 0.18. This value the dihydrate. For 1 < < 2 the formation of higher hydrates
for k\ equals the mean value found by Lebedev and Baltadzhi. has been neglected. If > 2 higher hydrates are formed ac-
Finally, unlike these authors, we measured a first-order cording to
dependence of the reaction rate of [FeCls]. These effects may nFeClg-nf^O —
FeCl3-H20 + (n -

l)FeCl3-(n + 1)H20
be caused by the complexing properties of the solvent used
(A4)
by Lebedev and Baltadzhi and by the influence of water which
they do not account for. and
Schmidt’s values for the first-order reaction rate constant
[FeCl3-H2Q][FeCl3-(n + l)H2Q]n-1
are about 0.45 X 10-3 s-1 at [FeCls] « 10-4 kmol m-3 which (A5)
is only 1% of the catalyst concentration used by Lebedev and [FeCl3-nH20]n
Baltadzhi. Schmidt’s values in pure B agree with our data for To calculate K for the equilibria mentioned, the free en-
[H20]/[FeCl3] * 1.6, and he claims that ki is independent of thalpy changes for the equilibrium reactions A2 and A4 must
[MCB], In view of the spreading of his results, we cannot agree be known. We assume that the differences of the free
with this conclusion. enthalpies of formation between the hydrates dissolved in the
As to the activation energy, we find that only the Ea value nonpolar solvent B are equal to the differences of the solid
found by Lebedev and Baltadzhi for chlorination of B in ni- hydrates. Thus for (A2): *µ = Gf° (FeCl3-H20) + 2Gf°
trobenzene accords with the value found in our experiments. (FeCl3.%H20) -

3Gf°(FeCl3.2H20) = RT In K. The free

—

The diversity in the other values may have been caused by the
addition of CCL and PhN02 to the reaction mixture (Lebedev
and Baltadzhi) or by inaccurate k measurements (Schmidt).
The essentially new point of our investigation is that, for
the first time, the activity of the iron trichloride catalyst as
a function of the water content of the reaction mixture has
been determined quantitatively. By studying the solubility
of FeCl3 in benzene as a function of the water content of the
mixture, we were able to get a better insight into the behavior
of the catalyst (Berg and Gerritsen, 1976).
The well-known phenomenon of “catalyst poisoning” has
enthalpies of formation are not given in the literature, how-
ever. They are estimated from the values known for the hy-
drates of MgCl2. The enthalpies of formation and the free
enthalpies of formation of the MgCl2 hydrates are given in
Figure 9 by triangle marks (Landolt and Bdrnstein,1961;
Perry, 1961). As to the hydrates of iron trichloride: only the
enthalpies of formation of FeCl3 and of FeCl3-6H20 and the
free enthalpy of formation of FeCl3 are known (Landolt and
Bdrnstein, 1961; Perry, 1961). See the dots in Figure 9.
As for the MgCl2 hydrates, a comparison of the free
enthalpies with the enthalpies shows that TSf° (Gf° = H°
—

been described. We are now able to prepare catalyst solutions TS{°) is small in comparison with Gf° and H°. Secondly, two

170 Ind. Eng. Chem., Fundam., Vol. 15, No. 3, 1976

parallel lines are observed in Figure 9 for the values of H{° of T -

To' = temperature difference measured over the flow

the hydrates of MgCl2 and FeClg. We assume, therefore, that reactor, °C
the same relation also holds for the values of Gf° of the hy- t = time, s
drates of MgCl2 and FeCls. Since G¡° for FeCls is known, we V, V = volume, m3
are now able to calculate Gf° for the hydrates of FeCls. If data
[ ]
=
concentration, kmol m-3
', = mean residence time, s
for Hf and Gf° of other metal chlorides (e.g. BaCl2, CaCl2, =
density of liquid, kg-3
and NiCl2) and their hydrates are used as a basis of the anal- oi, = liquid flow rate, m3 s-1
ogy, the same results are obtained quantitatively. A plot of the
values of G° (FeCl3-nH2) vs. [H20]/[FeCl3] is a straight line. Subscripts
It appears therefore, that for all equilibria between the hy- 0 = start, feed
drates of FeClg, K 1.
= tot = total
On the basis of the data mentioned above, we calculated the AT, AC12 = indication of the measuring method applied
fraction active catalyst, [FeCl3-H20]/[FeCl3] as a function of B, MCB = concerning benzene, monochlorobenzene
the degree of hydration, [H20]/[FeCl3], The results are given
in Table IV. Literature Cited
Berg, H. van den, Olst, H. van, Anal. Chem., 45 (11), 1967 (1973).
Nomenclature Berg, H. van den, Doctor’s Thesis, State University of Groningen, Groningen,
The Netherlands, 1973. (Available from University Microfilms, Ann Arbor,
B =
benzene Mich. 48106, under number 74-19,368).
cp
=
specific heat, J kg-1 °C-1 Berg, H. van den, Gerritsen, D. J., to be published in J. Chem. Eng. Data, 1976.
D =
diffusivity of Cl2 dissolved in B, m 2 c—1 Bourion, F., Comp. Rend., 170, 1319 (1920a).
Bourion, F., Ann. Chim. (Paris), 14, 215 (1920b).
DCB dichlorobenzene
=
Braendlin, . P., McBee, E. T., in “Friedel-Crafts and Related Reactions", Vol.
Ea = activation energy, J kmol-1 °C-1 Ill, Part II, p 1517 ff, G. A. Olah, Ed., Interscience, New York, N.Y., 1965.
=
heat capacity of the flow reactor, J °C-1 Donohoe, W. A., Ph.D. Dissertation, Princeton University, Princeton, N.J., 1961).
AHdii = heat of dilution, J kmol-1 Groggins, P. H., “Unit Processes In Organic Synthesis", 5th ed, p 212,
McGraw-Hill, New York, N.Y., 1958.
, = heat of hydration, J kmol-1 Kirkbride, F. W., J. Appl. Chem., 6, 11 (1956).
HT = enthalpy change over a reaction, J kmol-1 Lebedev, N. N., Baltadzhi, I. I., Kinet. Cata!., 2, 182 (1961).
k\ = first-order reaction rate constant, s-1 Lebedev, N. N., Baltadzhi, I. I., Kinet. Catal., 4, 778 (1963).
McMullin, R. B„ Chem. Eng. Prog., 44, 183 (1948).
k2 = second-order reaction rate constant, s-1 kmol-1 n Olah, G. A., Ed., "Friedel-Crafts and Related Reactions", Interscience, New York,
k3 = third-order reaction rate constant, s-1 kmol-2 m6 N.Y., 1963.
k2* = rl Cl2 FeCl3 _1
kmol Olah, G. A., Kuhn, S. J., Hardle, B. A., J. Am. Chem. Soc., 86, 1055 (1964).
k3* = rl Cl2 FeCl3; [B], s-1 kmol-2 m6 Perry, J. H., Ed., “Chemical Engineers' Handbook”, 4th ed, pp 3-145,
McGraw-Hill, New York, N.Y., 1963.
MCB = monochlorobenzene Rand, M. J., Hammett, L. P., J. Am. Chem. Soc., 72, 287 (1950).
Q = heat loss factor, J °C-1 s-1 Schmidt, E. H., Ph.D. Dissertation, Clarkson College of Technology, Potsdam,
r = rate of reaction per unit volume, first chlorination step, N.Y., 1968.
kmol m-3 s-1
r' = rate of reaction per unit volume, second chlorination step, Received for review October 8, 1974
kmol m-3 s-1 Resubmitted March 22, 1976
T = temperature, °C or K Accepted April 21, 1976

Controllability of Process Systems. Application of Harriott’s

Index of Controllability

Carl P. Jeffreson
Chemical Engineering Department, University of Adelaide, Adelaide, S.A. 5001, Australia

The problem of predicting the controllability of a system under feedback (proportional, integral) control from the
open loop dynamic equations was considered by Harriott, who proposed an index of performance, I, which com-
bines two easily calculated parameters of the open-loop system. In this paper, an attempt has been made to cor-
relate the reciprocal, 1, of Harriott’s simplified index against three commonly used indices of closed-loop sys-
tem performance. For systems consisting of a dead time and a simple lag, the minimum integral time-weighted
absolute error following a step disturbance was found to be related over a wide range of system parameters to
1 by the approximate formula: ITAE = M/-1)*1 where Ac- and k2 are tabulated constants. A similar correlation
resulted for the minimum Integral-square error for systems consisting either of multiple first-order lags or of a
dead time with one or two first-order lags. The minimum integral absolute error was found to be approximately
proportional to G1 only if a third parameter, , defined in the paper, is held constant.

The widespread availability of computers for the solution designer still needs rapid answers to relatively simple prob-
of complex systems of linear and nonlinear differential lems such as those listed below, if only to narrow the field of
equations has not removed the need for “short cut” methods investigation before applying more sophisticated techniques
of process control systems analysis. The process engineer or of analysis.

Ind. Eng. Chem., Fundam., Vol. 15, No. 3, 1976 171