152 Ind. Eng. Chem. Process Des. Dev.

1985, 24, 152-159

a lower cost of the reagents and a great facility for re- c = cation
generation. g = gas
Nomenclature aq = aqueous
1 = at the interface
A = nitrogen monoxide, NO 0 = in the bulk of solution
B = nitrogen dioxide, NO2 w = water
E = complex, Fe(NO)S04
R = ferrous sulfate, FeS04 Superscripts
D = diffusivity coefficient, cmz/s ’ = referred to the same conditions of NOz
F = enhancement factor, dimensionless - _- average
I = ionic strength of solutions, mol L
/
Ha = Hatta number, (kzRJIA/kL!) l 2 with film theory and
Registry No. NO, 10102-43-9; NOz, 10102-44-0; FeSO,,
with penetration theory 7720-78-7;H2S04,7664-93-9.
J = absorption rate per unit interfacial area, mol/(cmz s)
K = equilibrium constant for reaction 1, L/mol
k , = salting out parameters, L/mol Literature Cited
k2 = forward reaction rate constant for reaction 1, s-l
kl = reverse reaction rate constant for reaction 1, s-l Andrew, S. P. S.; Hanson, D. Chem. Eng. Sci. 1961, 14, 105.
Hlkita, H.; Asai, S.; Ishlkawa, H.; Hirano, S. J. Chem. Eng. Jpn. 1977, 10,
kL, k = liquid-side mass transfer coefficient in the absence 120.
of chemical reaction, cm/s Kustln. K.; Taub, I.A.; Weinstock, E. Inorg. Chem. 1966, 5 , 1079.
n = stirrer speed, rpm Onda, K.; Sada, E.; Kobayashl, T.; Kito, S.; Ito, K. J. Chem. Eng. Jpn. 1970,
p = partial pressure, atm 3 , 18, 137.
Sada, E.;Kumazawa, H.; Tsuboi, N.; Kudo, I.; Kondo, T. Ind. Eng. Chem.
t = exposure time, s Process Des. D e v . 1970, 17, 321.
z = empirical constant, L/mol Streuli, C. A.; Averell, P. R. “Analytical Chemistry of Nitrogen and Its
z = defined by eq 5, dimensionless Compounds”, Part 1, Vol. 28 of “Chemical Analysis”; WUey-Interscience:
a = Bunsen absorption coefficient, dimensionless New York, 1970; p 99.
Wilke, C. R.; Chang, P. AIChE J. 1955, 1 , 264.
v = kinematic viscosity, mz/s
Subscripts Received for review July 25, 1983
a = anion Accepted March 5, 1984

Kinetics and Mechanism of the Catalytic Hydrochlorlnation of

Acetylene to Vinyl Chloride by Use of a Transient Response
Technique
Ajlt K. Ghosh and John B. Agnew*
Department of Chemlcal EngineerlngsMonash University, Ckytm, Victoria, 3 168, Australla

Results are presented for an experimental study of the kinetics of acetylene hydrochlorinationto vinyl chloride over
mercuric chloride catalyst on activated carbon by a transient response technique. Transients are produced by
introducing step and pulse concentration changes in the feed stream to an internally recycled reactor. Elemen-
tary-step rate constants for a dynamic kinetlc model are estimated from measuredgas-phase concentration profiles.
A break in the slope of the Arrhenius plot at a temperature of 140 OC is shown to be due to a change in reaction
mechanism. Predicted transient behavior for a well-mixed reactor is closer to experimental data when the dynamic
reaction is used than is the case when a steady-state kinetic model is employed.

Introduction permits the experimental kineticist and design engineer

Steady-state kinetic models for catalytic reactions are
generally based on Langmuir-Hinshelwood rate expres-
sions (Hougen and Watson, 1948). However, this method
assumes the existence of a single rate-controlling step with
the other steps in equilibrium; the concept is restrictive
in the sense that instrinsic kinetics and reaction mecha-
nisms may not be properly revealed. On the other hand,
an elementary-step approach yields a more complete de-
scription as it more closely describes the microscopic events
involved, providing a more reliable basis for extrapolation.
The general availability of high-speed computers now
* Chemical EngineeringDepartment, University of Adelaide,
SA-5001, Australia.
0196-4305/85/1124-0152$01.50/0
to utilize more complex kinetic expressions which describe
fundamental catalytic processes more closely.
The use of transient response methods in homogeneous
catalysis is well documented. However, the application of
such techniques to heterogeneous catalytic systems gath-
ered momentum only during the mid-1970s. Yang et al.
(1973) and Kobayashi and Kobayashi (1973) were among
the first to implement the technique. Reactors ideally
suitable for transient studies, various method of pertur-
bation, and other criteria needed for better representation
of transient data are discussed elsewhere (Kobayashi and
Kobayashi, 1974; Bennett, 1976; Ghosh, 1981).
This paper is concerned with the implementation of a
transient response technique to study the kinetics of a
complex reaction system in which all the gaseous compo-
0 1984 American Chemical Society
 Ind. Eng. Chem. Process Des. Dev., Vol. 24, No. 1, 1985 153

nents adsorb onto the catalyst surface; also, catalyst

deactivation occurs and reaction mechanism appears to
change within the usual temperature range.
Vinyl chloride can be manufactured either from ethylene
or acetylene. In recent years, ethylene has almost com-
pletely displaced acetylene, although there are currently
indications that acetylene could well return to prominence.
Acetylene is reacted with hydrogen chloride over mercuric
chloride impregnated on activated carbon at a temperature
Wesselhoff et al. (1959) concluded from experimental
investigation that both hydrogen chloride and vinyl chlo-
ride are strongly adsorbed into the catalyst surface. Data
for adsorption equilibria of all those components have been
determined by Ghosh (1981). Depending on whether one
reactant and product or both reactants and product are
adsorbed onto the catalyst surface, the following reaction '

of about 140 OC and 1-2 bar pressure. The earliest com- sequences comprising elementary reaction steps can be
prehensive paper on acetylene hydrochlorination kinetics proposed
was published by Wesselhoft et al. (1959). Recently,
Shankar and Agnew (1980) studied the reaction a t higher sequence I
temperatures and examined the deactivation kinetics. In
all earlier studies, a single steady-state rate equation was H + S &k-ikH : S
derived by the conventional Langmuir-Hinshelwood ap-
proach with various assumptions regarding the rate-con- k
trolling step. Shankar and Agnew (1980) observed a break
H:S +A&
k-2
V:S
in the Arrhenius plot a t a temperature above 140 OC and k
postulated that this was due to a change in reaction v:s 9 .
k-a
v +s
mechanism. The main purpose of the study reported here
is to examine this proposal further by using dynamic re- sequence I1
action methods. k
Theory H + S1& H:S1
k-i
For a single chemical reaction occurring in a gradientless k
continuous stirred-tank catalytic reactor (CSTCR), the A + S z .&
k-2
A:S2
reaction can be represented in Aris (1969) notation as
k
N
CajA,=O ( j = 1 , 2,..., N) (1)
H:S, + A:S2 9
k-a
,V:S1 + S p
j=l

If the catalytic reaction consists of several elementary

steps, the set of equations may be written as
s N Sequence I1 is based on the assumption that both hy-
C C aijri = 0 (2) drogen chloride and acetylene are adsorbed onto the cat-
i=l j=1 alyst surface but on different types of active sites SI and
where i = 1 (1)s ; j = l(1)N. Sz, respectively; vinyl chloride is also adsorbed onto the
The dynamic mass balance for the j t h component in the same type of active site as hydrogen chloride. Mathe-
gas phase can be written as matical formulations can be developed based on general-
ized mass balance equations (3), (41, and (6), leading to the

dt = ($) cjf- (+)cj +

9 i=l aijri (3)
Similarly,the dynamic mass balance for the jth component
adsorbed onto the catalyst surface may be written as
evaluation of elementary rate constants.
For sequence I, the stoichiometric coefficient matrix and
the chemical species including the adsorbed species and
the active vacant sites can be represented as
H A V H:S V:S S

+
dCj
_
where j = N 1, ...,N*.
dt
s
-- Caijri (4)
q j =

['
0
0
0
-1
0
0
0
1
1
-1 1
0 - 1
-:] 1
(8a)

Summing the individual gas-phase mass balance equa- The elementary-step reaction rates are
tions a t constant temperature and total pressure gives
rl = k1CHCs - k-1CHs (9)
rp = kZCACHs - k-,Cvs (10)
r3 = k3Cvs - k3CVCs (11)
The volumetric flow rate of the reactor effluent stream is
related to the inlet volumetric flow rate by Dynamic mass balances for the gaseous species yield the
following first-order differential equations

At steady state, all the elementary rates are equal; also,

the derivatives of the gaseous-component and active-center
concentrations are zero; i.e.
- (
dCA = ;)CM -
dt
(+)cA- rp
(13)

dCV (+)cvf- (e)cv + r3

dCj
_- - 0 (j= 1, ...,N*) (7) - =
dt (14)
dt
dCI ($)CIf - (+)CI
The steady-state reaction rate may be derived from the
above equations. - =
The reaction studied can be written as dt
154 Ind. Eng. Chem. Process Des. Dev., Vol. 24, No. 1, 1985

Figure 1. Flow diagram for experimental equipment: (1,2,3,4) gas cylinders; (I) stream I to the reactor; (11) stream I1 to the vent; (C) common
port for solenoid valve; (Cl, ..., C6) unidirectional check valves; (FB) fluidized sand bath; (MS)
mass spectrometer; (NC) normally closed port
for solenoid valve; (NO) normally open port for solenoid valve; (NV1, ...,NC14) needle valves; (P)purification train; (PB1, PB2) backed beds;
(PI) pressure gauges; (R) reactor; (Rl, ..., R4) rotameters; (SD1, SD2) sinter metal disk; (SV1, SV2, SV3) 3-way solenoid valves.

where I refers to inerts. The corresponding equations for in sequence I can be estimated.
adsorbed species and vacant sites are Experimental Section
dCHS Equipment. The equipment used in this work was
-= rl - r2 designed to provide flexible experimental facilities which
dt
could be used for a number of gas-solid heterogeneous
catalytic reaction systems under both steady-state and
unsteady-state conditions. It consisted of an isothermal
internally recycled continuous stirred-tank reactor
(CSTCR) with associated continuous-gas-mixing and
gas-metering arrangements (see Figure 1). The reactor
where Cs is the concentration of the active vacant sites was similar in design to that of Yang et al. (1973) and Berty
available for adsorption. In addition, the total number of (1974), with provision for measurement of gas velocity
sites is assumed to remain constant across the catalyst bed. Two three-way solenoid valves
CHS + cvs + cs = cso
were coupled together to generate step and pulse changes
(19)
in concentration in the feed stream to the reactor.
Equation 6 can be rewritten as The reactor assembly was immersed in a heated fluid-
RTV ized sand bath. Temperatures at several points inside the
9 = 9f + p (-1 - r2 + r3) reactor were measured by thermocouples fitted through
the bottom lid of the reactor. Design details are presented
Equations 9 through 20 represent the unsteady-state be- elsewhere (Ghosh, 1981).
havior of the reacting system. A similar set of equations Materials. Hydrogen chloride was obtained in a li-
can be derived for reaction sequence 11with the generalized quefied form in compressed gas cylinders from Matheson
mass balance equations (3), (4), and (6) and the stoichio- Gas Ltd., New York, through Commonwealth Industrial
metric coefficient matrix in eq 21. Gases Ltd., Melbourne. The gas was stated to be 99%
H A V HS, AS, VS, S, S, pure and was used directly in the reactor. Commercial
r-1 o o 1 o o -1 01 grade acetylene was used; this was treated in a purification
train containing activated carbon and silica gel to remove
%= IL o
0
0
-
0
o
1 0
0
1
-1
0

o
1
-1
o -1
0
1
O
0
1
-1 l ( 2 1 )
1
OJ
impurities before entering the reactor. High-purity ni-
trogen and welding-grade argon of stated 99.9% purity
were also used. Vinyl chloride of 99.9% purity was ob-
tained from B. F. Goodrich (Australia) for calibration
Taking C , O , total active sites concentration, as a pa- purposes.
rameter, the nonlinear coupled differential equations (12) Tsurumicoal activated carbon was used as a catalyst
to (18) can be integrated numerically from t = 0 (at the support; this was obtained from Kogyo Ltd., Japan,
time of perturbation) to t = t, (time required to reach the through I.C.I. Australia Ltd. Two different sizes were used,
new steady state) with some initial estimates of kiand ki viz., 4 X 4 mm cylinders and 2 X 2 mm cylinders. The
and the appropriate initial conditions. From the calculated actual catalyst was mercuric chloride, which was impreg-
concentrations of the gaseous components and the mea- nated on the activated carbon support a t a concentration
sured gas-phase concentrations, the parameters kj,k+, and of about 9% w/w. The surface area of the support was
C , O can be estimated via optimization of a suitable ob-
measured to be 950 m2/g. The exact method of catalyst
jective function of the type preparation is given elsewhere (Shankar and Agnew, 1980).
Gas Analysis. Dynamic response studies can only be
effectively carried out if a reliable and accurate analytical
instrument is available for fast, continuous measurement
In an exactly similar way, the elementary rate parameters of concentrations of reactant and product components.
 Ind. Eng. Chem. Process Des. Dev., Vol. 24, No. 1, 1985 155

Table I. Summarized Operating Conditions for Transient

Reaction Runs
run no. temp, ‘C
Tl-T26 100-180 Ar -- scheme
(HCl + CzHz)
change
step
I

m .
j
51 I 1

T26-T40 100-170 Ar
T41-T49 100-170 (HC1+ Ar + C2H&
+ CzH2)z
-
(Ar + HCl + CzHz)
( H C l + Ar
step
step
6 3
2
=;
-
6 2-0
........, *e.
- 0 . .
*’. ............................-
- Z d x x x X X I x ix x x x x x i x XI,
T50-T57 100-160 Ar -+ (HCl + CzHz)-+ Ar
1 X I X X I
xx
pulse E ,xrx
T58-T64 100-160 Ar (HC1+ C2H2+ Ar) -+ Ar pulse 2
Y
1 -* I
i
Y 0 ~ , ~ o ~ o ~ Q p ~ ~ ~ ~ O ~ O O O O O o a o o ~ ~ o ~

The mass spectrometer is a useful analytical instrument ,o ‘;;:t:pcq”a 0 a 0,B 0 e 0 0 0 B 0 0 0 0 0 0 e 0

for this purpose. The instrument used in this study was 0 100 200 300 400 yx)
TIME, S
a magnetic-deflection mass spectrometer (Model MM6)
supplied by Vacuum Generators, U.K., through Oxford Figure 2. Typical transient experimental concentration profiles
Instruments, Sydney. During calibration, pure gaseous following step change in feed concentration: (0) argon ( X 0.1); ( 0 )
acetylene ( X 0.1); (0)
hydrogen chloride ( X 2); ( X ) vinyl chloride ( X
components were used to determine the sensitivity and 0.2).
cracking pattern coefficients of each component a t ap-
propriate mass numbers. These values were subsequently 5
used for analysis of reactor inlet and outlet streams. The
output signal from the mass spectrometer was logged au-
i
tomatically by a dedicated microprocessor (Intel 8086)
coupled with a minicomputer (DG NOVA 2/10). Details I

are available elsewhere (Ghosh, 1981).

Procedure. Transient reaction runs for the acetylene
hydrochlorination reaction were carried out over a tem-
perature range of 100-180 OC. Total reactor pressure was
101 kPa and the amount of catalyst used varied from 30
to 40 g (total weight including support, with +lo% HgClJ.
The mole fraction of hydrogen chloride in the reactant feed
mixture was varied from 0.1 to 0.5 and total volumetric
flow rates were kept within the range of 1.00 to 2.50 L/min.
The perturbation was applied by changing the concen-
tration of the reactant gas mixture in the inlet stream
L
00

Figure 3. Typical transient experimental concentration profiles

following pulse change in feed concentration: (0)
acetylene (X 0,l); (0)
argon (X 0.1); ( 0 )
hydrogen chloride (X 2); (X) vinyl chloride (X
TIME , S

according to the scheme shown in Table I. The procedure
for each set of transient reaction experiments using a step
input is summarized as follows: (a) The desired quantity
of catalyst was packed in the reactor under argon atmo-
sphere. (b) The reactor was heated up to the desired
temperature. (c) If the vacuum system of the mass spec-
trometer was under operating conditions and the elec-
tronics were turned on, the electronic multiplier of the
analyzer was powered on. It normally required 30 min to
stabilize the electronics to be set for analysis. Otherwise,
about 20-30 h was required for pumping the vacuum
system to the operating pressure (lo-’ to torr). (d)
The mass spectrometer was calibrated with pure gaseous
components to determine the sensitivities and cracking
pattern coefficients. (e) A constant flow of argon was
maintained through the reactor a t steady temperature.
The reactant gas mixtures, after passing through the re-
spective rotameters, passed through the by-pass line of the
switching valve. (f) The reactant mixture was then
switched to the reactor by actuating the step-function-
generating solenoid valve. Immediately, the reactor ef-
fluent stream was introduced into the mass spectrometer
sample line for continuous monitoring of the exit gas
composition. The compositions of the feed streams were
also monitored. (g) After each set of transient experiments
was completed the catalyst was removed from the reactor
and its mercury content was determined so that any
necessary correction could be applied for deactivation.
A few transient experiments were carried out by intro-
duction of a concentration pulse of reactant mixture in a
steady flow or argon a t constant temperature. Table I
shows the pulse input scheme. The operating procedure
for pulse perturbation was essentially the same as that for
a step change, excepting step (0.
The step-function-generating solenoid valve was
switched on to generate a step change from argon to the
0.2).
reactant gas mixture and allowed to flow for a particular
duration of time and then switched back to argon.
Computer programs were written in Assembler, Basic,
and Fortran for automatic data requisition, processing of
raw mass spectral data, and transferring the bulk data from
minicomputer to central computer for subsequent opti-
mization and nonlinear-least-squares estimation. The
transient response data were collected at time intervals of
2 s.
The catalyst, after conditioning in a stream of argon and
at constant temperature, was taken as the initial condition
for the transient experiments. One basic assumption made
was that argon was not adsorbed onto the catalyst surface.
Results
Typical transient gas-phase concentration profiles for
a step-change experiment are shown in Figure 2. During
the step change, the volumetric flow rates for the two
streams were kept as close as possible by manually regu-
lating the back-pressure regulating needle valve. The
constancy of the flow rate was confirmed from the constant
ion-gauge pressure reading of the ion-source of the mass
spectrometer during the entire transient period (500 8).
Typical transient experimental responses for pulse
concentration are shown in Figure 3, from which it can be
seen that the response of acetylene in the reactor effluent
stream is faster than hydrogen chloride and vinyl chloride.
The speed of response is in the order: argon > acetylene
> hydrogen chloride > vinyl chloride. Since argon was not
adsorbed onto the catalyst surface, the response was de-
tected immediately after the introduction of the concen-
tration pulse. The slower recovery after reverting to pure
argon was due to the slow desorption of adsorbed species.
Acetylene was less strongly adsorbed and then reacted
with more strongly adsorbed hydrogen chloride, producing
156 Ind. Eng. Chem. Process Des. Dev., Vol. 24, No. 1, 1985

Table 11. Adsorbed Gas Concentrations Calculated from Table 111. Kinetic Parameters for Reaction Sequence I
Transient Gas-Phase Concentrations T = 140-180
C&CL HC1, mol/cm3 X T = 100-140 "C "C
mol/cm3 x lo6 108 X E X E
run no. temp, "C ads" gas-phase ads" gas-phase k, 13.0 14.9 10.4 26.5
T1 100 0.64 16.1 1.71 3.84 k-1 7.8 43.9 7.4 42.8
T27 125 0.34 14.3 0.76 1.13 k2 19.0 123.5 28.7 63.0
T34 130 0.41 14.0 2.34 8.62 k-2 19.7 77.3 5.4 28.4
T37 135 0.34 10.6 2.80 8.36 k3 13.1 16.0 14.2 19.7
T15 140 0.19 8.9 0.47 2.99 k-3 3.4 39.9 5.7 43.7
T13 150 0.25 6.6 0.44 2.62
T22 160 0.23 7.9 1.57 4.27 Table IV. Kinetic Parameters for Reaction Sequence I1
T39 165 0.39 11.8 0.40 2.92
T23 175 0.10 10.2 0.76 6.51 T = 100-140 T = 140-180
T25 180 0.08 10.5 0.36 6.75 "C "C

" In mol/pellet volume.

vinyl chloride adsorbed on the surface. Adsorbed vinyl
chloride was found to desorb from the surface very slowly.
The maximum rate or desorption of vinyl chloride occurred
a t the time when the pulse ended or when argon concen-
tration began to increase; this phenomenon was observed
in all the pulse transient experiments.
Determination of Amount Adsorbed. Equations 9
through 18 can be rewritten to express the concentrations
of the adsorbed phases in terms of gas-phase concentra-
tions in the following manner
These equations were integrated numerically by use of
transient response data from t = 0 to t = t,, where t, is the
time to reach the new steady state. The calculated
amounts of adsorbed species a t steady state for selected
runs are shown in Table II. It can be observed from Table
I1 that a substantial amount of hydrogen chloride was
adsorbed onto the catalyst surface, the surface concen-
tration being of the same order of magnitude as the gas-
phase concentration. However, only very small amounts
of vinyl chloride were adsorbed. although the general trend
of adsorption followed the decreasing trend with tem-
perature rise, calculated adsorbed concentrations were
inconsistent. This was attributed to the inaccuracy of
numerical differentiation and integration of concentration
data, particularly in the "tailing" region. An attempt to
calculate the adsorbed concentration of acetylene using
equations derived from reaction sequence I1 proved un-
s u c d d because of the very small adsorption of acetylene
on the surface.
Estimation of Elementary-Step Rate Parameters.
Elementary-step rate parameters for sequence I were es-
timated by solving the differential equations (12) through
(18), in conjunction with minimization of the objective
function (eq 22). Parameters appearing in sequence I1
X E X E
13.0 14.9 10.4 26.5
7.8 43.7 7.4 43.8
12.4 17.9 12.7 19.1
3.7 17.9 2.3 37.8
11.7 18.1 26.7 71.4
3.5 4.9 4.7 9.0
13.1 16.0 14.2 19.7
3.4 39.9 5.7 43.7
were estimated similarly. Basic assumptions made were
the following. (i) Argon does not adsorb onto the catalyst
while conditioning a t constant temperature and steady
flow. The catalyst surface was assumed to be bare before
transient reaction runs were commenced. (ii) Concentra-
tions of adsorbed species were initially zero. (iii) At any
time the following condition is satisified
N'
c
j=N+1
cj* = CS" >0
where C,* is the concentration of an adsorbed complex
(including the vacant sites). (iv) Total active site con-
centration, Cso, was assumed constant for a particular set
of operating conditions. Although Cso may be assumed
to be a parameter and its value estimated, it complicates
the analysis and nonnegativity constraints are not normally
assured. Cso was assumed equal to the concentration of
the adsorbed complex (corresponding to complete mono-
layer coverage), calculated from independent adsorption
measurements. Calculated values ranged from lo4 to
mol/cm3 over the desired temperature range (Ghosh, 1981).
(v) For solving the equations derived from sequence 11,the
concentrations of the two different active sites Csl and Cs2
were assumed to be equal at t = 0; i.e. Csl = Cs2= l/zCso.
In sequence I, it is clear that steps (1)and (3) are purely
chemisorption; similar steps for sequence I1 are (l), (2),
and (4). Chemisorption rate is a function of temperature,
but specific to catalyst and the adsorbable gas concerned.
Independent adsorption studies to determine and ad-
sorption rate parameters under identical conditions of
temperature, pressure, and catalyst can reduce the number
of overall parameters to be estimated from reaction studies.
Adsorption of all the three gaseous components involved
in the hydrochlorination reaction were studied independ-
ently and the adsorption rate constants were accordingly
estimated for acetylene, hydrogen chloride, and vinyl
chloride (Ghosh, 1981).
Parameter estimation was based on the modified
damped least-square (MDLS) function minimization me-
thod of Mayer and Roth (1972), following the solution of
the differential equations using semi-implicit third-order
RungeKutta methods (Michelsen, 1976) and evaluation
of the gradients numerically. Details are available else-
where (Ghosh and Newell, 1981). Estimated rate param-
eters are summarized in Tables I11 and IV for sequences
 Ind. Eng. Chem. Process Des. Dev., Vol. 24, No. 1, 1985 157

1.0 L . 1

T1ME.S
,011.
1.9
" ' ~
21
" " ~ "
2.3
" ~ " "
2,s
" ' "
2.7
" ' " ~ "
2.9
' "
3j 3.3 Figure 5. Experimental and computed concentration profiles for
I l / T 1x1000 acetylene, run T34, T = 130 "C.
Figure 4. Arrhenius plot for similar concentration conditions: (0)
Wesselhoft et al. (1959); (A)Weston (1970); (A)Shankar (1976); ( 0 )
present work.

I and 11,respectively. The rate parameters are expressed

as
k = exp(x - E/R!l') (26)
Steady-state kinetics was investigated also, using the ok' ' 100
' 200 K13 400
final steady-state concentration data from the transient TI ME , S
experiments. At steady state, the reaction rate can be Figure 6. Experimental and computed concentration profiles for
expressed as vinyl chloride, run T34, T = 130 "C.

(4f/v) (C, - CVf)

1+-xc, 1
'=I (27)
RT
P

Reaction rates were calculated with this equation. The

reaction rate in units of mol/(cm3)(min)was converted into
conventional mol/(min) (g of cat.) units by multiplying by
the factor: reactor void gas volume/mass of catalyst. For
comparison with previously reported data, these rates were TIME, S

fitted to the following Langmuir-Hinshelwood model Figure 7. Experimental and computed concentration profiles for
(Shankar and Agnew, 1980; Wesselhoft et al., 1959) hydrogen chloride, run T34, T = 130 "C.

Kr(KHKAPHPA) 2.0 , 1
p= (28)
(1 + KHPA+ K v P v ) ( +
~ KAPA) ? I I
It can be observed from the Table V that good agreement
was obtained.
Discussion
y I . '
Mechanism Evaluation. Shankar and Agnew (1980) z . I

,'
have reported a change in slope of the Arrhenius plot a t 0 M zw m UXI 500
TIME S
a temperature of about 140 "C. This has been confirmed
by data obtained in the current study for similar concen- Figure 8. Experimental and computed concentration profiles for
tration conditions, as shown in Figure 4. Interphase heat vinyl chloride, run T23,T = 175 "C.
and mass transport resistances and intraparticle heat
transfer resistance were checked by use of established
criteria and were found to be negligible (Shankar, 1976;
Ghosh, 1981). Besides, the high-temperature branch of
Figure 4 is seen t o be well below the line of slope E / 2 for
complete diffusion control. Hence the break in the Ar-
rhenius plot cannot be due to simple diffusion effects alone.
Similar discontinuities have been observed in a number
of other systems despite independent evidence for the
apparent absence of transport effects (Shankar, 1976). TIME,S
However, discontinuities in the Arrhenius plot may occur Figure 9. Experimental and computed concentration profiles for
if the concentration of any adsorbed species changes from acetylene, run T23, T = 175 O C .
one temperature range to the other. Based on this concept,
Shankar (1976) proposed the following two possible reac- Mechanism 11. Because of the exothermic nature of
tion mechanisms. the adsorption process, as the temperature rises, the sur-
Mechanism I. For a temperature range below 140 "C, face concentrations of both adsorbed hydrogen chloride
both acetylene and hydrogen chloride adsorb a t two dif- and acetylene decrease. Acetylene being less strongly
ferent active sites. The adsorbed species react on the adsorbed, above 140 O C the surface acetylene concentration
surface to produce adsorbed vinyl chloride which slowly becomes so low that the reaction no longer proceeds by the
desorbs from the catalyst surface to the gas phase. This Langmuir mechanism but by collision between bulk-phase
corresponds to sequence 11. acetylene and adsorbed hydrogen chloride-the Rideal
158 Ind. Eng. Chem. Process Des. Dev., Vol. 24, No. 1, 1985

Table V. Comparison of Parameter Values for Data of Table VI. Statistical Comparison of Two Reaction
Earlier and Present Studies Sequences
K,, mol KH, KA, Kv, statist param reaction seq I reaction seq I1
ref h-' g-' atm-' atm-' atm-* Temperature = 116 "C
Temperature = 100 "C total
present work 1.15 4.73 0.29 4.2 sum of squares 18.45 4.56
Shankar (1976) 1.75 4.30 0.20 4.8 nd 994 4992
Gel'bshtein et al. (1972) 5.20 9.70 0.23 pure error
Weston (1970) 2.0 4.30 0.20 4.0 sum of squares 0.0468 0.0650
Wesselhoft et al. (1959) 1.3 2.70 0.46 3.8 nd 4 4
variance 1.16 X 1.62 X lo-'
Temperature = 140 "C lack of fit
present work 7.6 3.4 0.18 3.2 sum of squares 18.40 4.495
Shankar (1976) 7.6 3.4 0.18 3.2 nd 990 988
Gel'bshtein et al. (1972) 22.6 7.0 0.10 variance 1.86 X 4.55 x 10-3
Weston (1970) 8.6 3.4 0.18 4.0 F ratio 1.59 0.28
F95 2.37 2.37
Temperature = 165 "C
total
sum of squares 11.59 57.86
nd 994 992
pure error
sum of squares 0.15 0.21
nd 4 4
variance 3.75 x 10-2 5.25 X
lack of fit
sum of squares 11.44 57.65
Figure 10. Experimental and computed concentration profiles for nd 990 988
hydrogen chloride, run T23, T = 175 "C. variance 1.15 X 5.84 X
F ratio 0.308 1.12
mechanism. This corresponds to sequence I. F95 2.37 2.37
These two mechanisms were examined quantitatively
by using transient gas-phase concentration data. Two
typical temperatures, one below and one above the break
point in the Arrhenius plot, are chosen to illustrate dif-
ferences between the reaction sequences, viz., 130 "C and
175 "C. The calculated gas-phase concentrations of the
gaseous reaction components based on the above two
mechanisms have been plotted in Figures 5 through 10 and
are compared with the experimental concentration profiles.
At 130 "C sequence I1 is seen to give the better fit while
at 175 "C sequence I is in better agreement. Figure 11. Experimental and computed composition profiles fol-
A statistical evaluation was also made. Statistical pa- lowing a step change in feed composition: steady-state kinetic model.
rameters were calculated for both reaction sequences a t
two different temperatures; a summary of the calculations I

is shown in Table VI. It can be observed from Table VI i

that the F ratio of reaction sequence I1 is smaller a t 116
"C, indicating this sequence is favored at lower tempera-
tures. On the other hand, a t 165 "C, the F ratio for se-
quence I is smaller than that of sequence II. Thus at lower
temperature the reaction mechanism is more likely to x10-1
follow sequence 11,while a t higher temperature it is more =i 0.t I , , , , , , , , I
0 1w 203 3w 400 500
likely to follow sequence I. TIME S
Calculated and experimental concentrations of argon Figure 12. Experimental and computed composition profiles fol-
agreed well for both sequences, which is reasonably to be lowing a step change in feed composition: dynamic kinetic model.
expected as argon is an inert component. Average standard
deviations calculated for sequence I were 0.072 and 0.039 tical at new steady state. On the other hand, the dynamic
for temperature ranges 100-140 "C and 140-180 "C, re- kinetic model yields profiles which agree well with the
spectively, while corresponding values for sequence I1 were experimental results over the complete transient period.
0.041 and 0.072, respectively. Hence it was concluded that The steady-state rate expression does not account for the
reaction sequence I and I1 are favored at higher and lower adsorption dynamics, which is the reason for the discrep-
temperature, respectively. ancy.
Comparison of Dynamic Profiles. The steady-state Lehr et al. (1968) also concluded from a study of the
and dynamic reaction models have been used in conjunc- dynamic behavior of tubular reactor using the ethyl alcohol
tion with the C.S.T.C.R. mass balance equations (12) dehydration reaction that the incorporation of adsorption
through (15) to predict dynamic exit concentration profiles dynamics of reacting species was necessary to obtain sat-
following a step change in feed composition. isfactory agreement between actual and predicted reactor
Calculated and experimental concentration profiles are dynamic response. Lee (1974) similarly found that the
shown in Figures 11and 12. The calculated concentration predicted reactor dynamics did not agree with the mea-
profiles using steady-state kinetics are higher in the sured behavior via packed tubular reactor for acetylene
transient region than the experimental profiles for acety- hydrochlorination and postulated that this was due to the
lene, vinyl chloride, and hydrogen chloride, but are iden- reaction dynamics.

Usefulness of Transient Response Method. The
transient response method gives additional information
about a catalytic reaction concerned with the individual
steps. From the observed transient gas-phase behavior it
is possible to postulate various sequences of elementary
reaction rates on the surface of the catalyst in which both
gaseous and adsorbed species take part. Detailed eluci-
dation of elementary steps may lead to the simplification
of the rate expression and a better steady-state model can
be established. Steady-state reaction rates can also be
obtained from the transient method.
Another important advantage of the transient response
method is that a large number of experimental data points
can be obtained from a single reaction run. These data
can be analyzed for qualitative and quantitative evaluation
of reaction mechanism. Conventional steady-state kinetic
investigations require more experimental runs to procure
sufficient rate data for model characterization, which can
take a much longer time.
It is possible to estimate the elementary rate constants
by use of transient concentration profiles. The amount
of reactants and/or products adsorbed onto the catalyst
surface can be calculated with transient concentrations via
simplified equations derived from mass balances.
Conclusions
(1) The transient response method provides sufficient
data for estimation of elementary-step reaction rate pa-
rameters.
(2) For the acetylene hydrochlorination reaction, all the
gaseous components involved adsorb onto the catalyst
surface, but the extent of adsorption follows the trend:
hydrogen chloride > vinyl chloride > acetylene.
(3) Good agreement exists between reaction rate data
derived from the new steady-state conditions of the present
transient study and earlier investigations using conven-
tional steady-state approach.
(4) Reaction sequence I1 agrees well a t a temperature
below 140 "C, while reaction sequence I is favored a t a
temperature above 140 "C.
(5) The break in Arrhenius plot can be ascribed to a
change in reaction mechanism at a temperature above 140
OC.
Acknowledgment
A.K.G. wishes to thank Monash University for providing
financial assistance to carry out this study. The authors
also acknowledge the financial help from the Australian
Research Grant Scheme and assistance from Mrs. E.
Stacey in operating the mass spectrometer.
Nomenclature
A = reaction species
C = concentration, mol/cm3
C" = total concentration, mol/cm3
Ind. Eng. Chem. Process Des. Dev., Vol. 24, No. 1, 1985 159
E = activation energy, kJ/mol
K = adsorption equilibrium constant
k = reaction rate constant
M = number of equal time intervals
N = number of gaseous components
N* = total number of gaseous components and adsorbed
species
a d = number of degree of freedom
P = total pressure, atm
q = volumetric flow rate, cm3/min
R = gas law constant, cm3 atm/mol K
r = reaction rate, mol/cm3 min
r = steady-state reaction rate, mol/h g of HgCl,
S = active site
s = number of simultaneous reactions
T = temperature, K
t = time, min
V = reactor volume, cm3
x = defined by eq 26
Greek Letters
a = stoichiometric coefficient
u = standard deviation
Subscripts
A = acetylene
f = feed
H = hydrogen chloride
I = inert
i = reaction number
j = component number
S = vacant site
V = vinyl chloride
Ragistry No. Acetylene, 74-86-2;mercuric chloride, 7487-94-7;
vinyl chloride, 75-01-4.
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Received for review July 26, 1983
Accepted February 24, 1984