356

Bott & Schulz: Solubility of Chlorine in Brine at Duerent p H Values

SOLUBILITY OF CHLORINE IN A BRINE SOLUTION

AT DIFFERENT pH VALUES
By T. R. BOTT and S. SCHULZ
The solubilities of chlorine in a solution containing 250 g/litre of sodium chloride, at different pH values (in
the range 1-2.5) have been experimentally determined at different chlorine partial pressures and at temperatures of 50" and 75". The results show some slight divergence from data previously reported in the
literature but these were obtained by a different procedure.

Introduction
Absorption of chlorine in water involves not only physical
solution, C12(as), but also chemical reaction. The reaction
which takes place is:

CI2 (as) 2H20

HOCl H 3 0 + C1-. ...........(1)

The 'active chlorine', or the chlorine present in solution due to

absorption, C12 (act), is therefore made up of a proportion
each of Clz (aq), HOCl and C1-.
If, however, the solvent is not pure water but water containing a quantity of dissolved sodium chloride, the conditions become more complex since the common ion gains
importance. Several reactions are considered to take place
in addition to the physical absorption of chlorine (as with
pure water) i.e.:Cl5+2H50

+ HOCl+H,O++Cl- ...............(2)

..........(3)
HOCl+H20 k H 3 0 + +CIO- ..................... (4)
Clz + CI- % (213- ....................................... ( 5 )
3C12 9H20

% 6H,O++

5Clk-t CIOs-..

The different reactions suggest that there is a strong dependence of chlorine solubility on hydrogen ion concentration, since the equilibrium of the various reactions will be
affected by pH.
Similarly, sodium chloride being a strong electrolyte is
virtually completely dissociated producing C1- ions in solution which in turn at least affects the equilibrium position
of some of the reactions. The solubility of chlorine in brine

will be dependent upon partial pressure of chlorine, salt

concentration and p H in the salt solution and the temperature. Barr' has made theoretical investigations of this problem.
Solubility data of chlorine in brine without reference to
pH are given in the l i t e r a t ~ r e . ~A- ~paper by Yokota5 gives
data which makes allowance for hydrogen ion concentration.
Data on the solubility of chlorine in salt solution are important for the efficient operation of electrolytic cells producing chlorine, and in the design, and operation, of absorption towers for the recovery of chlorine with brine.
Experimental

A dynamic method for the determination of the chlorine

solubility was adopted, since it had the advantage of steady
conditions. The stirring action of bubbling the gas through
the liquid in the absorption cell avoided the possibility of
supersaturation.
Fig. I shows the apparatus in diagrammatic form. In
order to be able to vary the partial pressure of the chlorine
in the apparatus, nitrogen could be supplied from a pressurised
supply and mixed with gaseous chlorine from a liquified
supply. Before mixing, the nitrogen and chlorine could be
metered separately.
After mixing, the combined gas stream passed through a
heater and a series of water saturators maintained at constant
temperature in a bath. The temperature of this well-stirred
bath was maintained at a fixed temperature below the absorption cell temperature (to within +0*15"), so that the water
vapour content of the gas stream entering the absorption

-&N2

'I

1. Needle valve
5. Wash-bottle
9. 3-way tap

13. Manometer

Fig. 1. Apparatus for

2. Flow meter
6. Water reservoir
10. Side vessel
14. Trap for condensed water

the determination of chlorine solubility

3. Safety device
4. Heating coil
7. Heating jacket
8 . Heating coil
11. Tap
12. Absorption vessel
16. Water reservoir for adjusting water level in 15
15. Seal pot

J. appl. Chem., 1967, Vol. 172December

Bott h Schulz: Solubility of Chlorine in Brine at Different p H Values

cell was the same as that leaving the cell. If these precautions
had not been taken it would have meant that the solution in
the cell would have gained or lost water, according to conditions, and this would have led to erroneous results. The
partial pressure of the water vapour in the gas stream leaving
the test cell was quite considerable at the higher temperatures. Allowance was made for this water vapour content in
the subsequent calculation of the chlorine partial pressure.
The saturated gas mixture from the saturators was passed
immediately through heaters maintained at the second bath
temperature so that condensation was avoided, and then into
the cell where it bubbled through a sintered glass diffuser
into the salt solution. The bath was well stirred and maintained at a temperature within the limits of t0.05".At the
exit from the cell, a trap was provided to collect any water
condensed out due to the lower temperature and to prevent
interference with steady gas flow conditions-condensation
at this stage was not important provided the condensate did
not run back into the cell. Finally the gas stream was
allowed to bubble through a level device (Fig. 1, 15). The
height of the bottle (Fig. 1, 16) was adjusted to allow for
changes in atmospheric pressure, thereby maintaining a
constant pressure in the apparatus.
The cell was providcd with means of measuring the pH
in situ. The side vessel (Fig. 1, 10) was equipped with a
conical joint at the top which was designed to take the glass
electrode system of the pH meter when in use. The pressure
in the absorption cell (Fig. 1 , 12) was sufficiently high to
push the liquid into the side vessel with the tap (Fig. 1, 11)
open and the tap (Fig. 1,9) connected to atmosphere. The pH
measurement could be carried out while the temperature of
the brine was the same as for saturation and while the composition of the gas in contact with the solution in the cell.
Equilibrium conditions therefore were not disturbed. Closing
the valve (Fig. 1, 9) allowed the liquid in the side vessel to be
pushed back into the cell after measurement of pH. The
hydrogen ion concentration determination did not interfere
with the course of the experiment and could be made
periodically during the 'run'. A Marconi pM nicter with
miniature electrodes was used for the pH measurements.
Care was exercised according to the maker's instructions and
particularly as far as keeping the sensitive calomel electrodc
free from temperature fluctuations. Standardisation was
carried out outside the cell, and the electrodes only inserted
into the side vessel when experiments were being conducted.
The absorption cell was fitted with a rubber serum cap at
the top so that samples of brine could be taken by hypodermic syringe without leakage of chlorine or change in cell
pressure. As the ncedle was made to reach the bottom of the
brine cell it was possible to take samples while an experiment
was in progress, and working conditions were not affected.
The chlorinated brine rose into the syringe by virtue of the
pressure in the cell which was allowed to push the plunger
back slowly. After the needle was withdrawn, it was sealed
by pushing it into a rubber bung. The solubility of the
chlorine falls with temperature rise, and therefore as the
solution cooled there was no tendency to lose chlorine.
Saniples (usually three) were taken periodically and
analysed. When consecutive samples showed similar chlorine
contents it was considered that equilibrium had been established. The 'active chlorine' (i.e. Clz (a@, HOCl and C13-)
content of the chlorinated brine was determined by titration,
the basis of the method being the oxidation of arsenite to
arsenate by dissolved CIz and HOCI-as the reaction pro-

J. appl. Chem., 1967, VsI. 17, December

357

ceeds the equilibria of Equations 2-5 will be disturbed so that

eventually all the dissolved chlorine will react. A few
drops of phenolphthalein indicator were added to 25 ml
0.1 N-sodium arsenite solution, followed by a small quantity
of 2 N-sodium hydroxide so that thc solution remained
alkaline when the cooled 25 ml sample of chlorinated brine
from the test cell was added. 0.5 N-Sulphuric acid was
carefully added until thc colour of the phenolphthalein was
discharged, followed by 2-3 g of sodium bicarbonate and
starch indicator. The excess sodium arsenite was backtitrated with 0.1 N-iodine solution.
The test brine solutions were made up from distilled water
and 'Analar' sodium chloride. The initial pH was adjusted
by adding 0.01 N-HCI solution to the brine.
Results and discussion
Data on pH and chlorine solubility have been obtained for
brine of concentration 250 g/1 at SO" and different chlorine
partial pressures. At 75", results at one partial pressure only
are recorded. The results are shown in Figs. 2 and 3.

x-fl -I

2mc3

-x-x
I
0

I
2

PH
Fig. 2. Solubility of chlorine in brine (250 g / l ) at 5 0 " ~

Chlorine partial pressure: Curve 1 0'93 atm.; curve 2 0.5 atm.;

curve 3 0.1 atm.

ii

1001 0

20

1'5

25

PH

Fig. 3. Solubility of chlorine in brine (250 g / l ) at 15"c and a chlorine

partial pressure of 0-67atm.

358 Blake & Randle: Removal of Zn2+from the Ternary System Zn2+-Na+-H+ by Cation-exchange Resin Column

=l

E 1600

I
0

k5 1200

/
,

PH

Fig. 4. Sulubiliiy of chlorine in brine (250 g / l ) at 50C arid a chloriiie

partial pressure of 0.93 atm.
Bott & Schulz
- _ _ _ _ YokotaS
Over the range studied, the solubility of the chlorine decreases slightly with increasing pH up to values 1-1-5 but
thereafter increases with increasing pH. The solubility decreases with chlorine partial pressure in the gas mixture as
would be expected.
Yokota5 presented a nomograph based on his experimental
work for the prediction of the amount of Clz(as) and CISpresent in solution at different temperatures, partial pressures
and salt concentration. The effect of the pH of the brine
solution on solubility, however, is taken into account by the

addition of a third term allowing for the amount of HOCl

present. Correction factors are given for a chlorine partial
pressure of one atmosphere only. The curves given in Fig. 4
compare the results of the present work (data at a chlorine
partial pressure of 0-93 atmospheres and a temperature of
50) and data taken from Y ~ k o t a .The
~ two sets of results
show slight divergence over the range of pH studied. The
difference is only approximately 5 % at the greatest deviation.
The measurement of pH in situ, as in this work, is considered
to give a more reliable result than an inferred value.
Department of Chemical Engineering,
University of Birmingham,
Edgbaston, Birmingham, 15
Received 3 April, 1967;
amended manuscript 13 July, 1967
References

Barr, L., J. electro. chen?. Soc., 1954, 101, 497

Seidell, A., Solubilities of Inorganic and Metal Organic Compounds, Vol. 1, 1940, 3rd edn, p. 397 (New York: Van
Nostrand)
Ullmann, F, Encyklopadie der Technischen Chemie, Vol. 5,
1954, p. 291 (Munchen-Berlin: Urban & Schwarzenberg)
Washburn, E. W., ed., International Critical Tables, Vol. 3,
1928, 1st edn, p. 256 (New York: McGraw-Hill)
Yokota, N., Chem. Engng, Tokyo, 1958,22,476

REMOVAL OF Zn FROM THE TERNARY SYSTEM

Zn -Na+ -H+ BY CATION-EXCHANGE RESIN COLUMN
By W. E. BLAKE and J. RANDLE
Very dilute solutions containing zinc sulphate, sodium and sulphuric acid were passed down a column of
Zeo-Karb 225 cation-exchange resin, and the volume at which zinc first appeared in the effluent (breakthrough volume), together with the volume at which the concentration of zinc in the effluent became equal
to its concentration in the influent (equivalent volume), were determined.

For solution concentrations of: Na2S04, 0.1-0*9 %; ZnSO,, 0.07-0.3 %; H,S04, 0.1-0.3 %, the
following equations applied:
log (breakthrough volume) = - 0.124 (log% Na,SO,) - 1.57 (log % HZS04)- 0.987 (log% ZnSO,) 0.780(k 0.045)
and
log (equilibrium volume) = -0,139 (log% Na2S04) -0-987 (log% H,S04) -0.663 (log% h S 0 4 ) f
0.482( f0.021)

Nomograms were constructed relating breakthrough volume and equilibrium volume to solution concentration.
J. appl. Chem., 1967, Vol. 17, December