Int. J. Hydrogen Energy, Vol. 16, No. 10, pp. 677~82, 1991. 0360-3199/91 $3.00+ 0.

00
Printed in Great Britain. Pergamon Press plc.
1991 InternationalAssociationfor Hydrogen Energy.

GAS PHASE FORMATION OF HYDROGEN CHLORIDE BY

THERMAL CHLORINE-STEAM REACTION
A. K. GUPTA,*R. Z. PARKER* and R. J. HANRAHANt
*Solar Reactor Technologies, Inc., 2666 Tigertail Avenue, Miami, FL 33133, U.S.A.
tDepartment of Chemistry, University of Florida, Gainesville, FL 32611, U.S.A.

(Received for publication 8 July 1991)

A~traet--Electrolysi~ of HC1 solution to form H 2 and C12 is of interest in applications such as utility load leveling,
solar energy storage and commercial hydrogen production. In the latter case, the chlorine generated must be
reconverted to HCI for continued use in the process. The gas phase reaction of steam with chlorine to form hydrogen
chloride plus oxygen was investigated for this purpose. Flowing systems with 2, 4 and 8 cm3 min- i of chlorine and
25 cm3 min- ~ of steam were studied from 563 to 873 K. The reactant/product mixture was quenched in 50 cm3 of
water at 298 K. The yield of HC1 was determined by acid/base titration. After removal of HCI and residual chlorine
using alkaline KI solution, oxygen was measured by use of a gas burette. The HCI and 02 analyses were in agreement.
Using a C12/H20 mole ratio of 4/25, conversion of chlorine was 24.4% at 563 K, 39.7% at 648 K, 53.1% at 773 K
and 80.0% at 873 K. Strong photolysis at 563 and 648 K had no observed effect on the product yields. The
experimentally determined AH value from plots of log(Kp) vs 1/ T is in good agreement with the AH value determined
from standard thermochemical tables, for the reaction between chlorine and steam.

INTRODUCTION In a solar photochemical step, the strongly colored

IrCl~ complex is photochemically activated and reacts
Hydrogen is an important raw material for the manufac- with chloride ion to form nascent chlorine, probably in
ture of many important products, and is frequently used the form of atomic chlorine or a transient C12 complex.
as a chemical reducing agent. Although hydrogen is an These combine to release C12, which is swept out of the
environmentally desirable and clean burning fuel it has solution.
not made major inroads in terrestrial applications be- The cathode half cell reaction is shown in Reaction
cause of its high cost compared to other, less environ- (1). Reaction (2) shows the accompanying anode half cell
mentally desirable fuels. Several methods are known for reaction for the oxidation of IrCl~- to IrCl62- . Reaction
hydrogen production, the most c o m m o n being steam- (3) is the sum of the two half cell reactions, which shows
methane reformation, methane cracking and electrolysis. the formation of gaseous hydrogen and IrCl62 from
Currently, most commercial hydrogen is manufactured hydrochloric acid solution containing IrCl63- .
by steam-methane reformation, even though this pro-
cess consumes a non-renewable fossil fuel both as a 2H + + 2e---* H 2 Cathode
feedstream (source of the hydrogen produced) and for (Reduction) (l)
the thermal energy to drive the reaction, 2IrC163 --* 2IrC162- + 2e Anode
A n alternate source of hydrogen is water, which is (Oxidation) (2)
a b u n d a n t and virtually inexhaustible. Solar Reactor
Technologies (SRT) is developing a method for the 2H + + 2IrC163---* 2IrC162- + H 2 Net. (3)
production of hydrogen and oxygen from water in a
cyclic process involving electrolysis, solar photochemical The solar photolysis of IrCl~- formed during electrol-
and solar thermal steps. (If it is desired to use the process ysis is described by Reaction (4).
for energy storage or utility load leveling, the final
thermal step is not required.) 2C1- + 2IrC162- + (hv) --, 2IRC163- + CI 2. (4)
In the electrochemical stage, a solution of hydro-
The net result of the electrolysis, Reaction (3), fol-
chloric acid with added IrCl 3- is electrolysed. Hydro-
lowed by the solar photolysis step, Reaction (4), is the
nium ions are reduced to form gaseous hydrogen at the conversion of aqueous hydrogen and chloride ions to
cathode; at the anode, IrC13 is converted to IrC! 2- . The
gaseous, elemental hydrogen and chlorine, according to
addition of the iridium complex allows the electrolysis to
Reaction (5).
proceed at a lower applied voltage than electrolysis of
HC1 solution by itself. 2H + 2Ci---, H2 + C12. (5)

677
678 A. K. GUPTA et al.
When the system is used for energy storage, Reaction (5)
is carried out in the reverse direction in a fuel cell
arrangement.
In order to modify the above scheme for net pro-
duction of hydrogen as a fuel (or for any commercial
purpose), it is necessary to reconvert the product C12
from Reaction (4) into HC1 for reuse in the process. To
do this, chlorine will be reacted with steam in a gas phase
thermal process to form hydrogen chloride and oxygen
(The Reverse Deacon Process), Reaction (6):
C12(g) + H20(g) ~ 2HCI(g) + 1/202(g). (6)
When this reaction is combined with Reactions (3)
and (4), the overall chemistry is simply the decompo-
sition of water to its elements. Thus in the overall cycle
only water, solar energy and electricity are fed into the
system, hydrogen and oxygen are removed; chlorine and
the Ir-complex are recycled.
Our work on the electrolysis and solar photochemical
steps, including an analysis of energy savings (and
potential cost savings) will be described elsewhere [1].
The present paper is concerned with the final step of the
process, namely the gas phase reaction between chlorine
and steam to form hydrogen chloride and oxygen. This
reaction is applicable not only in the present connection,
but also in any other industrial process in which HC1 is
used as a reactant, and in which C12 is formed as a
by-product. The well known Dow process for producing
magnesium from brine or seawater is such a situation [2];
however, the method presently used by Dow is burning
CI: with hydrogen gas to reform HCI [3]. Use of the
Reverse Deacon Process in connection with other indus-
trial processes has been mentioned in the literature, but
details have usually not been presented [4-9].
Nanda et al. [10] have published a moderately detailed
experimental investigation of the reverse Deacon reac-
tion in which effects of temperature, water flow rate and
chlorine flow rate were examined in a 3 3 "factorial
design" study. Since Nanda et al. measured loss of
chlorine and formation of oxygen, whereas we measured
initial water, initial chlorine, and final HC1 and oxygen,
our data set supplements theirs in confirming the stoichi-
ometry of the reaction. Nanda et al. state that work on
the reverse Deacon process has been done by Funk [11],
by Kerns [12], and by Knoche and co-workers [13].
However, reports of these studies appear in conference
proceedings or in unpublished reports, rather than in the
open literature. Nanda et al. imply that these three
researches all emphasize thermodynamic aspects of the
system.
In the present study, experiments were conducted to
measure the thermochemical-photochemical conversion
of chlorine and steam to hydrogen chloride and oxygen
in the gas phase, as a function of flow rate, temperature
and application of a visible light flux. We also obtained
evidence that by-products such as oxyacids of chlorine,
which could be dis-advantageous in a practical industrial
system, were not formed in the reaction. Thermochemi-
cal calculations were carried out to establish yields
expected under equilibrium conditions.
EXPERIMENTAL
A corrosion resistant single stage regulator certified
for chlorine service was obtained from Matheson com-
pany. One end of the regulator was connected to the
chlorine cylinder and the other to the chlorine flow
meter. The flow meter was connected to a quartz reactor
tube filled with quartz chips. The reactor was a 60.9 cm
long quartz tube with 2.4 cm ID, the total volume of
which was 275.5cm 3. The steam generator with an
automatic pressure controller (5, 10 and 15psig) was
connected to the quartz reactor tube through two plug
valves, a steam pressure gauge (range 0-30 psig), and a
double pattern fine metering valve with a vernier handle.
The quartz reactor tube was placed in a tube furnace
with a temperature range of ambient to 1300 K. The
furnace temperature was measured using a cromel-
alumel thermocouple. Next to the tube furnace, two
300 W quartz-iodine light sources with aluminum reflec-
tors were placed together in "clam shell fashion" so that
the reactor tube could fit exactly in between the two light
source assemblies. The other end of the quartz tube was
bent downwards and immersed in a beaker containing
water. The effluent mixture of reactant and product
gases was quenched in 50 ml water at 298 K. The number
of moles of HCI formed during the reaction was deter-
mined by titrating the solution with NaOH. A schematic
diagram of the experimental setup is shown in Fig. I.
Oxygen was determined by passing the reaction mix-
ture through a solution of sodium hydroxide and potass-
ium iodide. The remaining oxygen gas was collected in
a gas burette. The volume of gas collected was measured
at atmospheric pressure. Using the ideal gas equation,
the number of moles of oxygen gas formed during the
reaction was calculated.
The chlorine gas used in these experiments was
Matheson "high purity grade", 99.5%. The steam gener-
ator was charged with tap-distilled water. Several re-
agents used in the analysis of the products were usual
laboratory grade.
In order to carry out an experiment, water in the
steam generator was heated to boiling and allowed to
equilibrate for approximately 10min, to produce a
Chlorine I [ ~ IIII I Meier
CG'yliaSrlder 1~ T ThermocoupIe
: Steam
t Plug Needle Plug
Valve Valve Valve
.....
Tube Quartz
_
Generator Furnace Iodine
Light Source
Fig. 1. Experimental setup for the formation of hydrogen
chloride and oxygen by chlorine-steam reaction.
 GAS PHASE FORMATION OF HYDROGEN CHLORIDE 679

Table 1. Computed AG, equilibrium constant and % equilibrium conversion for the gas phase reaction
between chlorine and water at various temperatures
Cl2(g) + H~O(g)--*2 HCI(g) + 1/202 (g)
Temp, K 500 600 700 800 870 900 1000
AG, kcal 5.91 4.32 2.71 1.10 0 -0.52 -2.15
Kv 2.6 x 10-3 2.7 x 10-2 0.14 0.50 1 1.34 2.95
% Equilibrium
conversion* 17.5% 38.8% 61.7% 79.4% 86.9% 89.5% 94.5%
* Based on initial 3.1 x 10-2moles of steam and 4.9 x I0-3 moles of chlorine; a pressure of I atm
was assumed.

steady head of 10 psi. Next, the chlorine reservoir was
opened, brought to a fixed pressure of 10psi, and
allowed to flow into the reaction tube using a calibrated
flow meter and precision needle valve. The steam flow
was then started; a desired flow was then established
using a calibrated precision valve. The chlorine and
water flow rates were calibrated in preliminary exper-
iments; both could be controlled and maintained accu-
rately with a precision of +2.5%. The CI~/H~O gas
mixture was passed for a desired time (typically 30 min)
through the hot tube furnace in/or through the photoly-
sis apparatus. The effluent was then bubbled into water
or alkaline KI solution for HCI and 02 analysis as
discussed previously. In some cases, a test was made for
possible presence of HOC1 in the beaker of water used
to quench the reaction gases. The addition of cobalt
nitrate solution should give a black precipitate of cobalt
oxide if any HOC1 was present. In fact, no precipitate
was observed indicating the absence of HOC1 in the
product gas mixture.
Experiments were done at three different flow rates (8,
4 and 2 cm 3 min- 1) of chlorine; the flow rate of steam
was 25 cm 3 min-l in all the experiments. Four different
temperatures were used (563, 648, 773 and 873 K).
Several experiments were carried out in the presence of
light to check for a possible photochemical component
of the reaction.
computations were done for a system with excess water,
to correspond with our experimental work.
Results of a set of six experimental runs are summar-
ized in Table 2. It will be seen that HC1 and oxygen are
produced in a 4:1 ratio, consistent with the stoichio-
metric equation. Within the precision of the analysis
(___3%), it can be inferred that the only products of the
reaction are hydrogen chloride and oxygen. Consistent
with this observation, a simple qualitative test for
hypochlorite ion gave negative results.
As required by the principle of le Chatelier, the
absolute number of moles of HC1 at equilibrium in-
creases when the initial pressure of chlorine increases,
but the percentage of chlorine converted to HC1 de-
creases. This is seen from either the computed or the
experimental values; see the three runs at 563 K for
example. It is perhaps unexpected that the experimen-
tally achieved percentage of the computed equilibrium
yield is best for the largest amount of reactant chlorine,
with all other conditions constant. This phenomenon
was seen also by Nanda e t al. [10].
L 7~

RESULTS A N D DISCUSSION
078 0~
Thermodynamic calculations summarized in Table 1
show that AG for the reaction system of steam, chlorine, -n
g~
hydrogen chloride and oxygen becomes zero at 870 K. 015 o76 0~.
Data obtained for the computations was obtained from 0
the J A N A F thermochemical tables [14]. Computations
done by N. Gat of T R W Space and Technology Group, 074

using a comprehensive computational package for

chemical equilibrium, predict that the reaction between
chlorine and steam forms only hydrogen chloride and L
oxygen in significant quantities [15]. The computations
indicate that Cl-containing species other than molecular
chlorine and hydrogen chloride amount to less than
5 ppm of total gas present. Table 1 shows the computed
AG, equilibrium constant and percentage of maximum O~ 500 4 CO0 0
700 800 O
aO0 1,000
Oea
1,100
possible (stoichiometric) yield at various temperatures Temperature, K
for the gas phase chlorine-water reaction. Figure 2 Fig. 2. Computed mole fraction versus temperature for the
shows the computed mole fraction of chlorine, water, reaction of chlorine and water vapor (initial mole ratio
hydrogen chloride, and oxygen versus temperature. All water/chlorine = 25/4).
680 A. K. GUPTA et al.

Table 2. Percentage experimental and equilibrium conversion at various flow rates and temperatures for the reaction
between chlorine and steam
Flow rate of CI2, c m 3 min ~ 8 4 2 4 4 4
Flow rate of steam, cm 3min-~ 25 25 25 25 25 25
Time of reaction, rain 30 30 30 30 30 30
Temp. of the furnance, K 563 563 563 648 773 873
Moles of C12 passed 9.7 10 3 4.9 x 10 3 2.4 1 0 - 3 4.9 1 0 - 3 4.9 1 0 - 3 4.9 x 10 3
Moles of steam passed 3.1xi0 2 3.1xl0 2 3.1x10 -2 3.1 x l 0 2 3.1 x l 0 -2 3.1x l0 2
Moles of HC1 formed 3.9 x l0 -3 2.4 x l0 -3 1.3 x l0 -3 3.9 x l0 -3 5.2 x 10-3 7.8 x l0 -3
Moles of 02 formed 9.6 x l0 -4 5.9 10-4 3.2 x l0 -4 9.6 x l0 -4 1.3 l0 3 2.0 x 10-3
% Experimental conversion 20.0% 24.4% 27.0% 39.7% 53.1% 80.0%
% Equilibrium conversion 21.5% 30.3% 42.5% 50,5% 75.5% 87.3%
% Conversion etficiency 93.0% 80.5% 63.5% 78.6% 70.3% 91.6%

As required by the van't Hoff reaction isobar, the
percentage yield of reaction increases with temperature.
Conversion of chlorine was 24.4% at 563 K, 39.7% at
648K, 53.1% at 7 7 3 K and 80.0% at 8 7 3 K for a 25:4
water:chlorine mixture. In a further set of experiments
not described in the tables, strong photolysis at 563 and
648 K was found to have no effect on the product yields.
The reaction appeared to be purely thermal under the
conditions studied. However, it is possible that our
experimental light flux, obtained from two 3 0 0 W
quartz-iodine lamps placed within ca 2.5 cm of the
reaction tube, was too low to produce a significant effect.
A literature survey of both gas and liquid phase
chlorine/water system shows that in aqueous solution, a
redox-state disproportionation reaction occurs between
chlorine and water which yields hypochlorous acid and
hydrochloric acid, Reaction (7) [16, 17]. However, the
equilibrium constant K~q is unfavorable and the reaction
occurs only to a very small extent, especially when
additional HCI is present, as in the present work:
Values of Kp at various temperatures were calculated
using experimental data given in Table 2; values ob-
tained from published thermochemical data are given in
Table 1. Based on the van't Hoff equation, a plot of
log(Kp) vs 1 / T gave a straight line graph. Experimental
and theoretical values of AH, respectively, were calcu-
lated from the slopes. Figure 3 shows the van't Holt
plots which we obtained. The computed value of AH is
13.7 kcal mol ~ (this is, of course, consistent with the
data set used to create Table 1). Neglecting one outlying
point, the experimentally determined value is 13.9 kcal
tool-l; the agreement appears to be satisfactory.
As explained in the Introduction, it is our ultimate
goal to use the Reverse Deacon reaction as one part of
an overall cycle for practical production of H2 by HC1
electrolysis. We are examining practical prospects of the
system both with and without the use of a "photochem-
ical assist" in the chlorine production step. The enthalpy
change for each step in a sequence of reactions for the
net production of hydrogen and oxygen from water

C12(g) + H20(aq) ~ HOCl(aq) + HCl(aq). (7) 10

Certain older literature (mostly from the 1880-1920

era, as recorded in Mellor [16, 17]) describes a more fL com0
0
interesting reaction between chlorine and liquid water, 5 f
namely, a photochemically initiated reaction which pro-
duces hydrochloric acid and oxygen, Reaction (8). Light
at the blue and UV end of the spectrum was thought to
be required: -05 "~ '"

Cl2(g ) + H20(aq) + (hv) ~ 2HCl(aq) + 1/202(g). (8) ,\

O) -1 o
o
We attempted to confirm this reaction in brief studies
conducted both at the University of Florida and at the
facilities of T R W , Inc., in Redondo Beach, California.
Positive results were obtained but the apparent q u a n t u m
yield was so low (ca 0.001) that the process did not
appear to be of practical use.
As mentioned above, we are interested in the possi-
bility that a process similar to Reaction (8) might occur
more efficiently in the gas phase, Reaction (9) (that is,
under photolysis rather than thermolysis conditions). -aO
OGO08
i I
0001
i
00012
[ i
00014
i I , r
0(~16 0.0018 O.0~ 00022
Although our preliminary attempts gave negative re-
sults, a more rigorous trial may be warranted: 1/r
Fig. 3. Plot of log (Kp) vs 1/T for equilibrium in the Reverse
CI2(g) + H20(g) + (hv) ~ 2HCI(g) + 1/202(g). (9) Deacon Process.
 GAS PHASE FORMATION OF HYDROGEN CHLORIDE 681

60.0
H, Kcal
Note 1 (a) Cl2(v) + H20(1) --> Cl2(v) + H20(v) +20.8
300 K 900 K
40.0

(b)~-~f(c) (e) (b) C12(v) + H20(v)

900 K
- - > 2HCI(v) + 1/202(v)
900 K
+14.1

20.0
T (c) 2HCI(v) + 1 / 2 0 2 ( v ) - - > 2HCI(v) + 1 / 2 0 2 ( v ) -10.9
900 K 300 K

0.0 L (d) 2HCl(v) + 1/202(v) --> 2HCl(aq) + 1/202(v ) -35.9

300 K 300 K

( e ) 2HCl(aq) + 1 / 2 0 2 ( v ) - - > 1 / 2 0 2 ( v ) + H2(v ) + C12(v ) +80.0

300 K 300 K
-20.0

Note 1 : Thermal energy reqt~'ement using solar-assisted

HCI electrolysis; see text.)
Fig. 4. Enthalpy diagram of thermochemical steps in the production of hydrogen and oxygen from water using
hydrogen chloride/chlorine intermediates.

using HCI/CI 2 intermediates was calculated in order to REFERENCES

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each step of the purely thermochemicai process. As
seen in the figure, the only major energy barrier is for
step (e), the electrolysis step releasing H2 and C12 from
aqueous HCI solution.
We are attempting to accomplish step (e) using a
combined electrochemical/photochemical process, as
noted in the Introduction. Absorption of a photon by
iridium (IV) hexachloride is actually endoergic in the
thermodynamic sense but we view the process as mov-
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chlorine.
Acknowledgements--We are grateful to Drs N. Gat and R.
Fleeter of TRW, Inc., Space and Technology Group, for the
thermodynamic computations and for their assistance with the
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