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Absorption of Chlorine in Aqueous Solutions of Sodium Hydroxide
Absorption of Chlorine in Aqueous Solutions of Sodium Hydroxide
1119-1133, 1983
Printed in Glsat Britain.
chloramines and chloroisocyanurates. The Olin Cor- ratio P has a very high value (1.4 x lo4 at’30”C) and
poration, U.S.A., has a few patents [5, 61 describing therefore the two reaction-plane model should be
the absorption of Cl, in alkali metal hydroxide solu- applicable. Under certain conditions the intermediate
tions (4&75% w/w) at elevated temperatures product HCIO could be desorbed from the first reac-
(50-2OO“C)in a spray column or a sweep reactor from tion plane A, into the bulk gas phase and the desorp-
which the HCIO vapours are recovered by scrubbing tion process may be liquid film or gas film controlled.
the gaseous mixture of Cl,, HClO and Cl20 with water Yadav [7] has studied the theoretical aspects of gas
at low temperatures. The use of rotating drums, absorption with an instantaneous two-step reaction
falling film absorbers, etc. has also been claimed. followed by desorption of the intermediate species. If
It was therefore thought desirable to study the the desorbed HCIO dissociates in the gas phase then
desorption of HClO when rich mixtures of Cl, are an enhancement in the driving force for desorption
absorbed in concentrated NaOH solutions at higher will be realised and this should result in high’er rates
temperatures. of desorption compared to the case when HClO does
not dissociate in the gas phase. Such a case is also
MECHANISM OF ABSORPTION-DESORFTION
considered in this paper.
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) Dissociation of HCIO in the gas -phase
has a forward rate constant of 2 1.4set - ’at 30°C and The desorbed hypochlorous acid might undergo
makes negligible contribution to the total rate of Cl, dissociation to chlorine monoxide in the gas phase. It
absorption. It was shown [4] on the basis of the is known that HCIO and Cl,0 co-exist in the vapour
penetration theory for gas absorption accompanied phase above aqueous solutions of HCIO; Cl,0 being
by an instantaneous two-step reaction that the mech- predominant at higher concentrations [8-131. The
anism of absorption depends on the ratio P (= ZCJKJ. following equilibria are relevant:
In the limiting cases, when P tends to be zero, there
exists a single plane in the liquid film at which the 2 HCIO (aq)AQO (aq) + H,O (I) (7)
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 where,
liquid film where the following reactions (5) and (6)
take place irreuersib!v, respectively, as shown in Fig.
(8)
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
- 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,
=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)
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
= 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
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.
vapour pressure of water would be the same as that knowledge of concentration of NaCl in the region I
over the NaCl solution at the operating temperatures is required to determine the concentrations of HClO
in the contactor, was introduced into the contactor. A and Cl2 in that region.
metered bleed of the outlet gas was absorbed in an The physical solubility of Cl, as well as HCIO in
acidified (HCl) potassium iodide solution in the 10 cm aqueous NaCl solution was calculated from the
i.d. mechanically agitated contactor where the gas was Henry’s law constant in water with the aid of the
dispersed into the liquid phase. The absorption and following equations proposed for solubility in electro-
desorption rates of Cl, and HCIO were calculated lyte solutions:
from the difference between the inlet and outlet con-
centrations and the total gas flow rate.
log % =-kJ
0 Iv
Analysis
k,=i+ +i_ +iB
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 k, is the salting out parameter and i, and i_ are the
acidic (0.1 N HCl) KI solution of known amount. The contributions to k, by positive and negative (Na + and
absorption was meticulously carried out over a known Cl-) ions and ir by the solute gases (Cl2 and HClO).
length of time in such a way that the liberated iodine The values of H, for Cl, in water at 55 and 75°C were
was always dissolved in the solution and did not es- estimated from the Henry’s law constant for
cape. Dehydration of HClO gas in the gas phase to C&-water system after correcting for the hydrolysis
Cl,0 cannot be distinguished owing to the hydrolysis constant [16-191 and were taken as 2.52 x 10-r and
of Cl20 to hypochlorous acid in the aqueous phase[S]. 1.55 x lo- 5 gmolejcm3 atm, respectively. The values
The determination of HCIO depends on the follow- of i for Na+ and Cl- were taken as 0.091 and
ing reaction: 0.021 I/gion from the data of van Krevelen and
IIoftijzer [20]. The values of ip for Cl2 up to 50°C are
Cl,0 + H,O --P HClO given by Hikita et al. [3]. The values of i, for Cl, were
estimated from the solubilities of Cl2 in water and
2KI + HClO -+ KC1 + KOH + I,
aqueous NaCl solutions [16] at 55 and 75°C from
and Equations (31) and (32) as -0.0327 and - 0.0408 l/g
ion, respectively. These values appear to be reason-
Cl, + 2KI +2KCl +I,. able when compared with the data of Hikita er al. [3].
The values of H, for HCIO gas in water were
The alkali liberated by HClO and the total iodine
estimated from the data of Secoy and Cady [9],
were determined. The liberated I2 was titrated with
Ourisson and Kastner [lo], Israel [ 111 and Imagawa
N/l0 NalSrOJ (the addition of starch was omitted).
[12] (u$ to 60°C) by extrapolation from plots of
The colourless solution was then treated with methyl
log H, against l/T. It should be noted that these
orange indicator and the excess of acid (HCI) was
solubility partial pressure data were obtained for
titrated with N/l0 NaOH solution. The KOH, pro-
aqueous HCIO-C&O(g) system wherein the vapours
duced by the action of HCIO on iodide, requires half
composed of HClO and Cl,O[S]. The values of H, for
as much acid for neutrahsation as the volume of
HClO were estimated as 28.7 x 10e3 and
thiosulphate required by the iodine set free by HClO.
8.94 x IO-‘gmole/cm3 atm at 55 and 75”C, re-
RESULTS AND DISCUSSlON spectively.
Imagawa [ 121 has given a value of it for HClO to
The theoretical predictions can only be compared
with the experimental results if the various physico- be - 0.054 I/gion at 5O”C, which is assumed to be the
chemical data are known. The two reaction-plane same at 55 and 75”C, ignoring the effect of tem-
model predicts that an aqueous solution containing perature on i,, in the absence of any data. The partial
HCIO and NaCl (in the form of Na+ and Cl-) exists pressures of Cl1 and HClO gases were corrected for
between the gas-liquid interface and the first reaction the vapour pressure of water over aqueous NaCl
plane (region I). The concentration of species CI- solution of strength [C’] given by eqn (A17) at the
(C’) is given by eqn (A17), 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
Equation (A17) shows that [C’] is a constant for the effect of temperature and viscosity of the solution
given g, and LT?and does not vary with time. The 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
(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
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
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
-
v---
Table 3. Effect of liquid-side mass transfer cocfficicnt on desorption of HCIO
~~-------~--~.--.~_ ---_-
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
--- - -_ -_--
---_-
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
0.534 0.250 0.172 190 4.395 9.60 2.941 30.60 35. 25.43 t.867 -165. 36.5
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
0.544 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
soluble in water). On the contrary, absorption of Cl, are practically the same. In general dissociation of
was found to have significant or negligible gas-side HCIO in the gas phase is always advantageous to
resistance, depending on the gas-side stirrer speed increase the driving force for desorption and the
and bulk gas phase partial pressure. Tables 1 and 2 yields and hence experiments at higher temperatures
show that, under otherwise similar conditions, the at u 100°C should merit attention.
rates of absorption and desorption increase with an The maximum yield of HClO found by us was
increase in the gas-side stirring speeds and also the about 46%; Olin Corporation (U.S.A.) have claimed
yield of HClO increases; this is expected for a a yield of 69% in a spray column. In a spray column
gas-film controlled desorption. Tables 3 and 4 show k, value can be relatively very large and k, value is
that with an increase in kL for a specified value of ko, very low and hence we can expect a higher yield. The
the value of ;1, - a, decreases and this results in types of reactor reported in the patents do combine
reduced resistance to mass transfer for HCIO and higher values of ko with relatively low values of k,
hence and this combination is conducive for higher yields of
desorbed HCIO.
MNCLUSIONS
[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;
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:
(Al’3
A+E+C+C’ Pa)
The average rates are given by:
2C + 2B+2E. w
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)
1=0,x20; [B]=[BJ W)
r>o,x=0; [A]=[A’],[C]=[r?]
(A7)
(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
[El