THE SOLUBlLlTY

SODlUM

OF CALCltJM

CHLORlDE

E. FURBY.

AND

E. GLUECKAUF

SULPHATE

SEA SALT
AND

IN

SOLIXIONS

L. A. MCDONALD

i3crni~lr.v Division, Arnmic Energy ftesearch fitubfishment.

Ifarwdl (f3t~hrnd~

(Rtrccivcd July 19. 1967)

t%c results of cxpcrimcnts

sulphatc in sodium chloride solutions and

Imc
are giwn.
They arc COmpatd
with
those uf simtiarexp&mtnts
by other workersand found to be in wtisfitctorv agrcemcnt. A tabulation
of the best moiaI whtbility products of C&501 arthydritc in sea s&t soluiions for the tcmpcmturc
ran*= from 50 10 ,lNOC is giwn in the appcndir.
in

simuhted

sea

water

on the soI?bility

SOhtiOnS

iit 1ctTlpCntUm

of cikium
Of

Up

IO

I_ INTRODUCFION
solubility
of calcium sulphate and its hydrates in sodium chloride solutions,
and in sea water has been studied over a wide range of temperatures and concentrations (I-9).
The

The above mentioned investigations show that above 45C approximately, C&SO,
(anhydrite) is the stable form_ and that below this temperature CaS0,2H20
(gypsum)
is stable. Above S3C the mctastable iorm CaSO~{H20 (hemi-hydrate) is more stable
than the dihydrate, though it is less stable than anhydrite. However, it appears &at
nucleation of CaSO, (anhydrite) even above 45C does not take ptace spontaneously,
and so. if a saturated solution of the dihydraie is heated above 45C, it does not
precipitated the anhydrite. On the other hand, if the temperature
is raised beyond
93C. and if its solubility
product is exceeded, the metastable
hemihydrate
will
readily precipitate. Once the solid hemihydrate has formed, a very slow change to
the anhydrite phase takes plxe. (These transition temperatures
vary slightly with
the ionic strength of the solution.)
A knowledge of the solubilities
is of considerable interest for the distillation of
sea water, as c&&n sutphate precipitated at high temperatures
forms an insoluble
deposit on heat transfer surfaces, thereby affecting adverseiy the efficiency of the heat
input sections.
in salt soiutioas of higher ionic strength, the calcium sulphate solubitity product
is considerably increased. It is generally assumed that, as far as the solubility product
of CaSO, is concerned, sea salt soh~tions behave like sodium chloride solutions of
identical ionic strength. Careful study of the data recorded in the literature leads

264
Desalinrrlion,4 (1968) 264-276

SoLUBlLlTY OF CI\LCIUM

SUI.Pt!ATE

265

one to suspect the validity of this belief, since the solubility product is significantly
higher for sea salt solutions in excess of I.5 molal. This is shown for equilibrations
of the
(sodium

dihydrate

at 25C

chloride).

(see Fig.

1) where

12) (sea salt) is compared

A similar ditrerence arises for anhydrite

equilibrations

with (7)
at 125C

and 150C when comparing the data of (?,I(sea salt) with the measured data of (6) 1
(sodium chloride)*.

Fig. 1. The wlubility of calcium sulphatc dih>dnte

In the present progmmmc

solutrifity experiments

in salt solutions at 15-C.

under

otherwise

identical

condi-

tions

have
hccn carried
out with
bcth
sodium
chloride solutions and sea salt
solutions. in the experiments using naturat anhydrire as the equilibrating solid, the approach to equilibrium by precipitation of excess calcium sutphatc was exceedingly slow,
In order therefore to be czrtain of the equilibrium concentration,
the fatter was
obtained both by dissolution in unsaturated solutions, and by deposition of excess
calcium sulphate from supersaturated
solutions which however were unsaturated
with respect to calcium sulphate dihydrate and hemihydrate.
2. EXPERIMENTAL

For the equilibrium

of sea salt solutions

multiples

of a simplified

composition

were

used:
N3Cl
MC&
MgS@,

0.4861 mofes per kg water

0.0363 moles per kg water
0.01813 moles per kg water

This sofution contains all the major components of sea water except calcium suiphate
l Marshall and Slusher, in a recent publication
of new results have also established this difference
by direct experimentation. (O.R.N.L. Annual Progress Report December 3lsl, 1966).This *as not
yet available when this paper was wxWen.

Desaiina~ion,4 (1948) 264-276

266

E. FURBS,

E. GLUECKAWF

AND

L.

A.

MCDONALD

(0.0103 molal). This simplified mixture is based on the sea water composition given
by Sverdrup, Johnson and Fleming (10) by replacing minor components;
K+ was
replaced by Na+, and Br- and HCO; by Cl-. Identical equilibrations
were then
carried out with sold&m chforide solutions and with these sea salt solutions of
comparabIe ionic strength.
Tlte solid seeds for 25C equilibrations
were gypsum (C&O,.
2H,O) and. for the
higher temperatures
two types of anhydrite designated as A and B, Type A was
freshly pr-ecipitated gypsum converted to hem&hydrate
by heating in an oven at
approximately
130C and finally converted to anhydrite by boiling in 3N sodium
chloride solution for several days. Type B was natural anhydrite supplied by Gregory
and Bottley of London and ground to pass 180 mesh (c 85 p dia.) The fines were
removed partly by elutriation
and partly by extensive boiling in sodium chloride
solutions. X-ray powder diffraction analyses gave identical patterns for each type of
material; both corresponding
to the dead-burnt
insoluble variety of anhydrite
(p-C&O,).
The calcium sulphate solubility products of the two materials were not signiticantly
different but equ~ib~um
was achieved more quickly with the Type A material,
which had a much greater surface area. fn general equilibration experiments were
ailowed to proceed for 2 week.
3.

ANALY!%

In the absence of magnesium+ a 5 ml aliquot of the calcium solution, dilutrd with

water to approximately
50 ml, was butTered to pH 10 by the addition of 2 ml of an
ammonium
chloride/ammonia
buffer and titrated with O.OlM E.D.T.A.
using
solochrome black (e&chrome
black) as iadicator. Where magnesium in significant
amounts was present, as in the sea salt solutions, a modification of the above procedure
was necessary. The solochrome
black indicator was replaced by calcon and the
E.D.T.A. titration was carried out at a pH of 12.3 obtained by the addition of diethylamine (5 ml per 100 ml of solution). The latter reagent precipitates the magnesium
quantitatively as the hydroxide after which the solution may be titrated to the magenta/
blue end point very similar to the solochrome change. There is in this case some little
co-precipitation
of calcium with the magnesium, and some adsorption of the indicator
on the hydroxide precipitate but the degree of reproducibility
did not appear to be
affected to a marked extent.
Other analyses, in particular the SO; - and Cl- contents, were carried out when
required using standard procedures.
.

The results of the equitibrations are given in

Tables I-V and these data are compared

with those from other sources in Figs. 1,2 and 3. The data from Tanaka, Nakamura
and Hara (2) have been utilised on the assumption that the ratio of excess sulphate
(So,- - - Ca+ +) to chloride in rheit sea water had the same value as that given in
lksalination, 4 (1968) 264-276

SOLUBILITY

(II/,
i.e. 0.0322 gives 0.0328.

this is very similar

towc

Fig.

Fig.

OF

2. Ihe

3. The

LT=EhoI*

CALCIUSI

257

SULPHATE

to the value obtained

0s

f3L1

SCLT~OY

from (10)

which

GVOLk1

solubility

of

mhydritc

in sait

solution

at 7SC.

solubility

of

anhydrite

in salt solution at IWC.

TABLE I
THE x)LIJBtLITY OF CALCIUM WLPHATE
DIHYDRATE
lr* SDDNM CHLORIDE SoLUTtOFis AT 25c

2.62
2.92
5.12

4.96
K,

solubility

product

or mass product.

Desalination. 4 (l%S)

264-216

268

E. FURBY,

E. GLUECKAUF AND L. A. MCDONALD

TABLE

THE
su

SOLUBILlTY
SALT

OF

soLInloss

II

CALCIUM

SULPHATE

N-FOLD

DIHYDRATE

CONCENTRATED

A-r

IB

25%

TOffli

ionicSZrel&?fh

K. x loi
moiaf

moial
0.79
z-g

1.0
2.74
3.5
4.0
7.0

16.1
30.4

34.5
37.7
32.7

2:90
5.12

TABLE
-WE

SOLUBIUTY
IS

N&l

sohrlion

mofai

OF

SODfUM

CALCIUM

111

WLPHATE

CHLORIDE

(XATUluL

SOLUTIOSS

CaSO4 conrent mofal

AT

AsHYDRtTF)

75C

r&al

iofric slrengzh

0305

0.0246

0.606

11.23
.o:!
2.08
3.17
4.z

0.0314
o.ou9
0.0386
0.0368
0.0342

I.14
1.37
2.23
3.32
4.46

u,

molol

101 InofaI

6.05

f:S

*
14.4
13.5
11.7

TABLE IV
THE

SOLUBILITY
IS

NaCl sdurion
molal

Na$Od

1.02

0.0332
0.0332
0.0166

432
2.08
2.08
2.08

CALCSUH

SULPHATE

CHLORIDE

<NATURAL

SOI.UTtOW3

content modal CaSO~~~ent

0.505

El
3.17

OF

SODIUM

0.0206
0.0256
0.0249
0.0290
0.0285
0.0285
0.0183
0.0170
0.0218

AT

AWYDRflE)

ImC

Toral
ionic strength mold

0.586
1.12
1.64
319
329
4.43
2z!i
223
2.21
Desalination,

K. x IW tndai

4.24
6.80
6.20
ii-t3
8:lO
t:
8:4
4 (1968) 264-276

SOLUBILITY

OF CALCIUM
TABLE

T-HE

5OLL;RILIN

OF

CALCWJM
AS0

N&l

CasoI

solurion

content

fnolal

.nwlai
1.

__

102

.-__...

-.

0.666

2.17
2.95
3.07
2.91
2.63

1.66
2.40
2.76
S.QZ

SlXPi1ATE

rutat
iO&

SOLUTIOSS

K. x IW
nrolof

fPREPARED

SEA SALT

ANIIYDRITE)
AT

St-u salr

strengrh

::

tv

_. ._...
0.753
I .9R

2.52

2.88
5.13

IN

SODlUbl

CIILORIDE

lw-c

CamJ
content
v $02

tnuiai

fnolai
__ .

269

SULPIIATE

Tozaf

K, x 10

ionic

mulai

smen.qrh
nmlai
..-_

._ _._.

.4.70
S.:O
9.40
8.45
6.91

5.

1.01
2.825
3.61
4.08
7.02

1.43
1.43
1.35
1.29
0.88

0.733
1.98.5
zss
2.88
5.10

4.67
9.:ti
IO.86
11.53
12.6

DISCL%SION

Fig. I shows that at 2sC there is a good agreement between data obtained in the
present work and those of Shternina (7) and Marshall and Stusher (9,) for sodium
chloride sotutions, and between the present work and the data of Tanaka, Nakamura
and Hara
f2f for sea-salt solutions.
It also shows that sodium
chloride and sea salt
solutions
of the same ionic strength definitely give different solubility
products
KS -= ([Ca]
[SO; -]I in solutions
of concentration
greater than I.5 molai. This

difference increases with the ionic strength. It might be suspected that the presence in
sea-water of excess sulphnte reduces the activity of the calcium and that the presence
of magnesium reduces the activity of the sulphate in solution thus giving higher
solubility

mass products for calcium

sulphste.

In the case of magnesium chloride this effect is shown clear@ from the calcium
sulphate solubility data by Shternina (7) in magnesium chtoride soiutions. Comparing
calcium sutphate solubiiity products at the same ionic strength, the solubility products
in magnesium chloride solution were shown to he substantiaiiy higher than those in
sodium chloride, the difference increasing with ionic strength. Those in sea salt SO~Utions take up a position between the two others.
At 75C and IWC this difference between sodium chloride and sea salt solutions
is even more strongly marked than at room temperature
(Figs. 2 and 3. reqxctively).
These figures give the solubility of anhydrite in solutions of sodium chloride and
sea salt by plotting molal solubility
product against the molal ionic strength
(3 ~mq<)?). For the comparison, moIa1 concentrations
rather than molar concentrations were chosen since the former do not change with the temperature
and density
of water.
The tOOC data in sea salt solutions obtained in the present work, using prepared
calcium sulphate as solid seed, agree wclI with those obtained by Hara and his collaborators with natural anhydrite. Similar!y in sodium chloride solutions, data obtained
in the present work with prepared anhydrite agreed with those obtained on finelyground natural anhydrite.
Desalhziion, 4 (1 %t?) 261276

270

E.

FURBY,

E. GLUECKAUF

AND

L.

A.

MCUOSALD

6. CONCLUS;OF;S
In conclusion,

present
The

work have confirmed

muIts

closely

the data obtained

from

sea salt solutions

results estabfished

of the tatter authors

at higher

at 25C

by Tanaka,

temperatures

can

and 100C in the

Nakamura and Hara.
be shown

to folfow

the pattern

which might be predicted from a consideration

of the behaviour
of activity coefficients in electrolyte
solutions,
and can therefore be accepted with
all the more confidence. The results of the present work show also that the soiubiiity
product of calcium sulphate is higher in sea water solutions than in sodium chloride
solutions of cquivalcnt ionic strength when the latter is in excess of 1.5 molal.
ACKNOWLEDCt3WNT

The assistance of Mr. 0. Flint.

gratcfuIIy acknowledged.

I.
2.
3.
.a.

5.
6.

7,
x.
9.
IO.

who

carried

out the X-ray diffraction

analyses.

is

E_ P. PATNIXX ASV A. H. WHIZ-E.

J. Amer. Chem. Sot., 51119?9) 360.
Y. TAXMA, K, NAYAMURAAKD R. HARA. Kogyn Kagaku Fashi. B(1931)

779.
T. KLWWAR~; A&V R. HARA. Kogyo Kagaku Fd.whi, 34 (1933) 1651.
F. G. STANDWORD
AND H. F. BJORK.
A&.
Ciwvn. Ser., 27 (1960) I IS.
F. G. StANotfom ASD J. R. SISEK.Chem. .&I!. progr.. g (1961) 58.
R. SLUWER
ASD
E. V. Josy
J. Chcm. and Eqq. Dam. 9(z)
(1%)
187.
w. t. MARsHALL,
E. B. SHTERNINA,
Dokkdy .&ad. Xa& SSSR, 60 (19-W 247.
Y/. F. LAIGELWR,
D.
H. CALDWELLAF;D W. 8. LA~RESCE. Ind Eqq. Chum., 32 (1950) 126.
s). t_. .%~ARsuALL &SD R. SLUSWER, 1. P/p.
chum..
70 (1966)
#fs.
H. V. !%ERDRUP,
M.
W_ Jofrxsos AND R. H. FLEMISG,77re Uceuns, Prentice and Half, Inc.,
7. Touruur.

Il.

MY* (I946).
Y. MATUNO,1. KUCANEMMUAND
(1941) 142.

fL
13.

N. F~JERR~W, Z. .E&trrochcm., U (i918) 32t.

E GLUECKAUF, The Structure of ETecrrofy~ic Solurionr (Ed. W. T. Hamer) J&n

R. HARA, Clwm. Sue., lirpan. Ind. Eng. Section, $I

Wily

&

Sons Inc.. (1959) p. 97.

Desalinutiott.

4 ( 1968) 264-276

SOLUBfLlTY

OF CALClVbf

271

SULPHATE

APPENDiX
c&o.,

SOLt'ltLtTl~~

OF TANAKA,

!%RSMUfU

&Xl3

ihRA

These
experimental
observations
not only agreed satisfactorify
with the authors
own observations at 25C and 1OOC. but showed also an excellent consistency when
data on anhydrite, hemihydratc and dihydrate were compared with each other.
The activity sotubility products can be expressed in the form

where 7 is the mean molal activity

cocfticicnt

of CaSO,

in the saline solution,

(I, is the water activity of the saline solution

II is the hydration number of the solid (O,& and 2)
Then,

if orte compares the moEA soiubility products mcJ - ~~ts04- tr,: for different
at the same ccmpetaturc
and for the same saline solution, the activity COefticicnt j of the CaSOa in the solution is identical for these, so that constant ratios
of this product ought to be oht;&uzd. This constancy is obtained (within ;I few per
cent) where the obssr\ed datit permit this comparison;
at SW and 75 for anhydrite
and dihydrstc, and at 100 and 125C for anhydrite and hemihpdrate. (An exception
to this agrccmcnt vvcrc the data zit the very bighcst concentrations
(chlorinity
14SO],o)
H here for unexplained
reasons this value ditkred
conside~bl~
for anhydrite
and
dihydratc
from that found for salinities of from 16 to l~~~~*. The water activity
which leads to the formula :
was computed on the basis of - log tt,,. =: x stat +Q, ,,jSS
hytfratcs

- Jogo,

.:- i0.010;s I i O.WOSS f2

(W

In order to earrj- out these comparisons,

the soiubility data of Tim&a, Naknmura
and Hara, originally given in wt ~~C$X3+ as function of the chlorinity given in
wtO!rno of Cl, [Cl] had to be converted to the modality scak (Irr,mofs/kg H20) using
for the weight ratio of total salt in sea water to the weight of chlorine a value of
R,

= 1.818

The molality of excess sulphate (,A) was based on the molar ratio in sea Water
R,
A nominal

ionic strength

SO;-

=a

= 0.0323

I was also defined on molal basis:

(A31

272

E.

FURBY,

E.

GLUECIAUF

AND

L.

A.

MCDONALD

As the data observed

by Tanaka, Nakamura and Hara were rather widely spaced

as regards the salinity of their solution (16.29, 49.64, 97.24 and 118.06 wt o/00 chlorinity). it was decided to rc-compute the table of solubititics, smoothing any small
deviation by means of the activity product equation, particularly
as no indication
was given by the Japanese authors of how they carried out their intcrpofations.
Bearing in mind that the activity coefhcients in Eq. (Al) at high concentration
arc
usually better represented by an equation of the tyxz

1% .

=z

Az,z,f.

+ Bf

GW

thrn b:r the conventional extended Debye Huckel equation

use for the smoothing operation a plot of
Q = logEi,
against

(II.

12) WC intended to

i trlo~.~,,. - Rrl,t If3

(AN

I.
n,,aos

where SA, -.=1.98 DT-

had the va!ues given in Table AI.

In the cz~sc of the dihydrate

this plot gives

paraltel

almost

straight

lines for all tem-

peraturcs.

Thus:
log INcz * mso< .+Zlogn.,

-=Q,O +8.4,1

3-0.326f

-t-O.166 x lo-I

Yalucs of Q~arc given in Table Al.

.-W
Q&r=0

i .927

25

I.990

50

75

100

15

150

57s1

200

2.046

2.128

2,224

2.316

2.428

2.5,%

2.700

5,092

5.430

5.785

6.142

6.485

4.68

4.97

5.30

4.522

f?&n = 1

Q&n = 2

4.386

4.392

4.458

J-785
(85 ;) 4.48

4.62

But for the anhydrite, it was found that slightly curved plots were obtained. On the
other hand a plot of Q not against I, but against the chlorinity in weight OfoOreduces
the curvature and gave effectively straight lines of constant gradients, very suitabfe
for interpolation.
The mass products of the observed anhydride could therefore be
accurately represented by an equation
I
logmc. * m,, = Qp- 1.379 x 10 [CI]
-!- 8AJ I3 i A
(A7)
Desahation,

4 (1968)

264-276

SOLUBILITY

OF CALCIUM

273

SULPHATE

where A is a small correction. The significance of Eq. A7 is merely that a not strictly
linear term in I of Eq. 5 for log y could be repiaeed by a linear term in [Cl], the
coefficient of which moreover happened to be independent of temperature.
Fig. Al shows plots of Q versus [C!] using the experimental results of Tanaka,
Nakamura and Hara. The values of Qrextrapoiated from this plot for [Ci] =0 are
shown in Fig. AZ together with the values of log K,, of Marshall, Slusher and Jones,
uhich though obtained from NaCt solutions should lead to a similar extrapolated

65

60
-002.D2SC

50
nPrnrOl?lTE

20

HEhWiYCIRATE

DIHYORATE

40

60

Al.

Plot of Q (from

EZq. A63 against

(.I\)

04TA

(HI

DATAID)

60

CHLORINITY

Fig.

EATA

chlorinity,

100

NAKAUURA

I20

I40

I60

I..

showing

straight

lines of constant

iksaharion,

gradient.

4 (1968) 264-276

274

E.

FURBY,

E. GLUECKAUF

..I

-65
0

AND

I,

50.

I00
TEYPEAANRE

Fig. XL Comparison of solubiiity

L. A.

MCDOSALD

;,,

150
Y

produc?s at inlinitc dilution,

Ref. (6).

values-as
indcvtd they do for values below 1WC-for
and dihydrate data.

Q of Ref. (2) and LogK. of

the anhydrite.

hemihydratc

The re-computed
data are given in Table Ail for log KS, and in Fig. A3 for the
molal solubilities of Ca for the whole range of temperatures and chiorinitics.
For the range of the temperatures
from 50% to 150C the original Japanese interpolations
(after scale conversion)
agree quite well with the smoothed data of
Table Aff and deviations of 4% or more are rare and mostly confined to chlorinities
over the whole extrapolated
above Iof *Joa. But deviations are very pronounced
range of 175 and 2OOC, where as a rule, they exceed 10%.
Our thanks are due to Mr. A. Gardner

for computing

tables and functions.

Dcsaha!ion,

4 (1968)

264-276

16.7

20.0

I50

17.3

21.2

17.03

140

18.70

17.8

22.5

l&43

18.5

18.7

130

35.5

ll.08

loo

18.7

&
h
;;

25.9

9.756

90

18.5

lt1.2

26.2

8,488

80

18.2

213.7

26. I

7.272

70

17.3

13.92

25.4

6.106

60

IS.9

I20

23.7

4,987

50

13.8

24.7

21.2

I91 I

40

11.2

8.04

12.47

17.6

2.871

30

WLUIiILl-I-Y

WXNXT

Or C&h

IO,29

l2.S

13.6

13.5

13.4

1x3

13.2

140"

6.38
6.68

7.46
7.72

8.85

8.30
8.66

9.29
9.61

10.46

11.9

I l-8

IO.74

7.83

8.60

10.05

11,s

HA4

9.72

Il.3

7.44

8.07

9.37

IAM

5.10

5.W

7.09

X.50

9.09

4.ii

5.54

6.62

H.03

7,83

7.40

6.94

657

6.16

5.78

5 45

4.07

4.95

G.OL

7.36

3.48

2,8 I

2.08

I ,34

0,GJ

ISO
..

427

3.49

2062

1.71

O.H2

.._.. .

._

7.24

6.74

6.29

5.88

5.50

5.12

4.75

4.33

3.00

3.41

2.88

6.72

6.36

5.74

5.2h

5,'lO

6.14

4.80

4,44

4.07

3.68

3.27

2.87

5.26

4.0

4.53

4.13

3.72

3.30

2.44

201

2.39
2.u

I.56

1 SH

I,11

1.36

I .68
?,30

0.07G

0.&40

0,296

4.75

4.70

4,66

4.20

3x

3.44

2.06
3.05

2,2G

1.86

1.12
I.48

0.770

0.452

0.187

180
200
____. ._. .._-_ -. _ ._....

0,377

170

I .06

0.487

160

SOLC;TIOHS

525

433

5.41
b.48

3.30

2.1%

1.oi(

4.16

2.80

1.41

I30
.-.

~SllSl)RI11? IN SFA SALT

1I,1

IO,87

9.80

12.0

13,o

9-06

II.?

lUe65

8,05

10.00

12.H

6078

5.27

3.60

1.85

8.50

6.68

4.62

2.43

120
I 10
100
_ _.. . .____. . -,. . _._,_..._

4.44

75

110

?
02
a
82,

13.1

I.882

20

7.5

_.

0.923

_. _..__.__.
.__

10

_.__...._

WM.

IARLE All

E
z
f

z
5
z
z

276

SOLUBlLlTY

SULPHATE

OF CALCWhf

- 2.5
- 2.0
:
!

-15

f
P
0

100
wt %,

Fig.

50

60

tdS

Cl

A3. Mohf sohbilitics of Ca in sea *mer solutions ~~ccn!rated

to a given wt 7; of cklotinc,
according to new ircitmtnt of data of Ref. (2) (me=: mols Cas01 per 1000 g of wter).

Desahhtion, 4 ( 196S) 264-276