Chemicof Enpeemg Scimce Vol. 38, No. 7, pp.

1119-1133, 1983
Printed in Glsat Britain.

ABSORPTION OF CHLORINE IN AQUEOUS

SOLUTIONS OF SODIUM HYDROXIDE

DESORPTION OF HYPOCHLOROUS ACID FOLLOWED BY

ITS DISSOCIATION TO CHLORINE MONOXIDE

R. N. LAHIRI, G. D. YADAV and M. M. SHARMA*

Departmentof Chemical Technology, Universilyof Bombay, Matunga Road, Bombay-400 019, India

(Received 16 January 1982)

Abstract-The absorption of chlorine in aqueous solutions of sodium hydroxide with concurrent

desorption of hypochlorous acid (followed by its dissociation to chlorine monoxide) was studied at 55
and 75°C in a model stirred contactor with a flat gasliquid interface. Theoretical and experimental aspects
of this unique case of desorption (followed by dissociation) have been considered.
A reasonably good agreement between the theoretical predictions and experimental observations has
been found.
INTRODUCTION Above a pH of 12.6 the forward part of reaction (2)
Absorption of chlorine in aqueous solutions of SO- was the rate controlling and the reaction was found to
dium hydroxide is of both commercial importance be very fast.
and theoretical interest. There have been a few studies Takahashi et nl. [2] have measured the specific
on this process on the basis of penetration mode1 for rates of absorption of chlorine into laminar jets of
gas absorption accompanied by an instantaneous irre- aqueous NaOH solutions in the range
versible reaction at a single plane [I, 21 and two planes 5 x IO ‘-2 x lo- ’gmole/cm3 and reported good
[3]. However, there are no detailed reports on the agreement between the observed rates and the theo-
process of desorption of the intermediate product retical rates, based on the penetration theory, for
hypochlorous acid, HCIO, during the process of ab- absorption accompanied by an instantaneous irre-
sorption of Cl> in aqueous alkaline hydroxides. Fur- versible reaction at a single plane within the liquid
ther, the dissociation of HClO to Cl,0 in the gas film between the dissolved Cl, and OH- ions. In the
phase after its desorption, which would result in foregoing analysis [l, 21 the forward part of reaction
enhanced desorption rates, has not been reported. (2) was assumed to bc the rate determining step.
The present work was undertaken to study, both However, Hikita et al. [3] have shown that in addition
theoretically and experimentally, the desorption of to this step, the rate is affected by the reaction of
HCIO under different conditions, when rich mixtures HClO with OH ions at a second reaction plane
of Cl, in nitrogen were absorbed in aqueous solutions farther from the first plane in the liquid film, in a
of NaOH. This system is very interesting and poten- strong hydroxide solution:
tially useful and is expected to bring out a novel
feature of gas-liquid reactions. The most important HClO + OH - :ClO - + H20 (3)
point is that HClO may be desorbed despite a large
excess of NaOH in the bulk liquid phase.
It would be relevant to make a brief reference to the (K, = 2.2 x lo6 I/gmole at 30°C).
work of Spalding [l], Takahashi et al. [2] and Hikita
ei al. [3]. Spalding has studied the absorption of Cl2 They have clarified the mechanism of absorption of
into water and aqueous solutions of H,SO, and Cl2 into aqueous solutions of NaOH of concen-
NaOH in a laminar jet apparatus and found that the trations from 0.125 x lo- 3to I x lo-” gmole/cm’ on
rate of absorption of Cl, was governed by one of the the basis of their penetration model for gas absorp-
following reactions depending on the pH of the solu- tion accompanied by an instantaneous two-step reac-
tion: tion [4] represented by reactions (2) and (3); the
overall reaction between the dissolved Cl, and OH
ions is as follows:
Cl, + H,O:HCIO + H + + Cl - (1)
Cl,+2OH-&I- +ClO- +H>O (4)
Cl> + OH - :HCIO + Cl - (2)
(K4 = K2K3 = 6.82 x lOI I/gmole at 30°C).
(K, = 4.5 x 10m4 (gmo1e/1)2, K2 = 3.10 x lO”at 30°C) The desorption of HClO has a considerable indus-
trial value in the manufacture of, for instance, pure
*Author to whom correspondence should lx addressed. calcium hypochlorite (i.e. free from chloride ions),
1119
1120 R. N. LAHIRI et OZ.

chloramines and chloroisocyanurates. The Olin Cor-
poration, U.S.A., has a few patents [5, 61 describing
the absorption of Cl, in alkali metal hydroxide solu-
tions (4&75% w/w) at elevated temperatures
(50-2OO“C)in a spray column or a sweep reactor from
which the HCIO vapours are recovered by scrubbing
the gaseous mixture of Cl,, HClO and Cl20 with water
at low temperatures. The use of rotating drums,
falling film absorbers, etc. has also been claimed.
It was therefore thought desirable to study the
desorption of HClO when rich mixtures of Cl, are
absorbed in concentrated NaOH solutions at higher
temperatures.
MECHANISM OF ABSORPTION-DESORFTION
Hikita et al. [3] have shown that the steps given by
reactions (2) and (3) are relevant in the case of absorp-
tion of Cl2 in strong hydroxide solutions. Reaction (1)
has a forward rate constant of 2 1.4set - ’at 30°C and
makes negligible contribution to the total rate of Cl,
absorption. It was shown [4] on the basis of the
penetration theory for gas absorption accompanied
by an instantaneous two-step reaction that the mech-
anism of absorption depends on the ratio P (= ZCJKJ.
In the limiting cases, when P tends to be zero, there
exists a single plane in the liquid film at which the
overall reaction (4) takes place irreuersibly; whereas
for P approaching infinity, two reaction planes at
x = A, and x = I, (12,> d, > 0) are formed within the
liquid film where the following reactions (5) and (6)
take place irreuersib!v, respectively, as shown in Fig.
ratio P has a very high value (1.4 x lo4 at’30”C) and
therefore the two reaction-plane model should be
applicable. Under certain conditions the intermediate
product HCIO could be desorbed from the first reac-
tion plane A, into the bulk gas phase and the desorp-
tion process may be liquid film or gas film controlled.
Yadav [7] has studied the theoretical aspects of gas
absorption with an instantaneous two-step reaction
followed by desorption of the intermediate species. If
the desorbed HCIO dissociates in the gas phase then
an enhancement in the driving force for desorption
will be realised and this should result in high’er rates
of desorption compared to the case when HClO does
not dissociate in the gas phase. Such a case is also
considered in this paper.
Dissociation of HCIO in the gas -phase
The desorbed hypochlorous acid might undergo
dissociation to chlorine monoxide in the gas phase. It
is known that HCIO and Cl,0 co-exist in the vapour
phase above aqueous solutions of HCIO; Cl,0 being
predominant at higher concentrations [8-131. The
following equilibria are relevant:
2 HCIO (aq)AQO (aq) + H,O (I) (7)
where,
(8)

Cl, + Cl0 - + H,O+2 HClO + Cl 2 HCIO (aq)&l,O (g) + H,O (1)

(5) (9)
(A) (JV (C) (C’)
2HClO+2OH~~2ClO- +2H,O where
(6)
(C) (B> (E)
[ClZO]M - 1 87 at 30°C (10)
It can be seen that reaction (5) represents the overall K9 = [HCIO];,,, - .
case of reaction (2) and the reverse of reaction (3).
Reaction (6) is the forward part of reaction (3) with XII

a multiplication factor of 2. In the present case, the HClO (aq)sHCIO (g) (11)

ir
region I+region
interfock
b-first
IlAreglon

redction
III-

Diane

Fig. 1. Concentration profiles for absorption of chlorine into aqueous NaOH solution followed by
desorption (liquid-filmresistancecontrolled) of HCIO
 Absorption of chlorine in aqueous solutions of sodium hydroxide 1121

where, Here [C,,] and [C*] represent the concentrations of

C at the plane 2, and at the gas-liquid interface,
K = ‘HC’o](g) = l.S9 at 30°C. respectively. DA and D, are the effective diffusivities
02) of dissolved A and C in the region I (A, > x z 0),
’’ [HClO];,,
respectively.
From reactions (9) and (1 l), the following equi- The average rate of absorption of Cl, is given by:
librium reaction and its equilibrium constant can be
established, & = 4AJW ‘1 (5)

KII where, 4n = enhancement factor for absorption of A

2 HClO (gWCl,O (g) + I&O (g) (13)
1
=- (6)
K = PJ,~l,,,FWl~~ = 2 = 0.9894 at 30°C. erftut)
I3 (14)
WJOI:,, II
The locations of the first and second reaction planes,
Thus, it is possible to calculate the equilibrium J., and &, are given by
concentrations of HCIO (g) and Cl,0 (g) above the
aqueous solutions of soldium chloride/hypochlorous A, = 2&J(U (7)
acid in the region I. In the present analysis, it is
il, = &T&J). (8)
assumed that the dissociation of the desorbed HClO
is nor the controlling step. Dissociation of HClO
The constants S, and u2 are evaluated from the
should be advantageous in desorbing HClO as it
following pair of simultaneous equations which are
increases the driving force for desorption in the case
based on the material balances at I, and 1,:
of a gas-film controlled desorption. Several cases can
be analysed depending on whether HClO dissociates
completely, partially or does not dissociate and these
will be discussed later.

Desorption controlled by liquid film resistance

The typical concentration profiles of each species,
namely Cl, (A ), ClO- (E), HCIO (C), Cl - (C’) and
OH- (B), are shown in Fig. 1 and the derivations are

- 2 exp[
presented in Appendix I.
The instantaneous (transient) rate of desorption of
the intermediate product HClO is given by,
E - 1)u,2]
erfJ($u,]
(9)
.
The average rate of desorption over a total exposure
time, rE, is given by,

(10)
(2) The value of [C,,] in eqn (2), being unknown, can be
substituted from eqn (A27) as:
where,

Qcd = enhancement factor for desorption

1
(3)
= erfL,/(DDW~l
k, = true liquid side mass transfer coefficient

=2 2. (4)
J( E> The concentrations of A and C in region I depend
1122 R. N. LAHIRI et al.

on the concentration of NaCl (C’), the latter can be and if the absorption of A is also gas-film controlled,
obtained from eqn (A17).
It can be seen that these equations are rather R, = ka,@,., -PM) (18)
complicated to visualize the actual process of
absorption-desorption. A simplified picture, al- where k,, p, and p. are the true gas-side mass transfer
though less realistic in the present case, can be arrived coefficient, interfacial partial pressure and bulk gas
at, for the case of equal diffusivities of all species. phase partial pressures, respectively.
Thus, However, when both the gas and liquid film re-
sistances to mass transfer are significant the following
[A “I equations hold:
erf(al)
=[A *] + [If,] + [Eo] (111
For desorpiion
tc*1 + 2[A *]
erf(az) = (12)
KC*1+ 2[A *I + ml
&, = k, (13)

Therefore,
R”= k,{[A*1+ ml1+ &I). (14) = 4&L
J(2 > 1
UC,,1- [c*l) (19)

where K,,, is the overall gas-side mass transfer

coefficient for desorption.
Since,

Thus, r represents the following cases: (i) r = 0, for cc,,1 = 4Pi,.c

2[&] + [L&l= [C’], the overall absorption of Cl, to
tC*l = &P,.c
give Cl0 and Cl ; (ii) r = 1, for [E,,] = [A *] + [C*],
the conversion of Cl, to HClO and Cl-; (iii) r = 2, for With the help of eqns (19)-(21), the overall resistance
[E,] % [A *], [&I, [C*], the conversion of ClO- and to desorption is obtained as:
Cl, to give HCIO.

Gas-film controlled process

The typical concentration profiles of each species in
the liquid acid gas phased are shown in Fig. 2, for the
absorption and desorption controlled by gas-film The partial pressure of C at the plane A,. pi,.= is
resistance. The concentration profiles on the liquid obtained from eqns (A27) and (20), and the inter-
side are the same as derived earlier, except that [C’] facial partial pressure, P,.~ is then given by:
approaches [C,,]. The specific rate of desorption is
then, c&c - PG.C)
P1.C = PG.C +- . (23)
1-c
k.
R, = kc.&,, - PG.C) (17) &.&&,j;&P,J >

gas-liquid cregion I&egion IL&egion III ____

interface *

Fig. 2. Concentration profiles for absorption of chlorine into aqueous NaOH solution followed by
desorption (gas-film resistarm controlled) of HClO
 Absorption of chlorine in aqueous solutions of sodium hydroxide 1123

The average specific rate of desorption of C thus can

be evaluated from eqn (19).
When

= PG.*
(28)
phc = pG,c (that is-no gas side resistance) (24) , + 4&A,
When k G.A

when kA % 4AHAkL,
pLAzpGeA(that is-no gas side resistance) (29)

pLc =pn,,= (that is-no liquid side resistance). (251 when kG.AQ 4,H.A
P,.~ 3: 0 (that is-no liquid side resistance). (30)
For absorption
EXPERIMENTAL

The apparatus used in our work is shown sche-

matically in Fig. 3. The absorption of Cl, in aqueous
= kPG,A sodium hydroxide solutions was carried out in a 10 cm
i.d. stirred contactor, with a plane liquid interface and
= 4,k,[A *I independent stirrers for the gas and the liquid phases.
The contactor was provided with internals made out
= 4AHhm. (26)
of polypropylene and was the same as that used by
Therefore, the overall resistance to absorption is, Yadav and Shanna 1141.The contactor was operated
at gas-side stirrer speeds from 120 to 3000 rpm and
1 1 1 liquid-side stirrer speeds from 90-to 280 ‘pm. The
-=-+-. (27) experiments were carried out at 55” and 75°C with
Ki.,, k,, 6PAL
30% w/w and 40% w/w NaOH solutions and at atmo-
spheric pressure. The mode of operation was con-
Hence, A, can be calculated from equ (26). The tinuous. Chlorine, diluted with nitrogen, and satur-
interfacial partial pressure of A is given by: ated with water at such temperatures so that the

Fig. 3. Schematic diagram of experimental set up. (1) Storage tank; (2) soap film meter; (3) soap film
meter; (4) thermostatic bath; (5) coiled heater; (6) thermostatic bath; (7) stirred contactor wound up with
heating coil and appropriate. insulation; (8) liquid levcller; (9) heating coil; (10) three-way stopcock; (11)
three-way stopcock; (12) mechanically agitated contactor; (13) soap film meter; (14) scrubber; (15)
scrubber; T,, thermometer for gas; T, thermometer for liquid.

CeS Vol. 38. No. 7-J

1124 R. N. Lumu er al.
vapour pressure of water would be the same as that
over the NaCl solution at the operating temperatures
in the contactor, was introduced into the contactor. A
metered bleed of the outlet gas was absorbed in an
acidified (HCl) potassium iodide solution in the 10 cm
i.d. mechanically agitated contactor where the gas was
dispersed into the liquid phase. The absorption and
desorption rates of Cl, and HCIO were calculated
from the difference between the inlet and outlet con-
centrations and the total gas flow rate.
Analysis
Chlorine and hypochlorous acid were analysed by
the iodometric method [IS]. The mixture of Cl*, HClO
and N, was absorbed in 200% excess 20”/, aqueous
acidic (0.1 N HCl) KI solution of known amount. The
absorption was meticulously carried out over a known
length of time in such a way that the liberated iodine
was always dissolved in the solution and did not es-
cape. Dehydration of HClO gas in the gas phase to
Cl,0 cannot be distinguished owing to the hydrolysis
of Cl20 to hypochlorous acid in the aqueous phase[S].
The determination of HCIO depends on the follow-
ing reaction:
Cl,0 + H,O --P HClO
2KI + HClO -+ KC1 + KOH + I,
and
Cl, + 2KI +2KCl +I,.
The alkali liberated by HClO and the total iodine
were determined. The liberated I2 was titrated with
N/l0 NalSrOJ (the addition of starch was omitted).
The colourless solution was then treated with methyl
orange indicator and the excess of acid (HCI) was
titrated with N/l0 NaOH solution. The KOH, pro-
duced by the action of HCIO on iodide, requires half
as much acid for neutrahsation as the volume of
thiosulphate required by the iodine set free by HClO.
RESULTS AND DISCUSSlON
The theoretical predictions can only be compared
with the experimental results if the various physico-
chemical data are known. The two reaction-plane
model predicts that an aqueous solution containing
HCIO and NaCl (in the form of Na+ and Cl-) exists
between the gas-liquid interface and the first reaction
plane (region I). The concentration of species CI-
(C’) is given by eqn (A17),
Equation (A17) shows that [C’] is a constant for
given g, and LT?and does not vary with time. The
knowledge of concentration of NaCl in the region I
is required to determine the concentrations of HClO
and Cl2 in that region.
The physical solubility of Cl, as well as HCIO in
aqueous NaCl solution was calculated from the
Henry’s law constant in water with the aid of the
following equations proposed for solubility in electro-
lyte solutions:
log % =-kJ
0 Iv
k,=i+ +i_ +iB
k, is the salting out parameter and i, and i_ are the
contributions to k, by positive and negative (Na + and
Cl-) ions and ir by the solute gases (Cl2 and HClO).
The values of H, for Cl, in water at 55 and 75°C were
estimated from the Henry’s law constant for
C&-water system after correcting for the hydrolysis
constant [16-191 and were taken as 2.52 x 10-r and
1.55 x lo- 5 gmolejcm3 atm, respectively. The values
of i for Na+ and Cl- were taken as 0.091 and
0.021 I/gion from the data of van Krevelen and
IIoftijzer [20]. The values of ip for Cl2 up to 50°C are
given by Hikita et al. [3]. The values of i, for Cl, were
estimated from the solubilities of Cl2 in water and
aqueous NaCl solutions [16] at 55 and 75°C from
Equations (31) and (32) as -0.0327 and - 0.0408 l/g
ion, respectively. These values appear to be reason-
able when compared with the data of Hikita er al. [3].
The values of H, for HCIO gas in water were
estimated from the data of Secoy and Cady [9],
Ourisson and Kastner [lo], Israel [ 111 and Imagawa
[12] (u$ to 60°C) by extrapolation from plots of
log H, against l/T. It should be noted that these
solubility partial pressure data were obtained for
aqueous HCIO-C&O(g) system wherein the vapours
composed of HClO and Cl,O[S]. The values of H, for
HClO were estimated as 28.7 x 10e3 and
8.94 x IO-‘gmole/cm3 atm at 55 and 75”C, re-
spectively.
Imagawa [ 121 has given a value of it for HClO to
be - 0.054 I/gion at 5O”C, which is assumed to be the
same at 55 and 75”C, ignoring the effect of tem-
perature on i,, in the absence of any data. The partial
pressures of Cl1 and HClO gases were corrected for
the vapour pressure of water over aqueous NaCl
solution of strength [C’] given by eqn (A17) at the
prevalent temperature.
The equilibrium data for C&O(g) and HClO (g)
over aqueous HClO solutions [8-131 were extrapo-
lated to 55 and 75°C by making a plot of log&
against l/T and the values of K,, at 55 and 75°C were
obtained as 1.13 and 1.26, respectively.
The liquid phase diffusivity of Cl,, D,, in the
reacting solution was predicted from the reported
value of 1.48 x 10-5cmz/sec for C&-water system at
25°C and infinite dilution [l, 31 after correcting for
the effect of temperature and viscosity of the solution
according to the StokesEinstein relation:
 Absorption of chlorine in aqueous solutions of sodium hydroxide 1125
of equal diffusivities. The inverse of error functions
was evaluated by using the following equation [24]

where p is the effective viscosity of the solution and erf- ‘(X) = Inverse of erf(X)
T is the absolute temperature. Cl* diffuses only in
region I (0 < x c 1,). The viscosity of that region was X = sin-’ sin-’ G(Y) (35)
taken as the same as that of aqueous NaCl of. total ( >
strength [C’] and [C*], the latter king concentration
where,
of HCIO in region I. This was done in order to
account for the effect of presence of HCIO of strength
X’ = erf(X) (35a)
[C*] in this region, as no viscosity data were avail-
able. The theoretical predictions showed that the
A general method was adopted to calculate the
concentration in region I was equal to [C*], which
values of overall gas-side mass transfer coefficients
was the same as [C,,], as discussed in the text later.
KC.A and KG,, for absorption and desorption, re-
The liquid phase diffusivities of HCIO (03, Cl-
spectively, and then the specific rates (average) of
(&), OCI- (DE) and OH- (D,) at 25°C and infinite
absorption, R,, and desorption, &, were obtained.
dilution were taken from the data of Hikita et al. [3]
In the case of desorption, the process was found to
as 1.54 x lo-‘, 2.072 x 10m5 1.163 x 10m5 and
be exclusively gas-film controlled whereas, the ab-
3.434 x lo-‘, respectively. The viscosities of regions
sorption was found to have different gas-side re-
I, II and III were different. The viscosities of region
sistance, depending on the speed of agitation of the
I and II were nearly comparable and were much less
gas-side stirrer. The deviations reported in the specific
than that of region III which mainly comprised of
rates are with reference to the experimental values.
OH- ions. Therefore, effective diffusivities of each
The values of kG.Aand k,,, were calculated for each
species at the operating temperatures were calculated
case of gas phase compositions.
for each region. The arithmetic mean of values
The calculations were performed for different cases
estimated in regions I and II was used for D, and D,
of dissociation of HClO(g):
and that in regions II and III for DE, for the
Case (i): no dissociation of HCIO. In this case, the
calculation purposes. The values of D, and D, were
partial pressure of HClO in the bulk gas phase, /I~.~,
those estimated in regions I and 111, respectively (see
was taken as the same as found by analysing the
Figs. I and 2).
liquid phase for total HCIO.
The values of true gas- and liquid-side mass trans-
Case (ii): complete dthociation of HCIO. The par-
fer coefficients, k, and k,, at various speeds of gas-
tial pressure of HCIO in the bulk gas phase was taken
and liquid-side stirrers are reported for SO,-N, and
as zero and it was assumed that entire HClO gets
CO,-water systems at 30°C by Yadav [6] and were
converted to Cl,0 in the gas phase.
corrected for the present system on the basis that true
Case (iii): partial dissociation of HClO. The calcu-
mass transfer coefficient varies as the square root of
lations were performed at different levels of con-
diffusivityf211. The values of gas-phase diffusivities
version of HClO(g) to Cl@(g>lO, 25,40, 70,80,90%
for the binary systems were estimated from Fuller et
and the equilibrium conversion value. The equi-
al. [22] as modified by Reid et al. (231. The values of
librium partial pressures were calculated from the
binary diffusivities for CIIHCIO, C@+&O,
knowledge of the equilibrium constant, K,,, at the
Cl,-H,O, Q-N,, HCIO-CI,O, HC10-H20 and
operating temperature and the total HClO found by
HCIGN, pairs were estimated as 0.0878, 0.0663,
liquid phase analysis. Since no gas phase analysis was
0. I%, 0.1476, 0.0747, 0.1574 and 0.1678 at WC, and
performed to find out Cl*, HCIO, Cl,0 and H,O in
0.0988, 0.0746, 0.176, 0.1646, 0.0842, 0.1777 and
the gas phase, our arguments in favour of different
0.18749 at 75”C, respectively. The effective gas phase
degrees of conversion, apart from the main three
diffusivities of Cl, and HClO, D,, in the mixture
cases (i)-(iii) are somewhat weak. However, it should
consisting of Cl,, HClO, CI,O, I-I,0 and N, were
indicate whether the gas HClO dissociates or not and
calculated on the basis of the following equation [23],
whether it affects the desorption rates.

1 - xj General observations
R,= -

i ,;;;
Typical trial and error procedure
1
.

=2
The distance I, of the first reaction-plane

were of order
1 x 1om4-5 x 1o-4 and 0.03-0.2,
of
from the
gas-liquid interface was very small. (Typically u, and
the magnitude
respectively).
A PDP-11 desk computer was used to obtain the Therefore, the effective value of true liquid side mass
values of o, and c2 which would simultaneously transfer coefficient for desorption for region I would
satisfy eqns (9) and (10). The trial and error pro- be very high. As a result, there was no liquid side
cedure was based on the Newton-Raphson technique resistance for desorption of HCIO and it was found
in that the first guess values of IT, and u2 were that the desorption was exclusively gas film con-
calculated from Equations (11) and (12), for the case trolled (> 99% gas-film resistance) (HClO is highly
 Table 1. Effect of gas-side mass transfer co&cient on desxption of HCIO
Llqnid-e$de rtirrer epead = 240 rev/tin ~aperature = 55% e
-3
- 4.51 x IQ c+ec CBel = 10.2 I x, -3 &801e/cmf
%J

Run Partial prceeure Outlet Gas-side kGx105 Bxperimental, Theoretical, Dcvia- Devia- Regitin
Hb. af Cl2, atm partid etlrrer tlon I Remarks
&or pole/orFeec pule/om2eeo u”E
pressure speed, HClO ce for
in R, in iiCd [RatZJ
Inlet Outlet of IiCl.O. rev/ndn
%

atm

I 0.625 0.382 0.082 120 6.12 7.913 1.050 13.2 - _ 4

0.0 92.4 22.14 0.924 -170.4 12 2.+ Complete
dissociation E
E
2 0.636 0.368 0.107 800 9.3O 6.73 1.326 15.2 - _ a
67.1 23.22 1.014 -166 10.6 2.1 Complete 5
?-
0 *owl
di660ClafiQn
0.0

3 0.636 0.280 0.153 2400 24.38 10.38 1.807 17.4 _ -

0.0 34.2 22.916 1.618 -120.8 10.4 2.2 Complete

diseociation

(N.B. The match in L&S and RHS of Equation (IO) wae wfthin 5-10 x )
 Table 2. Effect of gas-side mass transfer coefficient on desorption of HCIO

Liquid-side stirrer speed - 140 rev/tin [ E&Ii ] - 10.2 I 10’3 gmole/cm3

= 3.236 x lo-’ cm/set Temperature n 75’C
t
-u-

Run Partial pressure Outlet

;rr;;p kGx105 Experimental, Yield Gas-aide Theoretical, Detia- Devfa- Region
NO. of C12, ati pa&al
reslstan- gmole/cm2eec tion in tion I Remarks
ygy wed. for gmle/cm2atm Of
IiClO ce for
Inlet outlet , rev/tin so2-w2 ? Ln iiCd [NaCl..
$i:rp- x %
atm
l?wS? % &d g A %d
P0.A PG,A n
', x
pG,C cdsec x IO6 x lo6 % x 106 x 106
atm
--- --
5.
1 0.524 0.400 0.0607 500 8,122 6.46 1.156 17.90 48.6 17.13 1.035 -165.2 lo.4 2.5 No diesocla-
tion
0.0364 47.6 16.575 1.108 -158.7 4.1 2.4 Equilibrium

0.0 47.5 16.30 1.400 -152.4 -21.2 2.5 Complete

diseociation

2 0.544 0.353 0.1171 2000 20.5~ 6.912 2.136 30.91 23.3 17.78 1.0373 -157.2 51.5 2.8 NO dlaso-
elation
0.0503 22.8 16.77 1.392 -142.7 34.9 2.4 Equllibriua

0.0 22.7 16.105 4.056 -lJ3. -89.5 2.2 Complete

dls8ocietion

3 0.533 0.351 0.132 5000 28.0 7.057 2.591 37.0 17.5 18.00 1.78 -155.0 31.3 2.9 No diesocia-
ti on
0.0561 16.7 17.032 3.038 -142.1 2.1 2.5 Equilibrium

0.0 16.4 16.14 5.57 -128.7 -115. 2.2 Complete

diesociation

-
v---
 Table 3. Effect of liquid-side mass transfer cocfficicnt on desorption of HCIO

Gas-side stirrer speed = 2400 rev/tin Temperature = 55OC

-5
= 24.41 x 10 gmole/cm2sec atm [ NsOHI = 10.2 x 10-J gmo1e/cm3
kc

~~-------~--~.--.~_ ---_-
Run Partial pressure Outlet Liquid- %_,03 ExperimFtsl, Y;;ld Gas-side Theoretical, Devia- Devia- Region
No. of C12, atm partial side
-------- pressure stirrer gmole/cm set
Inlet Out1 et of HClO, speed,
atm r ev/min cm/se c % %d
po .A PC,*
x106 x106
pG ,C
--- - -_ -_--

0.635 0.280 0.153 240 4.57 lo.667 1.807 16.34 No solution

0.0644 0.0644 38.6 26.44 1.224 -140.0 32.3 3.3 Equilibrium

0.0 0.0 34.2 23.0 2.197 -114.9 10.1 2.3 Complete

dlsSoolation

0.651 0.62 0.145 190 3.613 9.180 2.0712 22.60 No solution

0.0615 0.0615 22.3 20.56 2.190 -124.1 -5.8 3.3 Equilibrium

0.0 0.0 20.0 18.05 2.683 -96.7 -29.6 2.3 Complete

dissociation

0,623 0.417 0.117 140 2.66 6.441 1.776 27.60 No solution

0.0507 14.5 14.80 2.183 -129.7 -22.7 3.1 Equilibrium

0.0 13.2 13.26 3.127 -106.0 -75.7 2.3 Complete

dissociation

0.637 0.471 0.104 90 1.72 5.236 1.704 32.54 Ho solution

0.0455 8.1 9.367 1.690 -79.0 0.9 3.0 Equilibrium

0.0 1.4 8.426 2.411 - 61.0 -41.5 2.2 Complete

dissociation

---_-
 Table 4. Effectof liquid-sidemass transfer coefficient on desorption of HCIO

Gas-side mass transfer speed = 3000 rev/mln c NeQHl - 10.2 x 10’3 gmole/cn3
-5 gmcle/cm2eec atm
= 28.0 x 10 !Cemperature = 75Oc
kG

Run Partial preaaure Outlet Theoretical, Devia- Devla- Region

Exparizwntal, Yield Gao-side Remark6
No. of Cl2, atm partial reaiatan- gmol e/cm2sec tibn tion I
;;e;gsae stirrer pole/cm2aec cf
HC10, ce for
speed, in i* in iicd @aCiJ
Inlet Outlet .
atm rev/min cm/set B Y. I g M
po ,A PG,A A %d 6
pG,C
X106 x106

0.534 0.250 0.172 190 4.395 9.60 2.941 30.60 35. 25.43 t.867 -165. 36.5

0.0707 33.4 23.75 2.564 -147.5 12.8 2.6 Equlllbrim

0.0 31.9 22.03 3.38 -129.5 -21.8 2.2 Complete

dissociation

o.s39 0.351 0.127 140 3.236 7.023 2.592 36.96 17.4 17.96 1.924 -155.8 25.8 2.9 No dieso-
ciation
0.0546 16.9 17.015 3.18 -142.3 -23.0 2.5 Equilibria

0.0 16.4 16.14 5.59 -129.8 -115.7 2.2 Complete

dirroclation

0.544 0.398 0.110 90 2.086 2.05 5.084 46.0 9.8 71.49 3.194 -q26.0 -36.7 2.8 No dieeo-
elation
0.0476 9.4 10.818 2.367 -112.8 -2.2 2.4 Equilibrlnm

0.0 9.2 10.33 4.367 -103.3 -86.9 2.2 Coslplete

dlsaociatlon
1130 R. N. LAHIRI ef al.
soluble in water). On the contrary, absorption of Cl,
was found to have significant or negligible gas-side
resistance, depending on the gas-side stirrer speed
and bulk gas phase partial pressure. Tables 1 and 2
show that, under otherwise similar conditions, the
rates of absorption and desorption increase with an
increase in the gas-side stirring speeds and also the
yield of HClO increases; this is expected for a
gas-film controlled desorption. Tables 3 and 4 show
that with an increase in kL for a specified value of ko,
the value of ;1, - a, decreases and this results in
reduced resistance to mass transfer for HCIO and
hence
increases. Thus, more HCIO goes to the reaction
plane at x = 1, to react with OH - and hence the yield
of desorbed HClO decreases. In no case, the concen-
tration of NaCl in region I was found to be above its
saturation value. Except for the entries in Table 1, the
theoretical rates of desorption of HClO (&) were
found to be in reasonably good agreement with the
experimental values for the case of equilibrium con-
version of HClO to Cl,0 (case iii) in the gas phase.
The other models based on the conversion of HClO
to Cl,0 around the equilibrium values also fitted the
data but less accurately. For case (iii) of equilibrium
conversion Tables 24 showed a deviation in & as
ls35, 2-22, 2.5-23 and 30-60x, respectively, where
the derivations were defined with reference to the
experimental values. Tables 24 show a deviation of
10&160% in the specific rates of absorption. The
above agreements between experimental results and
theoretical predictions should be considered as rea-
sonably good in tiew of the assumptions made and
errors associated with the estimations of physico-
chemical data. In the case of Table 1, the match in
left hand and right hand sides of eqns (9) and (10) was
within 5-10x and showed that the model based on
complete dissociation of HClO predicted the the-
oretical values of &,, with IO-15% of the experi-
mental values. In no case, data fitted for case (i) of
no dissociation of HClO in the gas phase.
The deviations in the rates of absorption can
perhaps be attributed partly to the stoichiometric
factor of the overall reaction, which might be within
1 and 2, depending on the experimental conditions. In
the case of a two-plane model Cl, reacts with 1 mole
of OH- to produce HClO whereas that of a single-
plane model Cl, reacts with 2 moles of OH- to
produce CIO- _The representative values of kL, under
the conditions prevalent in this work, are expected to
be somewhat different from those employed in this
work.
Further, the discrepancies in the experimental and
theoretical values could be assigned to the various
assumptions made and also to the predicted physico-
chemical data. However, the general trends given by
theoretical predictions and the experimental results
are practically the same. In general dissociation of
HCIO in the gas phase is always advantageous to
increase the driving force for desorption and the
yields and hence experiments at higher temperatures
at u 100°C should merit attention.
The maximum yield of HClO found by us was
about 46%; Olin Corporation (U.S.A.) have claimed
a yield of 69% in a spray column. In a spray column
k, value can be relatively very large and k, value is
very low and hence we can expect a higher yield. The
types of reactor reported in the patents do combine
higher values of ko with relatively low values of k,
and this combination is conducive for higher yields of
desorbed HCIO.
MNCLUSIONS
(i) Absorption of rich mixtures of chlorine with an
inert gas in concentrated aqueous solutions of NaOH
can be performed with concurrent desorption of
HClO despite a large excess of NaOH in the bulk
liquid phase. The HClO on desorption was found to
dissociate to Cl20 in the gas phase thereby increasing
the rate of desorption.
(ii) The agreement between theoretical predictions
and experimental observations was found to be rea-
sonably good.
(iii) The specific rate of desorption of HClO in-
creases with an increase in the value- of kG and a
decrease in the value of kL. Gas-liquid contactors
which offer high values of k, and low values of k,,
such as spray absorbers, are recommended.
REFERENCES
[I] Spalding C. W., A.1.Ch.E.J. 1962 8 685.
121
_ _ Takahashi H., Hatanaka M. and Konaka R., Can. J.
Chem. Engng 1967 45 145.
[3] Hikita H., Asai S. and Takatsuka T., Chem. Engng J.
1973 5 77.
[4] Hikita H., A& S. and Takatsuka T., Chem. Engng J.
1972 4 31.
[5] U.S. Pat.4,146,578 (to OlinCorporation) 1979; Chem.
Abstr. 1979 90 18924%.
[6] U.S. Pot. 4,147,761 (to Olin Corporation) 1979; Chem.
Abstr. 1979 90 189245f.
[7] Yadav G. D., Heterogeneacs reactions. Ph.D. (Tech.)
Thesis, Bombay University, Bombay 1980.
[8] Renard J. J. and Bolker H. I., Chem. Rev. 1976 76 487.
[9] &coy C. H. and Cady G. H., J. Am. Chem. Sot. 1940
62 1036.
[IO] Ourisson J. and Kastner M., Bull. Sot. Chim. Fr. 1939
6 1307.
[I 1] Israel B. M., Doctoral Dissertation, University of
Washington, 1962; cited by Ref. [8].
[IZ] Imagawa H., J. Electroche&. Sot. (Japan) 1950 18 382;
1951 19 271.
[I 31 Kirk R. E. and Othmer D. F., Encyclopedia of Chemical
Technology, 3rd Edn., Vol. 5. Wiley-Interscience, New
York 1979.
[14] Yadav G. D. and Sharma M. M., C’hem.Engng Sci.
1981 36 599; 1982 37 341.
[IS] Scott W. W., Standard Metho& of Chemical Analysti,
5th Edn., Vol. I. Von Nostrand, New Jersey 1956.
[16] International Critical Tables of Numerical Data of Phys-
ics, Chemistry and Technology, Vol. 3. McGraw-Hill,
New York 1928.
[17] Adams F. W. and Edmonds S., ind. Engng Chem. 1937
29 447.
[18] Brian P. L. T., Vivian J. E. and Piazza C., Chem. Engng
Sci. 1966 21 551.
 Absorption of chlorine in aqueous solutions of sodium hydroxide 1131

[I91 Connick A. E. and Chia Y. T., J, Am. Chem. Sot. 1959 true gas-side mass transfer
81 1280. coefficient, gmole/cm2set atm
[201 van Krevelen D. W. and Hoftijzer P. I., Chem. Ind., true gas-side mass transfer
Numero %&ale du XXI e Congress International de
Chimie In&strielle, Bruxelles, S&t 1948 p. 168. coefficient for A and C, re-
WI Yadav G. D. and Sharma M. M., Chem. .&cmz Sci. spectively, gmole/cm2 set atm
1979 ti 1423. true liquid-side mass transfer
WI Fuller E. N., Schettler P. D. and Giddings J. C. Ind. coefficient for A, cm/set
Engng Chem. 1966 58 (5) 18.
salting-out parameter, gion/l
~31 Reid R. C., Prausnitz J. M. and SherwoodT. K., The
Properties of Gases undLiquids, 3rd Edn. McGraw-Hill, overall gas-side mass transfer
New York 1977. coefficient, gmole/cm’set atm
1241H. T. Karhson and I. Bjerle, Comput. Chem. Engng overall gas-side mass transfer
1980 4 67. coefficient for A and C, re-
spectively, gmole/cn? set atm
NOTATION equilibrium constant of reactions
gaseous species Cl2 (lH13), respectively
concentration of dissolved Cl, in bulk partial pressure of gas, atm
liquid phase, gmole/cm3 bulk partial pressure of A and C,
concentration of dissolved Cl, at respectively, atm
interface, gmole/cm3 interfacial partial pressure of gas,
concentration of Cl* in water, atm
gmole/cm’ interfacial partial pressure of A
liquid phase reactant NaOH and C, respectively, atm
concentration of NaOH in liquid partial pressure of gas at plane A,,
phase, gmole/cn? atm
concentration of NaOH in bulk partial pressure of C at plane A,,
liquid phase, gmole/cm’ atm
intermediate reactive gaseous spe- K,IK,, equilibrium constant ratio
cies HClO &,/R,, ratio of average rate of de-
concentration of dissolved HClO sorption to that of absorption
in liquid phase, gmole/cm3 instantaneous rate of absorption/
concentration of dissolved HClO desorption, gmole/cm2set
at interface, gmole/cm3 average (specific) rate of
concentration of dissolved HClO absorption/desorption, gmole/cn?
at first plane x = L,, gmole/cm3 SW;

intermediate non-reactive species specific (average) rate of absorp-

Cl- tion and desorptian, respectively,
concentration of Cl- in liquid over exposure time tE,
phase, gmole/cm’ gmole/cm’set
concentration of Cl- at interface, time, set
gmole/cm3 exposure time, set
concentration of Cl in bulk liquid temperature, “K
phase, gmole/cm3 distance from gas-liquid interface
gas phase diffusivity of binary mix- into liquid, cm
ture i and j mole fraction of i and jth com-
gas phase diffusivity of ith com-
ponent in mixture iz?unction, (2/Jn)&,X e -y* dy
diffusivities of Cl?, OH-, HClO, complementary error function,
Cl- and ClO- in liquid phase, (1 - erf(X))
cm’/sec
final product Cl0 -
concentration of ClO- in bulk liq-
uid phase, gmole/cm’ enhancement factors for absorp-
Henry’s law constant for HCIO, tion of A and desorption of C, re-
gmole/cm) atm spectively
solubility of A, C in an electrolyte distance of reaction plane from
solution, gmole/cm3 atm gas-liquid interface in liquid-film,
solubility of gas in water, gmolej cm
cm3 atm distances from interface to first
ionic strength of solution, gion/l and second reaction planes, cm
contribution of positive ion, nega- parameters defined through eqns
tive ion and solute gas, re- (7) and (S), respectively
spectively, to k,, ljgion viscosity of solution, CP
1132 R. N. LAWIRI et al.

Subscripts where,
A gas A Cl,
C gas C, HCIO
d desorption
G bulk gas phase represent the values of a[C]/ax when x approaches I, from
.
ith and jth components region 1 and II, respectively. Similarly
planes 1, and AZ

APPENDIX
The reaction scheme for Cl,-NaOH system is of the form:
represent the values of ~[E~/L?.xwhen x approaches AZfrom
region II and III, respectively. The rate of absorption of A
A+&C+C’ (2a) and the rate of desorption of C at any instant f are given,
respectively, by:

C+B SE. (3aJ

(All)
Because P = K2/K3 is very high, two reaction planes are
formed where the following reactions take place irreversibly. and,

(Al’3
A+E+C+C’ Pa)
The average rates are given by:
2C + 2B+2E. w

The basic differential equations describing the diffusion of (A131

each species (Fig. 1 and 2) based on penetration theory in
region I (0 c x c I,), region II (d, < x -z 42) and region III
(1, i x < co) are as follows [3,7]: The solutions of eqns (A2HAS) for regions II and III are the
same as given by Hikita er al. [3]. The concentration profiles
%I1 WI of all specieJ in each region are obtained as follows [7l:
DA= = ar (region I) (Al)
Region I(0 c x 4 L,)

(region III) 642) (B]=[E]=O (A14)

D J2[Cl WI
c = dt (region I, II) c.43)
(AI51
D a*Vl W7
T = dt (region I, II, III) 644)
[Cl = IC’] + (Id!] - (AI@
a*Pl d[El
DV = at (region II, III) 645)

The initial and boundary conditions are:

1=0,x20; [B]=[BJ W)

r>o,x=0; [A]=[A’],[C]=[r?]
(A7)

[C’] = [fy] a[c7 = 0

’ ax

I > 0, x = 2,; [A] = 0, [C] = [C,,] 6417)

Region II (1, < X < &)
[E]=O (A181
[A]=[B]=O
a[Al WI atC1
2D,% = -2Ds = 2Dq

(As)
=Df$~L)

t>O,x=L,; [B]=O,[C]=O
aPI
D%=-D%=D wl (A9)

r>O,x+m; [B]=[Bd,[E]=[Ed
(Al’%
WI = Pa t
 Absorption of chlorine in aqueous solutions of sodium hydroxide 1133

[C’] will be the same as given by (AZI). The locations of the

first and second reaction planes are given by:

(A21) A, = 2u,J(D,O (A251

AZ= Zu,.,/(D,r). (A261

Region Ii1 (A2 < x -z co)

(A22) The values of the constants O, and b2 in the above equations
can be determined by solving eqns (4) and (5). The value of
[C,,] is obtained by putting x = 1, in Equation (A19) as
(A231

[El

Now the rate of desorption of C at any instant t is given

by eqn (1) and its average value by eqn (2). For a gas-film
controlled desorption process, the pertinent equations are
given in the text.