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The Experimental
Determination of Solubilities
Edited by
G.T. Hefter
Murdoch University, Perth, WA, Australia
and
R.P.T. Tomkins
New Jersey Institute of Technology, Newark, NJ, USA
Wiley Series in Solution Chemistry

Volume 6
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Contents
List of Contributors 7
Series Preface 73
Preface 73
Acknowledgements 77
List of Symbols 77
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Chapter 2.3 Solubility of Gases in Molten Salts and Molten Metals <A:
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Index E<A
List of Contributors
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Quantities, Units and
Conversions
John W. Lorimer
University of Western Ontario, Canada

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2 The Experimental Determination of Solubilities
1 QUANTITIES AND UNITS USED TO DESCRIBE SOLUBILITY
Table 1 Basic quantities used in definitions of solubility
Name Symbol Definition SI base units Notes
mass m kg 1
amount of substance n mol
volume V m3
molar volume Vm Vm,B V =nB m3 mol 1
2
partial molar volume VB VB (]V =]nB )T,p,nj , j6B m3 mol 1
3
stoichiometric n , n 1 4
coefficient of ion
sum of stoichiometric n n n 1 4
coefficients of ions
in a salt
charge number of an ion z 1
partial pressure pB p B yB p Pa 5
(of gas B)
Notes:
(1) The symbol m for mass should not be confused with the same symbol for molality in
Table 4.
(2) For pure substance B. For a mixture, the mean molar volume is Vm V =n, where n is the
total amount of all components in the mixture.
(3) For entities B. The entities may be thermodynamic components, labelled i 1, 2, 3, . . . , C.
(4) For a salt Mn Xn .
(5) For gas B; yB is the mole fraction of B in the vapor phase, and p is the total pressure. The
older units mmHg or Torr differ slightly: 1 Torr (101 325/760) Pa 133.322 Pa;
1 mmHg 13.5951 980.665 10 2 Pa 133.322 Pa; the two units are equal numerically
to better than 2 10 7 Torr.
Table 2 Quantities used to describe solubilities : Based on mass

Notes/
Name Symbol Definition SI base units References
P
p
mass fraction w wB m= mj 1 1
j1
P
s
solute mass fraction ws ws,B w = wj 1 2
j1
P
c
solvent mass fraction wv wv,B wB = wj 1 3
js1
mass ratio z zA,B mA =mB 1 [2], [3]
Notes:
(1) For entities B; summation is over all entities, total number p. The entities may be thermo-
dynamic components, labelled i = 1, 2, 3, , C . Mass per cent of entity i is 100 x B or % as a
unit. Use of the equivalent terms weight fraction, weight per cent and g(1)/100 g solution is
discouraged.
(2) Summation is over all solute components s.
(3) Summation is over all solvent components s + 1 to C.
Quantities, Units and Conversions 3
Table 3 Quantities used to describe solubilities : Based on amount of substance
Notes/
Name Symbol Definition SI base units References
x, y P
p
mole fraction, xB nB = ni 1 1
amount fraction i1
species (ionic) x , x xB nB x B 1 2
P
s
amount (mole) 1 (ni 1)xi
i1
fractions of salt
B xBn
x B
nB
species (ionic) xA0 xA0 P xA 1 2
s
amount (mole) 1 (ni 1)xi
i1
fraction of solvent
P
s
solute amount xs xs,B xB = xi 1 3
(mole) fraction i1
P
p
solvent amount xv xv,A xA = xi 1 4
(mole) fraction is1
amount ratio (mole r rA,B nA =nB 1 [2], [3]
or number ratio)
Notes:
(1) For entities B; summation is over all entities, total number p. The entities may be thermo-
dynamic components, labelled i = 1, 2, 3, , C . Symbol x is usually used for entities in
condensed phases, y for those in gaseous phases. The entities may also be particular
assumed species in the system. Thus, the nature of the entities must be specified. Amount
(mole) per cent of entity B is 100 xB or % as a unit.
(2) These quantities are special forms of amount fractions for ionic species, are generalizations
of those given in Robinson and Stokes ([4], pp. 31–32), and refer to a mixture of s binary salts
i, each of which ionizes completely into ions, and a mixture of p non-electrolytes j, of which
some may be solvent components. B refers to any one of the s electrolytes, and A is
substance s 1 of the p non-electrolyte solutes. The sum of the ionic amount fractions of
salt and solvent is unity, so that, with c s p ,
X
s X
c
(xi x i ) xi0 1
i1 is1
The quantities are used in formulating solubility equations for electrolytes, in defining
activity coefficients of salts, and in tabulation of salt effects on solubilities of gases. Clearly,
the concept can be applied to non-ionic species as well, where the quantity species amount
(mole) fraction is appropriate.
Conversions to other units in multicomponent systems are complicated, and specific
equations should be developed for particular cases.
(3) The summation is over all solute substances, s in number. Where these quantities are used in
representations of phase diagrams, they are often called Jänecke solute (mass) fractions [5].
Friedman [6] has used equivalent terms in defining excess chemical potentials in mixed
electrolytes.
(4) The summation is over all solvent substances, p s in number.
Table 4 Quantities used to describe solubilities : Based on mass and amount of
substance
Name Symbol Definition SI Base Units Notes
nB 1
molality m mB mol kg 1
P
p
ni Mi
is1
aquamolality m (C)
mB(C) mBM=MC mol kg 1
2
Notes:
(1) The definition applies to a solute B in a mixed solvent containing p s solvent components,
where Mi is the molar mass of solvent component i . The standard molality is given the symbol
m0 , and is usually taken to be 1 mol kg 1 .
(2) The definition applies to a solute B in a mixed solvent with components A, C or to a solute B in
pure solvent A. Component C is a reference component. Usually, C is ordinary water, but the
definition applies equally well to any reference component, in which case the term solvomol-
ality is more appropriate. The average molar mass of the mixed solvent is
M xv,A MA (1 xv,A )MC
and xv, A is the solvent mole fraction of component A. This term is used most frequently in
discussing comparative solubilities in water (component C) and heavy water (component A)
and in their mixtures. La Mer and Noonan [7] introduced the amount ratio (mole salt) divided
by (55.51 mole total O atoms in solvent) in 1939, while Kerwin [8] introduced the term
aquamolality in 1964. See also Reference [9] for a review of the these concepts. The
numerical equivalence of the special mole ratio and aquamolality was shown by Lorimer [10].
Table 5 (Quantities used to describe solubilities : Based on volume alone, or on

mass or amount of substance and volume)
xB Vm ,B
Volume fraction f fB c 1 1
P
xj Vm ,j
j1
fB
Solvent volume fraction fv fv,B 1 2
P
c
fj
js1
3
Mass concentration r rB m=V kg m
(mass density)
3
Amount concentration c cB nB =V [solute] mol m 3
Notes:
(1) The true volume fraction of component i is c i Vi . Lack of knowledge of partial molar volumes
has led to the convention that volume fractions are calculated in terms of the molar volumes of
the pure components, Vm .
(2) For solvent component B. Summation is over all solvent components s 1 to p. The term is
used frequently to express the solvent composition for a solute in a mixed solvent.
(3) Both symbols c B and [formula of solute B] are used. The older terms molarity, molar and moles
per unit volume are still encountered, but are discouraged. The standard amount concentration
is given the symbol c 0 , and is usually 1 mol dm 3. To avoid ambiguity, the term concentration
should not be used as a general term for the composition of a solution or mixture; e.g. ‘the
composition in terms of mole fraction’, not ‘the concentration in terms of mole fraction’.
Table 6 Quantities used in specifying conditions under which solubility is meas-
ured or in interpretation of solubilities
P
ionic strength, Im Im 12 mi zi2 mol kg 1
1
(molality basis) i
P
ionic strength, (amount Ic Ic 12 ci zi2 mol m 3
1
concentration basis) i
salinity S See Note 2 1 2, [8]
chlorinity Cl See Note 2 P 1 2, [8]
3
mass density r,g r m=V ri kg m 3
i
relative (mass) density d d r=r0 1 4

fB
Henry’s law constant kH lim Pa 5
xB !0 xB

]fB
lim
xB !0 ]xB
Q2
solubility constant Ks (gi mi =m 0 ) 1 6
i1
P
n
exp ( rMw fm mi )
i1
Notes:
(1) The summations are over all ionic substances. For a solution containing a single completely
ionized salt B with ions of charges z , z , the definitions become
Im (1=2)jz z jnB mB Ic (1=2)jz z jvB c B
(2) Used widely in reporting the composition of seawater. Chlorinity, Cl, is defined as the mass of
chlorine (in all forms, usually chloride) divided by mass of seawater. The usual unit is permille
(or per mille, per mill, permil, pro mille) or (here) 1000 mass fraction of solute; the SI units
are therefore g kg 1 . Salinity, S, is defined relative to chlorinity as S 1:80655 Cl . The
conventional salinity, ST , is defined as mass of total salt divided by mass of seawater. The
relation between conventional salinity and chlorinity is ST kS where k (total mass of
salts)/1.80665 Cl% . For a full discussion of these terms, see Clegg and Whitfield [11].
(3) m is the total mass of the system. Mass density is equal to the total mass concentration. The
term density may be used where there is no confusion with other quantities such as energy
density, etc.
(4) The ratio of the mass density of a mixture at temperature t, pressure p to the mass density r0
of a reference substance at temperature t 0 , pressure p0 . For liquid solutions, the reference
substance is often water at 4 8C, 105 Pa. (In some cases 1 atm is used instead of
1 bar 105 Pa.) The older term specific gravity is discouraged.
(5) The Henry’s law constant has also been called the Henry coefficient, the Henry’s law coeffi-
cient or the Henry constant. For further discussion, see Chapter 1.1 on thermodynamics of
solubility. At the infinite dilution limit in the definition of the Henry’s law constant, the total
pressure is the vapor pressure of the pure solvent, pA . Other analogous definitions of the
Henry’s law constant arise if the composition variables are chosen as molality (kH, B (m) ) or as
amount concentration (kH, B (c) ). Conversions between them are made using the relations
between composition quantities given in Table 7 below. Thus,
kH, B (pA ) kH(m) (c)
, B (pA )=MA kH, B (pA )rA =MA
where rA is the density of the pure solvent. SI base units: Pa kg mol 1 (molality scale) and
Pa m3 mol 1 (amount concentration scale). Henry’s law constants are used often at finite
mole fractions if the solution phase is sufficiently dilute that activity coefficients are unity, and
the gas phase is at a sufficiently low pressure that fugacity and partial pressure are equal.
For gases that react with the solvent, care must be taken to distinguish between stoichio-
metric Henry’s law constants and species Henry’s law constants. Very often, the stoichiomet-
ric coefficient is tabulated. For example, gaseous carbon dioxide dissolves in aqueous
solution and partially hydrolyzes to produce hydrogen carbonate, carbonate and hydrogen
ions. The stoichiometric Henry’s law constant is calculated from the total amount fraction or
molality of dissolved CO2 , while the species constant is calculated from the actual
amount fraction or molality of CO2 as derived from calculations based on the equilibrium
constants for formation of hydrogen carbonate and carbonate ions.
(6) Formerly called solubility product. The definition is for a hydrated salt B that dissociates
completely in water:
Mn Xn r H2 O n Mz n Mz rH2 O:
In the definition gi is the activity coefficient and fm the osmotic coefficient (both on the molality
scale), and Mw is the molar mass of water. In the absence of added electrolyte with one or
more common ions,
Ks (n g mB =m0 ) exp ( r nMw fm mB )
Analogous solubility constants may be defined using amount fractions, with the correspond-
ing activity and osmotic coefficients. A definition based on amount concentrations is difficult
because of lack of a simple and consistent definition of the corresponding osmotic coefficient.
See Chapter 1.1.
Table 7 below contains formulas for conversions between pairs of the most frequently
encountered quantities used to describe solubilities. The formulas are given for multicompo-
nent systems, with simple directions for use with two-component systems.
8

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2 QUANTITIES AND UNITS USED TO DESCRIBE SOLUBILITIES

OF GASES
2.1 Special Quantities

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Table 7 Interconversions between quantities used as measures of solubility for c-component systems containing C 1
solutes `i' and single solvent C
xB wB mB cB
1 1
xB xB C 1
C 1
P C 1
1 P
P mj r cj Mj
M 1 MC wj 1
1MB 1 1 1m mB 1M1 cB MB cB 1
C wB Mj wB B MC C MC
j6B j6B j6B
1 1 cB MB
wB C 1
wB C 1 r
M 1
P Mj xi 1
P
1MC xB 1 1 xB 1m 1 mj Mj
B MC B MB
j6B j6B
1 1 1
mB C 1 C 1
mB C 1
1
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1
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1
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j6B j6B j6B
r rwB r
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cB
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1
P
MB MC xB 1 MC 1 xB mB 1 Mj mj MB
j6B j6B
r, density of solution; Mi , molar mass of substance i. For 2-component systems, set summations to 0.
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2.2 Relation of Special Quantities to Amount Fraction, Molality

or Henry’s Law Constant of Dissolved Gas
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Table 8 Special quantities used to describe solubility of gases
Symbol
Coefficient (for gas B) Definition Notes
Ostwald, solution LB V (T , p B , nB ) =V (T , p , nA , nB )
g l
c B =cgB
l
1
reference
Ostwald, pure LB V g (T , p B , nB )=V l (T , p , nA ) 2,3
liquid reference
Bunsen, solution aB V g (T 0 , p 0 , nB 0 )=V l (T , p 0 , nA , nB 0 ) 4
reference
Bunsen, pure aB V g (T 0 , p 0 , nB 0 ) =V l (T , p 0 , nA ) 2,3
liquid reference
Kuenen, solution SB V g (T 0 , p 0 , nB 0 )=m l (T , p 0 , nA , nB 0 ) 5
reference
Kuenen, pure SB V g (T 0 , p 0 , nB 0 )=m l (T , p 0 , nA ) 2,3,5
liquid reference
Notes:
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multiplying the volume ratio by nB= nB, and noting that nB is the amount of gas dissolved
by the liquid. The amount concentration ratio is not an equilibrium constant, as has been
claimed [13].
(2) Battino [14] has made careful distinctions between Ostwald coefficients with solution refer-
ence and with pure solvent reference, distinctions that have not been made correctly in the
literature.
(3) The pure solvent reference is indicated by an asterisk .
(4) Often called, unspecifically, absorption coefficient [14]. The Bunsen coefficient is sometimes
divided by the pressure. Here, the dimensionless coefficient is preferred in analogy with the
Ostwald coefficient.
(5) The Kuenen coefficient is similar to the Bunsen coefficient, but uses the mass of solvent or
solution in the denominators of the definitions. The symbol m is used for mass.
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2.4 Sechenov Parameters for Salt Effects on Solubility of Gases

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Table 9 Relation of special quantities of amount fraction and molality of dissolved gas
Relation Notes
Ostwald coefficient (quantities at partial pressure p B of measured gas):
1 1 VB RTZB
1 1 1
xB mB MA VA VA p B LB
1 1 RTZB
1 1 1,2
xB mB MA Vm, A p B LB
RTZB1 f1 B
L1 1
B LB 3
kH, B (pA )Vm , A
Bunsen coefficient (quantities at standard partial pressure p 0 and

standard temperature T 0 of measured gas):
1 1 RT 0 ZB0 (T 0 )
=1+ = 1+ 1,4,5
0
xB (p ) 0
mB (p )MA p 0 VAαB
1 1 RT 0 ZB0 (T 0 )
= 1+ =1+ 1,2,4,5
0
xB (p ) 0
mB (p )MA p 0 Vm , AαB
Kuenen coefficient (quantities at standard partial pressure p 0 and
standard temperature T 0 of measured gas):
1 1 RT 0 ZB0 (T 0 )
0
=1+ 0
=1+ 1,4,5
xB (p ) mB (p )MA p 0 MA S B
1 1 RT 0 ZB0 (T 0 )
= 1 + = 1 + 1,2,4,5
xB (p 0 ) mB (p 0 )MA p 0 MA SB
Notes:
(1) MA is the molar mass of the solvent component.
(2) Note the particularly simple relations between molality and any one of LB , aB or SB .
(3) See text for equations for Henry’s law constant at other pressures.
(4) The Bunsen and Kuenen coefficients refer to a fixed pressure and temperature. Equations
relating these coefficients to Henry’s law constants under the given conditions may also be
derived easily, as described in the text.
(5) The quantity mB (p 0 ) has been called weight solubility, Cw by Cook [16] (quoted in [14]), a term
that is to be discouraged.
Table 10 Approximate relations connecting Ostwald, Bunsen

and Kuenen coefficients
LB αB SB
0
LB LB aB T =T SB rA T 0 =T
aB LB T =T 0 aB SB rA
SB LB T =rA T 0 aB =rA SB
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0
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3 REFERENCES
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PART 1
Fundamentals of Solubility

2 3
© ** 4 5 6 / 7. ISBN: 0-471-49708-8 .
CHAPTER 1.1
Thermodynamics of Solubility
John W. Lorimer
University of Western Ontario, Canada
and
Roger Cohen-Adad
Université Claude Bernard, Lyon, France
1 INTRODUCTION
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2 BASIC DEFINITIONS IN THERMODYNAMICS OF SOLUBILITY

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CHAPTER 1.2
Kinetics and Mechanisms

of Crystal Growth and Dissolution
Jørgen Christoffersen and Margaret R. Christoffersen
Department of Medical Biochemistry and Genetics (IMBG), The Panum Institute University of
Copenhagen, Denmark
1 INTRODUCTION

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(18)
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7
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dn dc
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dt dR R
%
jDcj
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r
E" %


dr
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dt r
$ j U= W j

! 1" U ! !" j DF j
3.4 Effect of Change of Size Distribution

F

@

-

@
"
#

#

$
5 6 U
5
L6"

n "
1=3
3ni
ni (4p=3)r3i or ri (22)
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U
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t2 t2
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q
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q q
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3.5 Separation of the Rate Expression into a Product

of One-parameter Functions
;

" 2

+ <.= <./= + <.=

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+ <./=

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8
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dr
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r
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D
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3

@

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7 . , . 4 H 8* . 4 * H </E= 6
6 6
;

4 COMPARISON OF DISSOLUTION AND PRECIPITATION KINETICS
$
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A

5 6

--

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56
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#

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<9="

5 KINETICS OF APPROACH TO EQUILIBRIUM

'
'
"
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- '


F '

F
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- D'
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9 ."

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F "
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F " @ .

@ 9

" ' F

@ 9
@ .

F

-%
F

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J

F "
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F "

k1 t
c(satd) c (c(satd) c0 )e (45)
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5
6" F! W

- F F "

W 9=. F " – F
W 9 =.
" -
? $- 56

F

5 -6

56 F " #

"

)

<8!=%

W
W + t t
;
# 8 "
%
k1 ti k1 (ti t)
di cti t cti (c(satd) c0 )(e e )
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(46)
(c(satd) c0 )(1 e )e K 0e k 1 ti
Table 1 The relation between rate-controlling mechanisms and kinetics for dissol-
ution and growth of ionic crystals in aqueous media
Rate-controlling Approximate dependence Dependence of the
mechanism of the rate on concentration rate on stirring
Diffusion (‘pure’) / jS 1jp , p 1 No
Diffusion with convection / jS 1jp , p 1 Yes
Spiral (screw dislocation) / jS 1jp , 1 p 2 No
Surface nucleation / jS 1jp , p 2 No
Rough growth, n* 1 / jS 1jp , p 1 No
Compound mechanism / jS 1jp , p 1 Possible
. 0 G "

- 5 6
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F F! W
F "

#

6 SUMMARY OF RATE-DETERMINING MECHANISMS

- #

9
S 6 S
Q:

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7 ACKNOWLEDGEMENT
$ , 0 K
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8 REFERENCES
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PART 2
Gases

2 3
© ** 4 5 6 / 7. ISBN: 0-471-49708-8 .
CHAPTER 2.1
Solubility of Gases in Liquids

H. Lawrence Clever
Emory University, Atlanta, Georgia
and
Rubin Battino
Wright State University, Dayton, Ohio
1 INTRODUCTION
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2 QUANTITIES USED AS A MEASURE OF GAS SOLUBILITY

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3 THE SOLUTION COMPONENTS

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Table 1 The solubility of oxygen (gas B) in water, ethanol and benzene at 298.15 K,
and an oxygen partial pressure of either 0.1 MPa (1 bar) or 0.101325 MPa (1 atm) in
commonly used gas solubility quantities and units.
Quantity/unit Watera Ethanol Benzene
0 3
cB ( p 1 atm)=mol dm 0.001274 0.00995 0.00906
cB ( p 0 1 bar)=mol dm 3 0.001257 0.00982 0.00892
mB ( p 0 1 atm)=mol kg 1 0.001278 0.01267 0.01035
mB ( p 0 1 bar)=mol kg 1 0.001261 0.01249 0.01022
aB =cm3 (STP) cm 3 atm 1 0.02855 0.2226 0.203
aB =cm3 (STP) cm 3 bar 1 0.02818 0.2197 0.200
SB =cm3 (STP) g 1 atm 1 0.02864 0.284 0.232
SB =cm3 (STP) g 1 bar 1 0.02827 0.280 0.229
bB =cm3 cm3 (0.03117) (0.2430) (0.222)
rB, A =(molB) (mol A) 1 2:302 10 5 5:837 10 4 8:09 10 4
Csm =mol (55:509 mol) 1 0.001278 0.03240 0.04488
Asm =L(STP) (55:509 mol) 1 0.02864 0.7263 1.006
100 w2 0.004085 0.04038 0.03315
xB (p 1 atm) 2:2996 10 5 5:825 10 4 8:10 10 4
xB ( p 1 bar) 2:2695 10 5 5:749 10 4 7:99 10 4
LV =cm3 cm 3 0.031153 0.2430 0.222
HB, A =MPa 4:4038 103 1:7395 102 1:25 102
Note: The absorption coefficient, ß, for an ideal gas that obeys Henry’s law is numerically the same as the
Ostwald coefficient. However, it is measured at a gas partial pressure that is equal to the total gas pressure
minus the solvent vapor pressure. For solvents of very large vapor pressure or non-ideal systems the,
absorption coefficient will differ from the Ostwald coefficient. It is important to remember that there will be
less gas dissolved in the solvent when one uses the absorption coefficient at a total pressure of 1 atm than
when one uses the Ostwald coefficient at a gas partial pressure of 1 atm.
a
Taken from values in Reference [12].
4 DEGASSING THE SOLVENT

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Figure 4 The variable volume, high-pressure solubility apparatus of Huang et al.

[48, Figure 1, p. 23]. See text for description. Reprinted from Fluid Phase Equilibria,
Volume 19, Huang, Leu, Ng and Robinson, The phase behavior of two mixtures of
methane, carbon dioxide, hydrogen sulfide and water, pp. 21–32, Copyright 1985,
with permission from Elsevier Science
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Table 2 Recommended values of the solubility of selected gases in water at 0.101325 MPa (1 atm) partial gas pressure and
several temperatures as determined by a Benson–Krause type high-precision gas solubility apparatus. Thermodynamic changes
for the solution process are also given.
1 1 1 1 1
T/K 105 xB 102 L Dsln HB0 =kJ mol Dsln SB0 =JK mol Dsln Cp , B 0 =JK mol
Helium
273.15 0.76907 0.9572 4.00 112.5 156
278.15 0.74738 0.9473 3.23 109.8 149
283.15 0.73118 0.9419
288.15 0.71962 0.9441 1.82 104.8 135
293.15 0.71204 0.9495
298.15 0.70789 0.9590 0.54 100.4 122
303.15 0.70676 0.9721
308.15 0.70831 0.9887 0.62 96.6 110
313.15 0.71226 1.0085
318.15 0.71836 1.0313 1.67 93.2 99
323.15 0.72644 1.0569
328.15 0.73633 1.0853 2.61 90.3 90
333.15 0.74788 1.1163 3.05 89.0 85
Neon
273.15 1.01159 1.2590 7.59 123.4 174
278.15 0.95585 1.2116 6.73 120.3 167
283.15 0.91079 1.1749
288.15 0.87447 1.1473 5.13 114.6 143
293.15 0.84539 1.1273
298.15 0.82241 1.1141 3.64 109.6 143
303.15 0.80459 1.1067
308.15 0.79122 1.1044 2.27 105.0 133
313.15 0.78171 1.1068
318.15 0.77560 1.1134 0.99 100.9 123
323.15 0.77249 1.1239
(continues)
139
Table 2 (continued )
140
1 1 1 1 1
328.15 0.77209 1.1380 0.20 97.3 114
333.15 0.77413 1.1555 0.76 95.6 110
Argon
273.15 4.3353 5.3882 17.25 146.7 239
278.15 3.7992 4.8096 16.11 142.5 225
283.15 3.3738 4.3468
288.15 3.0326 3.9740 13.94 134.9 209
293.15 2.7562 3.6712
298.15 2.5306 3.4244 11.92 128.0 195
303.15 2.3451 3.2222
308.15 2.1918 3.0564 10.04 121.8 181
313.15 2.0645 2.9204
318.15 1.9587 2.8094 8.29 116.2 169
323.15 1.8706 2.7194
328.15 1.7972 2.6469 6.65 111.1 159
333.15 1.7364 2.5898 5.87 108.8 154
Krypton
273.15 8.9352 11.085 21.25 155.3 257
278.15 7.5897 9.5905 19.99 150.7 248
283.15 6.5457 8.4202
288.15 5.7249 7.4908 17.59 142.3 232
293.15 5.0717 6.7454
298.15 4.5463 6.1433 15.34 134.6 218
303.15 4.1197 5.6527
308.15 3.7706 5.2511 13.24 127.6 204
313.15 3.4830 4.9210
318.15 3.2447 4.6487 11.25 121.3 192
323.15 3.0465 4.4237
328.15 2.8811 4.2384 9.38 115.5 182
333.15 2.7429 4.0865 8.49 112.8 177
Xenon
273.15 18.193 22.478 25.75 165.9 286
278.15 14.922 18.783 24.33 160.7 278
283.15 12.457 15.965
288.15 10.570 13.781 21.63 151.2 264
293.15 9.1035 12.066
298.15 7.9500 10.715 19.06 142.4 250
303.15 7.0321 9.6188
308.15 6.2944 8.7393 16.61 134.3 239
313.15 5.6962 8.0236
318.15 5.2076 7.4402 14.28 126.9 228
323.15 4.8061 6.9609
328.15 4.4747 6.5680 12.05 120.0 219
333.15 4.2002 6.2439 10.97 116.7 214
Nitrogen
273.15 1.9308 2.4017 16.36 150.2 259
278.15 1.7049 2.1597 15.09 145.5 250
283.15 1.5265 1.9679
288.15 1.3842 1.8150 12.68 137.0 232
293.15 1.2699 1.6924
298.15 1.1774 1.5940 10.45 129.4 214
303.15 1.1022 1.5151
308.15 1.0409 1.4520 8.39 122.6 197
313.15 0.99085 1.4020
318.15 0.95003 1.3629 6.51 116.6 179
323.15 0.91686 1.3330
328.15 0.89798 1.3109 4.81 111.4 161
Carbon monoxide
273.15 2.9388 3.6555 16.51 147.2 244
(continues)
141
Table 2 (continued ) 142
1 1 1 1 1
278.15 2.5911 3.2824 15.30 142.8 238
283.15 2.3157 2.9854
288.15 2.0955 2.7476 12.98 134.6 226
293.15 1.9181 2.5563
298.15 1.7744 2.4023 10.78 127.1 215
303.15 1.6575 2.2783
308.15 1.5621 2.1791 8.69 120.2 203
313.15 1.4844 2.1004
318.15 1.4213 2.0390 6.71 113.9 191
323.15 1.3703 1.9923
328.15 1.3296 1.9583 4.86 108.2 180
Methane
273.15 4.6666 5.8055 19.43 154.0 262
278.15 4.0221 5.0959 18.13 149.3 257
283.15 3.5192 4.5377
288.15 3.1224 4.0946 15.61 140.4 247
293.15 2.8062 3.7405
298.15 2.5523 3.4559 13.19 132.20 237
303.15 2.3469 3.2267
308.15 2.1802 3.0420 10.87 124.5 226
313.15 2.0445 2.8936
318.15 1.9340 2.7752 8.66 117.5 216
323.15 1.8442 2.6821
328.15 1.7717 2.6103 6.55 110.9 206
Ethane
273.15 7.9940 9.9553 26.66 176.0 Ð
278.15 6.5103 8.2410 25.21 170.8 Ð
283.15 5.3998 6.9586
288.15 4.5561 5.9761 22.32 160.6 Ð
293.15 3.9066 5.2104
298.15 3.4006 4.6061 19.43 150.7 —
303.15 3.0024 4.1258
308.15 2.6864 3.7421 16.55 141.2 —
313.15 2.4341 3.4373
318.15 2.2317 3.1977 13.66 132.0 —
323.15 2.0690 3.0129
328.15 1.9384 2.8763 10.77 123.0 —
Ethene
273.15 18.420 22.870 22.93 155 285
278.15 15.442 19.515 21.54 150 275
283.15 13.163 16.925 20.18 146 265
288.15 11.395 14.899 18.88 141 256
293.15 10.005 13.294 17.62 137 248
298.15 8.899 12.011 16.40 133 239
303.15 8.010 10.976 15.23 129 232
308.15 7.289 10.136 14.09 125 224
313.15 6.700 9.450 12.99 121 217
318.15 6.216 8.889 11.91 118 210
323.15 5.816 8.429 10.88 115 203
Helium, neon, argon, krypton and xenon data from Reference [67]; nitrogen data from Reference [70]; carbon monoxide data from Reference [71]; methane data from
Reference [71]; ethane data from Reference [93]; ethene data from Reference [94].
143
Table 3 Recommended values of the solubility of oxygen in water at 0.101325 MPa
(1 atm) partial pressure of gas at several temperatures as determined by a Benson–
Krause type high-precision solubility apparatus. Also given are thermodynamic
changes for the solution process, and the Henry’s law constants at several tempera-
tures as a sub-table.
T/K 105 xB 102 L Dsln HB0 = Dsln SB0 = 0
Dsln CP;B =
1
kJ mol 1 JK 1 mol JK 1
mol
1
273.15 3.9594 4.9261 17.43 143.2 239

278.15 3.4651 4.3900 16.26 140.2 230
283.15 3.0736 3.9628 15.13 137.2 222
288.15 2.7603 3.6194 14.04 134.2 215
293.15 2.5071 3.3414 12.99 132.2 207
298.15 2.3009 3.1152 11.97 129.2 200
303.15 2.1317 2.9304 10.98 126.1 194
308.15 1.9923 2.7793 10.03 124.1 188
313.15 1.8769 2.6560 9.11 121.1 182
318.15 1.7813 2.5557 8.21 118.1 176
323.15 1.7021 2.4748 7.35 116.1 170
328.15 1.6365 2.4104 6.51 113.1 165
T/K 10 9 kH, B (T , pAs )=Pa T/K 10 9 kH, B (T , pAs )=Pa
273.15 2.5591 303.15 4.7533

278.15 2.9242 308.15 5.0859
283.15 3.2966 313.15 5.3985
288.15 3.6708 318.15 5.6882
293.15 4.0415 323.25 5.9531
298.15 4.4038 328.15 6.1917
Oxygen data from Reference [12].
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9 SUMMARY AND RECOMMENDATIONS

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CHAPTER 2.2
Solubility of Gases in Polymers

Yuri Yampolskii
Russian Academy of Sciences, Moscow, Russia
and
Russell Paterson
University of Glasgow, Glasgow, Scotland, UK
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Figure 3 Dependence of the specific retention volume Vg (mL/g) on flow rate Fc

(mL/min): (a) column with poly(vilnyltrimethyl silane), T 150 C; (b) the same
column, the solute is n-heptane [59,60]
(b)
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Figure 3 (continued
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3 4
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1
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6
Figure 4 Gas chromatograph apparatus [65]: 1: cylinder with the gas studied; 2:
Cylinder with carrier gas (He); 3: sampling valve; 4: injection block for a syringe; 5:
chromatographic column; 6: thermostat; 7: thermostated detector block; 8: recorder;
9: foam flow meter; 10: precise manometer
Table 1 Advantages and disadvantages of the determination of gas solubility in
polymers by means of IGC
Advantages Disadvantages
Express method Only highly soluble gases and vapors
can be studied
Convenient for the measurement of Diffusion limitations hamper the study
temperature dependence of S at high of many important (mainly glassy)
and low temperature polymers
Infinite dilution conditions are easily Certain additional data are necessary
satisfied for the determination of solubility of
gases
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CHAPTER 2.3
Solubility of Gases in Molten Salts

and Molten Metals
Reginald P.T. Tomkins
New Jersey Institute of Technology, Newark, New Jersey
1 SOLUBILITY OF GASES IN MOLTEN SALTS

1.1 Introduction
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1.2 Quenching or Chilling Method

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Solubility of Gases in Molten Salts and Molten Metals 175
VACUUM
PORT PURGING GAS
TUBE
3-WAY VACUUM
STOPCOCK
GAS
BUBBLER
HAMILTON VALVE PYREX

AND SAMPLE LOOP
COLD TRAP THERMOCOUPLE
GAS
BUBBLER
WATER INLET
WATER OUTLET
VACUUM AND QUENCHING

GAS INLET COMPARTMENT
SILICA TUBE
SAMPLE TUBE
(STAINLESS)
WELD
Au-Pd CRUCIBLE
ALUMINA CRUCIBLE
LEVEL OF MELT
Figure 1 Quenching method for solubility measurements of gases in molten salts

[4]. Reproduced by permission of The Electrochemical Society, Inc.
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Figure 2 Apparatus for the quenching (chilling) method [5]. A-carbon dioxide inlet;
B-tube furnace with Kanthal heater windings; C-alumina tap rod; D-silica glass con-
tainer with molten salt; E-thermocouple sheath; F-auxiliary furnace with nichrome
heater windings; G-silica glass capillary; H-stopcock on nitrogen inlet; J-mercury
seal (to avoid organic polymer gaskets that may absorb carbon dioxide); K-water
cooled chilling chamber with silica crucible; L-drying tube with dehydrite; M-mercury
relief valve; N-ascarite/dehydrite absorption vessels; P-glycerol-filled bubble traps
on gas outlets. Reproduced by permission of TMS, the Minerals, Metals and Mater-
ials Society
4 6
10-100
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Active Cu, 200⬚C

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Figure 3 Stripping method for gas solubility measurements in molten salts [9].
1-Furnace with Kanthal heater windings, containing a nickel vessel consisting of
saturating section (left) and stripping section (right) joined by transfer line (bottom).
Movable nickel probe is shown on top of saturating section. Thermocouple wells are
not shown. 2-Auxilliary furnace with divided heating element. Top element heated for
transfer of melt between nickel sections. Both elements heated for emptying nickel
vessel. 3-Drying tube (P2 O5 ) and safety outlet for protection gas. 4-Same for CO2
saturating gas. 5-Purification train (active Cu, magnesium perchlorate, and ascarite)
for stripping gas. 6-Absorption train (magnesium perchlorate U-tube, and ascarite
vessels for CO2 absorption). Reprinted with permission from Reference [9]. Copy-
right (1958) American Chemical Society
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Figure 4 Stripping apparatus for solubility measurements of HF [11]. A-HF cylinder

in constant-temperature bath; B-surge tank with filter; C-molten salt saturator; D-
KOH scrubber; E-molten salt receiver; F-salt-transfer line with frozen plug; G-pres-
sure gauges; H-standard KOH solution; I-wet-test meter; J-anhydrone–dry ice traps;
cross-hatched areas, furnaces and heaters. Reprinted with permission from Refer-
ence [9]. Copyright (1967) American Chemical Society
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He
to QMS 1
He + Ar
He or Ar
2
3
5
7
He or Ar
Figure 5 Experimental arrangement for Ar solubility studies [16]. 1-He injection

tube; 2-Ar saturating tube; 3-gas collector tube; 4-quartz tube; 5-crucible;
6-thermocouple; 7-molten salt; 8-water-cooled caps
A
M
B
L
K
D
J
E
F H
0 10 20 30 cm
Figure 6 Apparatus for volumetric measurements [17]. A-Gas burette; B-leveling

tube; C-glass piston to adjust level of mercury; D-platinum crucible with molten salt;
E-concentric silica glass tubes; F-tube furnace with Kanthal heater windings; G-fan
motor; H-power control for thermostat heater; J-to rotary vacuum pump; K-gas inlet;
L-Pirani gauge; M-stopcock shut during volume measurement. Reproduced with
permission from reference 17. Copyright (1966) Blackwell Monksgaard
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B A
D.C
ELECTRONIC
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2 kC/s
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H
D G
0 10 20 30 cm
Figure 7 Apparatus for the thermogravimetric method [17]. A-Position transducer;

B-force element (permanent bar magnet suspended in solenoid); C-suspension wire, 60
Pt–40 Rh; D-silica glass container with molten salt; E-tube furnace with Kanthal heater
windings; F-thermocouple sheath, Pt/90 Pt 10 Rh thermocouple; G-to forevacuum
pump; H-oil diffusion pump with baffle valve; J-gas inlet; K-Pirani and Penning gauges;
L-mercury manometer, manually operated weight change mechanism on balance not
shown. Balance and electronic circuit schematic, rest of equipment drawn to scale.
Reproduced with permission from reference 17. Copyright (1966) Blackwell Monksgaard
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A B
Figure 8 Silica glass vessels for thermogravimetric measurements [17]. A-Shape
prior to filling; B-shape during measurements. Reproduced with permission from
reference 17. Copyright (1966) Blackwell Monksgaard
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60
45
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30
15
0 1 2
Weight / mg
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mission from reference 17. Copyright (1966) Blackwell Monksgaard
1.0
0.8
0.6
F
0.4
0.2
0.0
2 4 6 8 10
t / min
Figure 10 Data (from Figure 8) plotted versus square root of time [17]. Repro-
duced with permission from reference 17. Copyright (1966) Blackwell Monksgaard
Gas
proportioner
CO2
P 2 O5 Silica gel
CO
Stainless steel rod

Ar
Mullite
T.C. reaction tube
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SiC Furnace (4 kW)
Figure 11 Thermogravimetric method used by Maeda and McClean [21]. Repro-

duced by permission of ASM International and The Minerals, Metals & Materials
Society
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jacket Water supply
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13.692 cm/g
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pump
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furnace
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bath (59.2⬚C) (65⬚C)
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supply
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blower
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quartz crucible
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Figure 12 [23] Apparatus for gravimetric methods: (a) spring balance apparatus;
(b) torsion balance apparatus
STIRRER
THERMOCOUPLE
INSULATION WELL
VACUUM
JACKET
RADIATION
SHIELDS
Figure 13 Cell used for cryoscopic determinations [25]. Reproduced by permission

of The Royal Society of Chemistry
A
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Figure 14 Apparatus using cryoscopy for water solubility measurements [26].

A-Solenoid; B-glass enclosed iron cylinder; C-cryoscope head; D-chromel–alumel
thermocouple; E-nitrogen–water vapor delivery tube; F-small nichrome wound fur-
nace; G-stirrer; H-melt; I-sand for support; J-vacuum stopcocks; K-water heating
coils; L-water reservoir; M-nitrogen inlet; N-to vacuum pump: 1–4 numbers refer to
the operation of the apparatus. Reproduced by permission of the Electrochemical
Society, Inc.
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1.8 Electrochemical Methods

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Figure 15 Apparatus for measurement of chlorine solubility in molten chlorides

using chronopotentiometry [27]. Reproduced by permission of The Electrochemical
Society, Inc.
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Figure 16 Chronopotentiometric cell for molten chlorides [27]. Reproduced by per-

mission of The Electrochemical Society, Inc.
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o
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Figure 17 Apparatus for determining water solubility in molten salts [28]. A-Flask
of known volume (700 mL); B-jacketed flask containing water; C-free space over the
melt (250 mL); D-aluminum block thermostat; E-precision manometer; F-magnetic
stirrers; G, H, I-vacuum stopcocks; L-thermometer; M-100 g of melt. The numerical
value of the reported temperature refers to a given experiment. Reprinted from
Journal of Electroanalytical Chemistry, Vol. 28, Zambonin, Gardetta and Signorile,
solubility and detection of water in the (Na, K)NO3 entectic melt, p. 237. Copyright
(1970), with permission from Elsevier Science
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1.9 Spectroscopic Methods

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Figure 18 Apparatus used in the spectroscopic determination of gas solubilities

using chromium sulfate [32]. Reproduced by permission of the Electrochemical
Society, Inc.
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1.10 Manometric Technique

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Figure 19 Apparatus for measuring solubility using the manometric technique [34].
A-Quartz glass cell; B-top plate of furnace; C-calibration volume bulb; D-capillary
from the Bourdon tube; E-manometer; F-reference port (to vacuum pump); G and
H-thermostated water inlet and outlet, respectively; K-vacuum line and gas (argon)
inlet; L-chlorine gas inlet; M-plastic tube for thermostated water, v1, v2, v3–‘Interflon’
valves, v4, v5–‘torsion’ valves, J–‘Rotulex’ flexible joints with Viton O-rings [34].
Reproduced by permission of Blackwell Monksgaard. Copyright (1983)
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Gas
reservoir Pi Ps Ps Ps
Vr
Gas
Pl Pi Ps Ps Pu
tube
Vt
Quartz Pl Pi Ps Ps Pu
melt
container
Vq
(a) (b) (c) (d) (e)
Figure 20 Schematic diagram of the procedure used in the manometric method for
gas solubility measurements in molten salts [34]. (a)-A lower equilibrium pressure,
P1 , is established. Except for a few measurements, a chlorine pressure of 1 bar was
maintained above the melts. (b)-The valve to the melt container is closed and the
pressure in the two thermostated volumes is increased to an initial pressure, P1 . (c)-
Then the valve to the melt container is opened and a start pressure, Ps , is obtained in
the gas volumes. (d)-With the assumption that the pressure Ps is rapidly established
before chlorine dissolves in the melt, the valve to the reservoir is closed. This is done
to obtain a large pressure drop reading. (e)-Due to the increased pressure above the
melt, chlorine dissolves in the melt until a new upper equilibrium pressure, Pu , is
obtained [34]. Reproduced by permission of Blackwell Monksgaard. Copyright (1983)
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1.11 Radio Tracer Method

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WKH VROXELOLW\ RI &2 LQ FU\ROLWH 7KH SULQFLSOH RI WKH WHFKQLTXH LQYROYHV
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Rubber Balloon
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BaCO3
MgClO4
Ar Cylinder CO2 Gas

Sampling System A Trap
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Dead Volume
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Figure 21 Radio-tracer method for determining solubility of gases in molten salts

[35]. Reproduced by permission of the Minerals, Metals & Materials Society.
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O2 Sensor
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Port (SiO2)
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Upper Part
(BN)
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[Head for Oxygen Saturation]
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[The Second Head and Crucible]
Figure 22 Measurement of oxygen partial pressure in contact with the melt [35].
Reproduced by permission of the Minerals, Metals & Materials Society
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Figure 23 The structure of the ZrO2 oxygen sensor [35]. Reproduced by permis-
sion of the Minerals, Metals & Materials Society
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Figure 24 Schematic diagram of an experimental assembly [40]. A-Oxygen gas

inlet; B-gas outlet; C-brass cap; D-thermocouple; E-SiC resistance furnace; F-
mullite reaction tube; G-thermocouple; H-silica crucible; I-silicon melt; J-alumina
crucible; K-support brick; L-mullite tube; M-water cooled cap; N-brass cap; O-
argon or oxygen gas inlet. Reproduced by permission of the Japan Institute of
Metals
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Figure 25 A gas – equilibration apparatus [42]. Reproduced by permission of

TMS, The Minerals, Metals and Materials Society
Prism
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Figure 26 Levitation melting apparatus [43]. Reprinted with permission of the

American Foundry Society, Des Plaines, Illinois, USA (www.afsinc.org)
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Figure 27 The reaction chamber [44]. Reproduced by permission of the Indian

Institute of Metals
2.4 Electrochemical Method Using Solid Oxide Electrolytes
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Figure 28 Electrochemical cell for determining solubility of oxygen in liquid metals

[46]. Reprinted from Journal of Electroanalytical Chemistry, Vol. 130, Heshmatpour
and Stevenson, An electrochemical study of the solubility and diffusivity of oxygen in
the respective liquid metals indium, gallium, antimony and bismuth, p. 47. Copyright
(1981), with permission from Elsevier Science
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2.5 The Coulometric Titration Method Using a Solid-oxide

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ity coefficient of oxygen in liquid metals and alloys by solid state coulometric titration
[47–50, 52]. (a) A-Electrolyte crucible containing Pb and iridium probe; B and C leads
to electrometer and a coulometric circuit via silica bollards; D and E leads to earth and
coulometric circuit respectively, via silica bollards; F-Pt foil; G-semicircular metal
+metal oxide pellets; H-alumina spacer; J-thermocouples. Reproduced by permission
of the Royal Society of Chemistry.
(b)
9
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Figure 29 (b) B1-Pt wire; 2-reaction tube; 3-ZrO2 tube; 4-ZrO2 crucible; 5-Cr2 O3 ;
6-copper; 7-Pt crucible; 8-current lead; 9-thermocouple. Reproduced by permission
of Carl Hanserverlag, München, Germany
(c) Ar
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Figure 29 (c) Reproduced by permission of the Japan Institute of Metals
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CHAPTER 2.4
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Nagasaki University, Japan
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The Queen’s University of Belfast, Northern Ireland
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Backing Absorption
pump system
McLeod gauge
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coil
Backing
Sample pump
Liq, N2 trap Hg diffusion pump
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Figure 3 Schematic diagram of the apparatus for equilibrate–quench–analyze

method [17]
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Figure 4 Schematic diagram of an experimental setup for simultaneous measure-

ment of length changes and hydrogen concentration in the same sample [19]
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Figure 5 The relationship between DV and the H-to-metal atomic ratio, r, for a
series of f.c.c. metals and alloys (258C) [27]. e, : palladium, j: nickel, ,:
iridium±palladium, u: gold±palladium, s, g: silver±palladium, n,y: platinum±palla-
dium .: copper±palladium, d: copper±nickel
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Figure 6 Electrochemical cell for hydrogen introduction and EMF and resistivity
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compensator; RC: recorder; SP: specimen; CE: platinum counter electrode; SW1:
reversal switch for four-points technique; SW2: switch for current pulse; RE: Ag/
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Figure 7 Hysteresis of relationships between H/Pd and R =Ro at 25 8C [4]

60 3
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50
~ 760 torr
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E / mV
30
p ~ 18 torr
20 1
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Figure 8 Diagrammatic plots of changes with time in hydrogen-saturated solutions

at ca 258C of the electrode potential and corresponding hydride vapor pressure of
catalytically active palladium electrode [4]. Time to attain equilibrium (E 0 mV) is
ca 2 h with 0.012 cm diameter wire specimens and ca 7 h with 0.027 cm diameter
wire
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Figure 9 Diagrammatic plots of relationships at ca 258C, during both absorption

and desorption of hydrogen, between hydrogen content and electrode potential
measured w.r.t. a Pt=H2 electrode in the same solution and equivalent derived p–c
relationship [4]. p 760 torr 105 Pa
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PART 3
Liquids

2 3
© ** 4 5 6 / 7. ISBN: 0-471-49708-8 .
CHAPTER 3
Liquid–Liquid Solubilities
G.T. Hefter
Chemistry Department, Murdoch University, Western Australia
I INTRODUCTION
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Liquid–Liquid Solubilities 239
TEMPERATURE
PROGRAMMER COOLANT
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PHOTO
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INSULATION THICK WALLED

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Figure 1 General view of an apparatus for measurement of liquid–liquid solubilities

via the synthetic method, employing laser photometry [14]. Reproduced by permis-
sion of the Royal Society of Chemistry
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Figure 2 Detail of apparatus in Figure 1, showing mixing device
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PART 4
Solids

2 3
© ** 4 5 6 / 7. ISBN: 0-471-49708-8 .
CHAPTER 4.1
Solubility of Solids in Liquids

Roger Cohen-Adad and Marie-Thérèse Cohen-Adad
Université Claude Bernard, Lyon, France
1 GENERAL REVIEW OF METHODS

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V variance of the system
Solubility of Solids in Liquids 261
Table 1 Some properties used in synthetic determinations of solubility

Temperature Electrical conductivity or resistivity
Composition Refractive index
Volume UV, visible or IR absorption
Vapor pressure X-ray diffraction
Magnetic susceptibility Dielectric constant
Electromotive force Osmotic pressure
pH Viscosity. . . .
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2.2 Characterization of Liquid and Solid(s) Phases

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2.3 Experimental Techniques

Solubility Apparatus
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Experimental Difficulties
Supersaturation
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Figure 12 Heating curve when supersaturation on cooling is observed

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DH melting enthalpy
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Figure 28 The binary system CoCl2 H2 O at atmospheric pressure. The field of

liquid is limited by ebullition of the saturated solution
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Figure 29 Influence of the dead volume on the composition of condensed mixture

for the binary system CoCl2 H2 O
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Figure 30 Influence of the dead volume on the apparent solubility in the binary
system CoCl2 H2 O
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Solubility of Sparingly Soluble

Ionic Solids in Liquids
Heinz Gamsjäger and Erich Königsberger
Montanuniversität Leoben, Leoben, Austria
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Figure 1 Test of the Debye–Hückel limiting law. Solubilities of sparingly soluble

cobaltammine compounds (I–III) have been measured in aqueous solutions con-
taining more soluble electrolytes NaCl, m KNO3 , r BaCl2 , d K3 Co(CN)6 ; I
[Co(NH3 )4 (NO2 )(CNS)][Co(NH3 )2 (NO2 )2 C2 O4 ], II [Co(NH3 )4 C2 O4 ]2 [S2 O6 ], III [Co
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ical slopes for the uni-univalent (I), uni-bivalent (II) and tri-univalent salts (III) [20]
Reprinted with permission from Reference [20]. Copyright (1924) American Chem-
ical Society
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Figure 2 Solubility data of FeCO3 (s), 25 8C, 1.0 mol dm 3 NaClO4 [26]. 4pCO2
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given in equations (14), (15) and (16). The dash-dotted, dashed and dotted lines
refer to the concentrations of Fe2 , FeCO3 (aq) and Fe(CO3 )22 respectively. Re-
printed from Geochimica et Cosmochimica Acta, Vol. 56, Bruno, Wersin and
Stumm, On the influence of carbonate in mineral dissolution II, pages 1149–1155,
Copyright 1992, with permission from Elsevier Science
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respectively. Reproduced by permission of Verlag Helvetica Chimica Acta AG
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m Smith [55]; j Reiterer [56, 57]; d Greenberg and Tomson [58]; . Bruno, Wersin
and Stumm [26]; solid line: Preis and Gamsjäger [59], Dsol H ( 17:3
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From [22] reproduced by permission of Oldenbourg Wissenschaftsverlag GmbH
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From [77] reproduced by permission of J. Nỳvlt
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placed in reaction compartment (1) with ca 80 mL of the solution which percolates
through a sintered glass frit (a) of porosity No. 3 into the filtrate compartment (2)
where the saturating gas (e.g.CO2 ) is bubbled through the solution (b). When the
level of the solution in (2) reaches the end of the solvent recycling tube (c), a few ml
of the solution are pushed into (1) by the gas stream, thus closing the cyclic pro-
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(d) of porosity 2. (4) Thermostating jacket, (5) cover, (e) ground joint for reference
electrode, (f) thermometer holder, (g) ground joint for glass electrode, (h) ground
joint for condenser. Reprinted from Environment International, Vol. 2, Gamsjäger
and Reiterer, Investigation of equilibria involving carbon dioxide, carbonates and
water, pages 419–424, Copyright 1979, with permission from Elsevier Science
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Figure 13 Chemical potentiometer [99]: 1, reaction compartment; 2, measuring

compartment; 3, gas inlets; 4, gas outlet; 5, solvent recycling tube; 6, glass frit; 7,
condenser; 8, water jacket; 9, ground joints for electrodes. See text for detailed
explanation. Reprinted from Geochimica et Cosmochimica Acta, Vol. 53, Königsber-
ger, Bugajski and Gamsjäger, Solid–solute phase equilibria in aqueous solution II,
pages 1149–1155, Copyright 1989, with permission from Elsevier Science
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CHAPTER 4.3
Solubilities of Salt–Water Systems

at High Temperatures
and Pressures
Vladimir M. Valyashko
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences;
and
B.R. Churagulov
Department of Inorganic Chemistry, Moscow State University, Moscow, RUSSIA
1 INTRODUCTION

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Solubilities of Salt–Water Systems at High Temperatures and Pressures 361
2 PHASE DIAGRAM CONSTRUCTION (THEORY)
2.1 Possible Types of Fluid Equilibria

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Figure 1 Global diagram for binary mixtures of Lennard–Jones molecules of equal

size (central panel); P–T projections of different types (I–VII,F1–F5) of fluid phase
diagrams (surrounding central panel) [3, 4]. K, critical points of component A and B;
N, O, R, invariant points of binary systems (L1 = L2 –G; L1– L2 – L3– G; L1 = G–L2 ). See
text for description
2.2 Complete Phase Diagrams

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(b), P–T (c), P–X (d) projections) for binary system A–B of type 1 without liquid–
liquid immiscibility. T and K, triple and critical points of component A and B; E,
eutectic equilibrium (L– G– SA– SB ). Solid circles, invariant points; open squares, in-
variant critical points. Heavy lines, monovariant curves in one-component systems
(A, B); solid lines, compositions of liquid phases in monovariant equilibria of binary
systems; dashed lines, compositions of vapor (gas) phases in monovariant equilibria
in binary systems; dash–dotted lines, critical curves; thin lines, isothermal cross-
sections of the P–T–X diagram and tie-lines in T–X and P–X projections. For clarity,
only tie-lines between equilibrium liquid and gas phases are shown
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' 0 – ( – – F
Systems of type 2
)

6
-

0 = (
0– ( – F
G

$

$

)

=> =D>
$

0= ( – F #

$

$

0 – ( – F 0(

)

$

0 – F ( – F

$

6 –F )

(a) KB
(b)
T
Q
KB
P TB
KA p
Q
TB p
KA
TA T
E
TA
E
A x B A x B
(c) P (d)
P
Q Q
KA p
p
KA KB
TA
KB
E TA
TB E TB
T A x B

(b), P–T (c), P–X (d) projections) for binary system A–B of type 2 without liquid–
liquid immiscibility. p, Q, critical end points (L = G –SB ); line values and points as for
Figure 2
$

=>
=D>

$

Systems of type 1 with solid-phase transformations (polymorphism of

component A, formation of binary compounds (crystalline hydrates) )

&

5

6
9
)

6

$

!!"!! °#

)

&

3

$

7 !8
)

-! !!! G ,

6
- )
$

0 – a – #

' 0 – ( – a – #

)

a b g

4 .
$

0 – a – b 0 – b – g

$

44 0 .. 0
6
9 ) $

$

0 – a– # 0 – b– # 0 – g –# 0 – # – 2 0 – γ – B 0 – # –2 0 – 2 – F
( – a– # ( – # – 2 ( – 2 – F

$

3±7 ±; 3±; 7 ±;

3±7 5

)
44 0 ..0
4 .

α β γ

3

4 0 0 – α– β –# . 0 0 – β – γ – #

1

# 2 )
$

0(

T (b) KB
(a) W⬘
P
C⬘ KA
KA
TB
F⬘ KB
Z⬘ W⬘
D Z⬘
Z
TB W
J D C⬘
J⬘ F⬘
I W T Z
I⬘ F
TA TA J⬘
F E
I⬘
E
A x B
(c)
A x B W⬘ (d)
P W⬘
P F⬘
C⬘ F⬘
g C⬘
Z Z
J⬘ Z⬘
J KA
J⬘ Z⬘
I⬘ b I
KA
I⬘
a D D
W
TA
KB
W F
F TA
E
E
TB
T A x B

(b), P–T (c), P–X (d) projections) for binary systems A–B of type 1 without liquid–
liquid immiscibility and with solid phase transformations (polymorphism of compon-
ent A ( a, b, g forms) and binary compounds (C, D) formation. I, J, invariant points of
component A (Sα –Sβ –L; Sβ –Sγ – L); C0 , Z, D, Z 0, congruent melting points of binary
compounds C and D (SA –SC –LC ; SC –SD – LC ; SD – LD –G; SD –SB –LD ); F, F 0, W,
W0 , I 0, J 0, eutectic and peritectic invariant points (SC –SD – L –G;SC –SD– SA– L; SD–
SB –L– G; SA –SB –SD –L; SC – Sα– Sβ – L; SC – Sβ – Sγ – L). Points with arrows corres-
pond to the compositions of solid phases in non-variant equilibria E, F, F 0, W,
W 0, I 0, J0 . Dotted lines, compositions of liquid (fluid) solutions in metastable part of
monovariant equilibria. Line values and points as for Figure 2
' 0– ( – a– #

) F

6 0– ( – # – 2
0 – ( – 2 – F

# 2 F

#

2

2 )

$

) 3±7 7 ±; 5
$

0( $

)

)

$

0
(

)

6 6 0
0 – # – 2 0 0– 2 – F

$

( – # – 2 ( – 2 – F

# 2 F
)
$

2

)

#

H H 0

–

7
6 6 0

0 – # –2 0 0 – 2 – F 8

)

6 6 0
0
H# 0 2 H0 7 $

0

8
)

$

0 –

$

0– # 0– 2 0 –F

'4 0 .0 # 0 6 0 0

)

'6 2 ) F

# H# 0 2 H 0 2

)

'6 2 ) F

2 )

$

0– – #

# 0

*

$

$

6
"

3

&

6
9

)

$

0– – F

$

(b) KB
(a) T
P TB
KA KB
N⬘ KA
TB N⬘
TA T
N
E N
TA E
A x B A x B
(c) (d)
P P
KA
KA
N⬘
N⬘ KB
N⬘ KB N
E
TA
N E
TB TB
T A x B
Figure 5 Complete phase (three-dimensional P–T–X scheme (a), T–X (b), P–T
(c), P–X (d) projections) for binary system A–B of type 1 with limited immiscibility
region. N, N 0, critical end-points (L = L– G). Line values and points as for Figure 2
Binary Systems with Liquid–Liquid Immiscibility

)
$

$

3

4

Systems of type 1 with limited immiscibility region

G
$

0 – 0 " – (

6
< 4

$

A 0 = 0 " – (
4 3±7 ±; 3±; 7 ±;
$

0 – 0 " – (

A
A 0 4 3±7 5
$

A A0
0 – 0 " – ( $

0 – 0 " )

$

3±7 ±;

$

$

0 – 0 "– (

0 = 0 "

A
A 0 )

)
=
>

)

$

$

$

0(

Systems of type 1 with continuous transition of liquid–liquid immiscibility

into liquid–gas equilibrium
) $

0 – 0 " – (

A
0 = 0 " – (

6
< * 6
:

$

0 – 0 " – (

A 0 = 0 " – (
+ 0 = ( – 0 "

(

$

0

+

0 = (

%
4

$

$

$

0 – 0 "
6 0

$

(0 #

A% F

A $

0 = 0 "

0 = (

%
Systems of type 1 with two types of immiscibility regions

6
I

$

)

6
<

$

$

$

$

6
:

3
$

0 – 0 " – 0 – 0 " – ( – 0 = 0 " –

6
?
(a) T (b) K
KB
R
P
KA
R
TB R R
N KA
T
TA N
E TA
E
A x B A x B
(c) (d)
P P
KA R R
R
KA
KB KB
TA
N
TA
E E
TB TB
T
A x B
(c), P–X (d) projections) for binary system A–B of type 1 with continuous transition
of liquid–liquid immiscibility into liquid–gas equilibrium. R, critical end-point
(L1 = G–L2 ) and Line values and points as for Figures 2 and 5
Systems of type 1 with limited immiscibility region in saturated

and unsaturated solutions
)

$

0– ( – F 0 – 0 " – (

$

0 0 – 0 " – ( – F 6
? )

A 0 = 0 " –(

5

$

') F
$

0 – ( – F )
0G

$

F $

0 – 0 " – F

$

$

0 0 – 0 " – ( – F

)
$

G 0 = 0 " – F

GA 0 = 0 " 4

KB
T
P R TB
KA KB
R
N⬘ KA
TB
N⬘ N
TA T
N
E N
TA
E
A x B A x B
P P
KA R
R
KA
N
KB
N N⬘
KB
N⬘ TA
E
N E
TB TB
T A x B
(c), P–X (d) projections) for binary system A–B of type 1 with two three-phase
immiscibility regions of different types. Line values and points as for Figures 2, 5
and 6

3

6
I )

Systems of type 1 with immiscible saturated and unsaturated solutions and

continuous transition of liquid–liquid into liquid–gas equilibrium
)

0G

6
@

4

6
@

6
:

6
< ?
6
: @

3

* &

(a) T (b) KB
P KB
TB
KA
M
N
TB
T KA
N
L L
TA L
L
E
TA
M
E
A x B
A x B
P (c) P (d)
KA
M
KA
N M
KB
TA KB N
E L TA L L
E
TB T
TB
A B
(c), P–X (d) projections) for binary system A–B of type 1 with limited immiscibility
region in saturated and unsaturated solutions. L, non-variant equilibrium
(L1– L2 –SB – G). M, critical equilibrium (L1 = L2 –SB ). Line values and points as for
Figures 2 and 5

0 – 0 " – ( )

6
!
Systems of type 2 with liquid–liquid immiscibility under the vapor pressure

of the system
4
6
!

$

6
:
4 6
:

$

0 – 0 " – (

+ 0 = ( – 0 "
$

0 – ( – F 0 – 0 " – (

$

0 0 – 0 " – ( – F

$

KB
(a) (b)
T
KB
P TB
R R
KA R R
M TB
KA M
L L L T
L L L
TA
E
TA
E
A x B A x B
(c) (d)
P P
M
M
KA R R
R
KA
KB KB
L
L L
E TA
TB E TB
T
A x B

(b), P–T (c), P–X (d) projections) for binary system A–B of type 1 with immiscible
saturated and unsaturated solutions and continuous transition of liquid–liquid equi-
librium into liquid–gas. Line values and points as for Figures 2, 6 and 7

$

6

$

0 – ( – F 0

$

F

=> 0 = ( – F )

% 0 = (

%

=> 4

0G 0 – 0 " – F

G
0 = 0 " – F

AG 0 = 0 "

A 0 = 0 " – (

" D

$

D 0 = 0 " – F

$

(a) T (b) KB
KB
TB
Q
TB
P
Q
M
p M
p T
KA
L
L
L KA L
N
N N
N
TA
E E
A x B
A x B
P (d)
(c)
P Q
M M
KA p
p
TA KA KB
L L
KB
N L
E TA N
TB E
TB
T
A x B
(c), P–X (d) projections) for binary system A–B of type 2 with immiscibility arising at
vapor pressures. Q, critical end-point (L1 = L2 –SB ). Line values and points as for
Figures 2, 3, 5 and 7

$

$

$
$

B $

0 – 0 " –F ( – 0 – F

D) F $

0 = 0 " 0 = (
D% F $

0 – 0 " ( 0
$

) F % F
Systems of type 2 with metastable three-phase (L1 – L2 – G) immiscibility

4
6

$

0 –0 " –(

)

$

0 = 0 " 0 – 0 "

D 0 = 0 " – F )

$

" 6

!

*
TB
T (b)
(a)
KB
Q
TB
P
p
KA
p Q
TB
KA
T
TA
E TA
E
A x B A x B
(c) (d)
Q P
P
Q
p p
KA
KA
KB KB
E TA
E
TB
TB
T
A x B

(b), P–T (c), P–X (d) projections) for binary system A–B of type 2 with metastable
three-phase immiscibility region. Line values and points as for Figures 2 and 9

$

&

Systematic Classification of the Main Types of Complete Phase Diagrams

)

7 ! -8 *

)

7 ? <8

P
KA NR
KB
T
ad
P 1a P
P 2a
KA KA pQ KA Q
TA KB KB p KB
E TB T
T 12a T
P P
KA KA
KB KB
NN’
NL
T T
ab ab’
P M P
P 1b’ P M 2b’ M
KA KA KA pQ KA Q
P KB KB N’ N’
1b N’ N’ p
R L
KA NL
T L T E TB
KB 1bb’ T 12b’ T
TA N’
TB P 1b’‘ P P
N P 2b’‘
T M M M
KB KA pQ KA Q
KB N
N p
N N’L L L TB
T TB T L
1bb’‘ T 12b’‘ T
P
KA NR
KB
N’
N T
bc
P P P
1c’ P M 2c’ Q
M KA KA p
R R
P N
1c N pR
R NL T L KB T E KB
1cc’ T 12c’ T
N P MQ P
N N’ KB P 1c’‘ P 2c’‘ Q
T M
pR KA
p p p
L L L
N TB KB T TA KB
T T T
1cc’‘ 12c’‘
P
KA
R
KB
N’N
N
T
cd
P P P P
1d’ M 2d’ Q
KA R M KA KA p
P R
1d TA TA
pR
KA R NL T L T TB
E KB
TA 1dd’ T 12d’ T
N TB KB P P 1d’‘ P Q
P MQ 2d’‘
T
p p M p
KA pR
N N L N L
T KB T N L TB KB
1dd’‘ T 12d’‘ T
P
KA
KB
NR
T
da

)

6

3

$

)

7@ ! 98

&

7 ! 98

6
" )

"

J= > 44 ;4

7 <8E
$

$

$
$

J=> 444 ;

+ 7 <8E

0 – 0 " – ( $

J=> 4; ;44
+
798 7 <8 =>

4

+ 7 <8 )

6
"

$

&

)

"
) $

6
"

)

3 5

""

4

6
"

)

& $

5 + 5

Figure 12 Systematic classification of the main types of complete phase diagrams

for binary systems, in P–T projections [10, 14]. Diagrams in frames: boundary
versions of diagrams with higher-order invariant point LN, RN, pR, pQ, MQ
(empty points), corresponding to equilibria L1 = L2 –G–S; L1 = L2 = G; L1 = G –L2 –S;
L = G –S; L1 = L2 –S. Filled points: invariant equilibria in one-component (T, K) and
two-component systems (points E, L, N, p, Q, R) Thin lines, monovariant curves for
one-component systems; thick lines, monovariant curves for binary systems;
dashed lines, monovariant critical curves; dotted lines, metastable parts of monovar-
iant curves boundary regions of immiscibility

&

0 = 0 "

$

$

1
6
6

&
Derivation of Complete Phase Diagrams for Ternary Systems

)

6
"

&
7 !8 ) &

$

4

)

$

4

6

"

$

2.3 Some Regularities of Phase Behavior in Various Types of

Water–Salt Systems

&

$

>

$

1

$

&

)

$

$

$


Hydrothermal Equilibria in Binary Systems

)

$

$

0(

=

>
5

$

"

9!! º# 4
-I9 º#

$

$

#

$

"
)

"

$

4

=> 0 = ( –

$

&

0(
4 $

(0

&

( = 0

0 – 0 " – (

$

$

0 – 0 " – ( – 4

$

&
6
? @ 4
$

"
6
! 00 00 00
6
"
'
&

"

6

&


4

&

( –0 – 0 "

4

6
< : I 4

6
? @

6
" 4

$

( – 0 – 0 "

#

6
 => F

$

$

+

$

6
:
@
6
" =>
)

"
6

)

$

)

"

B
)

D

D) F D% F
3

&

$

& '

"

6
-

3±7 5

"

(0
" )

D% F

%
7 ±; 5

6
-

%
- ) 3±7 5
$

D) F

$

(0
$

0 – 0 " –

9 )

D 0 = 0 " –

=> ( = 0 –

D

=> 6
-
P (MPa )
(a) (b)
250
8
200
7
T ( ⬚C)
1
150 2
500 4
3
2
Q
9
100 3 14
4
450 5
6
Q
5 1
6 13
50 10 12
11 13 Q 7
400 8
9 10 Q
14 N Q
KB
0
200 300 400 500 600 T ( ⬚C) 0 2 4 6 8 10
x (mol % )
Figure 13 P–T (a) and T–X (b) projections of critical curves of liquid–liquid immis-
cibility [1–12 in (a), 3–9 in (b)] and of liquid–gas (L = G) equilibrium [13 in (a); 1 and
2 in (b)] with parts of monovariant curves L1– L2 –S [1–9 in (a)], L–G–S [13 in (a)];
equilibrium L–G for pure H2 O (14) and supercritical extrapolations of liquid–gas
(L–G) curve of H2 O (14). Open circles, critical points of water (K) and binary
systems (Q, N). (a) Aqueous system with Na2 CO3 (1), Na2 SO4 (2), BaCl2 (3),
Li2 SO4 (4), K2 SO4 (5), KLiSO4 (6), Na2 SiO3 (7), 1.8 SiO2 *Na2 O (8), 2 SiO2 *Na2 O
(9), UO2 SO4 (10), Na2 WO4 (11), Na2 MoO4 (12), NaCl (13), pure H2 O (14). (b)
Aqueous system with NaCl (1), NaOH (2), BaCl2 (3), Na2 CO3 (4), Na2 SO4 (5),
K2 SO4 (6), Li2 SO4 (7), KLiSO4 (8), Na2 WO4 and Na2 MoO4 (9)
Binary Water–Salt Systems at High Pressures

$

!!"!! º#

) 3±7

6
9 7 :8

)

4

– "" º# "!I G, )

)

;4

! < º # :": G, ? : º# ""!! G ,

;44

P (MPa)
3⫻104
1⫻104 ICE VII
VII
1⫻103 VI
V
II
Logarithmic scale
100 III
KH O
10 2
LIQUID
1.0
0.1 ICE
I
1⫻10 2
VAPOUR
1⫻10 3
4
TH O
5⫻10 2
0 100 200 300 400 T (⬚C)
Figure 14 P±T diagram of H2 O [16]

6
9

)

$

A# % " 1 9 A * 9 A1 -

"< º# 7 I @8 )

#" · * " 1 :! º# "I<!
G , 7"!8
" )

!!!
G, 7" 8 ,

!!! G , 7 I "! ""8 4

&

!!! G , "< º# )

A " 1 9 · !* " 1 A " 1 - · I* " 1 A " #1 9 · !* " 1 7" 8
- #

$

!!! G ,
9!!! G,
7"! ""8 )

3

$

7"- "98

#1 9 · * " 1 #1 9 · !.<* " 1

7"<8
9 1
&

$

4

$

H H 0
6
9 )

$

$

&

$

7" 8

HF " · -* " 1 #A 1 - " · :* " 1
A " 1 9 · !* " 1

H#" · ".<* " 1 HA 1 - " · :* " 1

< )

7":"?8

3 B
•

B

E

E

E

• = &>

4

E
•

)

4 "!
"

:!!?!! G, "< º#

)

7"I "?8
Hydrothermal Equilibria in Ternary Systems

)

7 !8

$

7 ! 9 "@ -!8 &


)

3
$

0(

3±7

$

)

)

$

3

4

4
&

)

3

"

$

)

3±7

0 = ( 0( $

0 = ( –

4

$

6
:
" 6

% " 1 9 – %0
1 9 – * " 1
1 " – A "
" 1 < –* " 1 7 !8
4
"

$

$

6
" 0
6
"

0 – 0 " – (
)
$

3
$
B
"0 – " 0 – 0 – 0 – – 0 – 0 – "0 – "0 6
"

"

)

"

! < ·L 7@ ! -8

$

$

$
$

6
:
6
"

6
"
6
"

$

A+ 0 = 0 " = ( =

>

7 ! 98
4

$

0 00 0 00 0 00

6
"

3±7

$

0A 0 = 0 " – ( – + 0 = ( – 0 " –

, & 7"@ -!8

$

0

$

B
0– – 0– – 0– – –0 – 0 0– – 0– – 0 6
"

A+ = >
6
"

A 0 A =>
6
"

)

=

>

7-!8
3 METHODS AND EQUIPMENT FOR STUDYING PHASE

EQUILIBRIA IN AQUEOUS SYSTEMS AT HIGH PRESSURES
AND TEMPERATURES
'

$

*

$

$

$

$


3±7

4

$

7- -?8

$

$

)

$
3±7 ±;

5

'

&

$

$

)
B

$

$

$

J

= &
>

E

C

F

$

$

4

$

* 7-@9 8

&

79!8

+ 79 8

$
3

) &

)

3

)

&
3.1 Methods of Visual Observation
G

$

)

B

&

6 <"< G ,

& :- "!?
"<<

6
< 79"9I8 )

7999:8 , 79" 9- 9I8
% $

$

)

3

$

*

&

6
< 79" 9- 9<9I8

$

0
A1 - -! L
AA1 - 9 L %A1 - <: L 7 - # AA1 - 9:
L %A1 - <9 L 7 """ # 7998 '

$

&
&

Figure 15 Assembly of rocking furnace with metal thermostat block for visual
observation of phase transformation in sealed glass capsules (optical path is shown
by dashed line)
)

)

$

#
G

± " %

$

& 9!!9?! º #

)

<"< G,

$3 79? 9@8

7<!: 8

6
: I

± !" º#

± ! L
<!! º# -<! G,

2

#1
7<9:!8 6

9<! º #

#1

@
& 7:!8 6
:
1 <

'

< % &

&

)

4

6
I

7< <"8 )

)

$3

4

&

&

(a)
cw in cw out
7
fresh salt C
water water B
1 2 supply supply
6
P
8
effluent
5 A D collection
gravity
reactor
P
3 4
(b) 7.98
theno-
couple
Window
hot finger 1.91 2.86
Window
Figure 16 Schematic representation of the flow apparatus (a) and schematic

drawing of the 1.91-cm Swagelok cross (b) from which the optical cell with windows
was fabricated, showing hot finger, sapphire windows and thermocouple locations
(the flow is in and out of the page) [60]
;

$

$

+ 7: 8
2

7:"8

7:-8 ;

:!!@!!
G, 7:"8

##1 -
#1 9 F#1 - G 9 #1 - - 1* " · -* " 1 #

3

$
"< º #
@!! G , 6
9 9

+
(a)
7
7 7
3 5
T 7
6
1 4
7
2
solution
(b)
1 2 3 5 6 4 7
Figure 17 High-pressure optical cell with a piston for static method of investigation
[51, 52]. (a) Schematic diagram of equipment including high-pressure optical cell
with a piston (1), heater (2), pressure–temperature recorder (3), spindle press (4),
pressure gauges (5), piston position indicator (6), valves (7). (b) High pressure
optical cell: sapphire window (1), pressure vessel (2), thermocouple (3), piston
(4) with platinum mirror (5), clad magnetic stirrer (6), cooling jacket (7). Arrows
show inlets/outlets for solution and cooling water

y )

y
)

$

4

$

)

$

)

$

4

$
&

4
3
&

$

$

&

$

$

$

$

&

"!!-!! º #

&

$

0( 0 – 0 "

&

&

3.2 Methods of Sampling

G

$

3±7

$

6

&
$

M
$

F 7
+ -"8
$

$

4


)
7-<8

4

4

6
?

& I!! º # -!!
G , 7-I -?8

-!! º #
-! G , 7-? :98

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Figure 18 Flow system. Configuration of the reaction vessel with two cans to
increase the length of the interior flow path [35]. 1, pressure vessel; 2, metallic
mesh for solid solute; 3, thermocouple. Arrows show the flow path of solvent
(steam)
Sampling with Temperature and Pressure Drops

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Figure 19 Schematic diagram of apparatus for solubility determination by method

of sampling with temperature and pressure drops. 1, pressure vessel; 2, rocking
furnace; 3, thermocouple well; 4, sample tubing for liquid and vapor solutions; 5,
sample line heater; 6, condenser; 7, valve; 8, sample collector; 9, pressure gauge
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to sample
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to pump
10
11
Figure 20 Schematic diagram of flexible cell system for solubility determination at

elevated pressure by the method of sampling with temperature and pressure drops
[82, 83]. 1, pressure vessel; 2, rocking furnace; 3, flexible sample cell (Teflon, gold);
4, thermocouple well; 5, sample tubing; 6, capillary pressure line; 7, separator; 8,
pressure gauge; 9, valve; 10, electromagnet; 11, clad magnetic stirrer

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Figure 21 High pressure vessel for solubility measurements by the method of

sampling with temperature and pressure drops [84]. 1, stainless steel high-pressure
vessel; 2, reaction volume; 3, pressure transmitting oil; 4, Teflon ball; 5, piston;
6, O-ring; 7, copper packing; 8, glass filter; 9, flexible stainless steel tube; 10, valve;
11, outlet

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Figure 22 Two-chamber pressure vessel for solubility determination by method of

sampling with pressure drop [10, 13]. (a) Hydrothermal bomb for sampling non-
crystallizing saturated solutions; (b) hydrothermal bomb for sampling crystallizing
saturated solutions. 1, pressure vessel where the charge is placed; 2, thermocouple
well; 3, filter from pressed fine silver wire; 4, channel between two chambers; 5,
sampler; 6, valve needle; 7, valve packing (Teflon, asbestos with graphite); 8,
screw; 9, extension tube; 10, separate stainless steel cup for a sample of crystalliz-
ing solutions; 11, screw stopper
)

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Figure 23 Scheme of apparatus for sampling without pressure and temperature

drops [90]. 1, high pressure vessel; 2, coupling nut; 3, seal ring; 4, lock needle; 5,
sleeve gate; 6, sealing cap; 7, needle valve; 8, washer; 9, nut; 10, sampler
I

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(a) (b)
1
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5
4
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S
S
Figure 24 Device for sealing (a) and squeezing (b) of flexible capsules into high-
pressure vessel [37]. 1, high-pressure vessel; 2, metallic body of the device; 3, rod
with wedge-shaped cut-outs that moves without rotation; 4, clamps for sealing and
squeezing of capsules (5) to separate equilibrium fluid (F) and solid (S) phases
6
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Figure 25 The two-chamber Teflon cell with a magnetic stirrer for solubility meas-
urements at high pressures up to 600 MPa and 75 ºC [100]. 1, Teflon cylinder
(14 mm in diameter and 70 mm in length); 1a, Teflon stopper; 2, Teflon partition
(6 mm in height); 3, hosing from non-magnetic stainless steel; 4, magnetic core; 5,
Teflon stirrer; 6, electromagnetic coil reeled up the Teflon bushing; 7, shutter; 8, inter-
rupter; 9, salt solution; 10, solid phase

<

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3.3 Methods Using Radioactive Tracers

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1 2 8
9 3 4
9
H2O
10 5
11
12
Figure 26 Isopiestic system with in situ electrobalance [103]. 1, light source;

2, sapphire window; 3, platinum mirror; 4, electromagnet; 5, isopiestic vessel;
6, thermostat block; 7, cups with solutions; 8, weighing cup; 9, dual photocell; 10,
current controller; 11, standard resistor; 12, voltmeter. The system consists of a
balance, a constant temperature block and a number of sample cups in well-thermo-
stated vessel. An in-place torsion balance is operated optically by reflecting a light
beam from a mirror on the balance beam. The current through a coil is adjusted to
bring the beam to a null position

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6
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Figure 27 Schematic diagram of apparatus using a method of radioactive tracers

for solubility determination [37, 105]. 1, air thermostat; 2, scintillation counter; 3, low-
temperature thermostatting jacket; 4, pressure gauge; 5, spindle press; 6, bellows
position controller; 7, reaction vessel; 8, bellows chamber, where solid is placed; 9,
thermocouple and thermometer well; 10, syringe
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3.4 Method of Potentiometric Solubility Determination

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Cd(s) Hg2 I2 (s) CdI2 (s) 2Hg(l) (1a)

DGm (Ia) 2FE(Ia) m2 * 2m*(Hg, l) m*(Hg2 I2 , s) m*(Cd, s) (1b)

$

CdI2 (s) CdI2 (satd soln) (2a)

m*(CdI2 , s) m2s (2b)
)

DVm (Ia) 2F [dE(Ia)=dP]T Vm, 2 * 2Vm (Hg, l)

(3)
Vm (Hg2 I2 , s) Vm (Cd, s)
* )
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E (V)
0.500 1
2
0.490
3 5
0.480 P*
4 P*
P*
0.470 P*
100 300 500 700 900

P (MPa)
Figure 28 Pressure dependencies of the EMF of cells Ia and Ic at 25 ºC. Mass-%

CdI2 in cells Ic: (1) 15; (2) 20; (3) 30; (4) 40; (5) emf of cell Ia. PN, pressure at which
the mass fraction of CdI2 in cell Ic becomes equal to the solubility in cell Ia
4

4 $

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Figure 29 Teflon potentiometric cell with a common solution to study the solid–
liquid phase equilibria at pressures up to 1000 MPa and temperatures 10–80 º C
[114]. 1, Teflon vessel; 2, cylindrical stainless steel plug; 3, Teflon cup; 4, 1-mm
diameter stainless steel wire; 5, electrode (Zn, Cd or Cu); 6, Teflon washer; 7, Teflon
screw; 8, small Teflon vessel for mercury; 9, Teflon sheath
) @

@

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3.5 Methods of Quenching

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± !! G , ± <I º#

(a) (b)
P (MPa) P (MPa)
SiO2 Na2O H2O SiO2 1.3Na2O H2O
400
400
300
300
200 200
100 100
300 500 700 T (⬚C) 500 700 900 T (⬚C)
Figure 30 P–T projections of phase diagrams for quasibinary sections of

Na2 O-SiO2-H2 O systems at constant ratio of Na2 O /SiO2 on the results of quench-
ing experiments [10]. Quenched phase assemblages: open circles, liquid (homoge-
neous fluid at experimental conditions); solid circles, liquid + glass (fluid and liquid
at experimental conditions); open triangles, liquid + crystals (fluid and crystals at
experimental conditions); solid triangles, liquid + glass + crystals (fluid, liquid and
crystals at experimental conditions). Curves, corresponding to critical (L1 = L2 ) and
three-phase (L1-L2-S) equilibria and intersecting at the critical point (L1 = L2-S)
(square), are the boundary lines drawn between the experimental points

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10 7
5
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8
12
11
4 4
3
3 3 4
1 2
Figure 31 Schematic diagram of cold-seal pressure vessel for high temperature/

high pressure phase equilibria studies with the quenching method. 1, pump; 2, pres-
sure intensifier; 3, valve; 4, pressure gauge; 5, furnace; 6, thermocouple; 7, device
for quenching; 8, high pressure cold-seal vessel; 9, stainless steel filler rod; 10,
sealed capsule with a charge; 11, cold seal vessel for internal isobaric quench; 12,
electromagnet supported filler rod and capsule in a hot region of vessel during
experiment

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Methods of P–V–T–X Curves

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Method of P–X curves

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Figure 32 Schematic diagram of autoclave for P–V–T–X measurements [13].

1, high pressure vessel; 2, rocking furnace; 3, thermocouple well; 4, capillary filled
by mercury; 5, valve for admission and release of mercury; 6, pressure gauge;
7, capsule with holes (for crystals)

4

4

)

3

3±; ;

6
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4

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(a)
(P X )1
P T-const (P V curves) 3
3
4 2 4
(P X )2
L
1 2 1
L S
Fl
5
5
G L Fl S
G S
A x V (g Hg) A x
(b)
X const (P T curves)
P 3 3
1 2 Fl
S 4 4
G-
L- Fl S
T A x
(c)
T L1 S P const (T V curves)
Fl S
L1 L2
L Fl
L S
1 1 2 3 2 3
A x V(g Hg) A x
Figure 33 Behavior of P–V–T–X curves at phase transformations during experi-

ments. Fl, fluid phase; S, solid phase. (a) P–X and P–V curves. Isothermal sections
of binary phase diagram and P–X paths followed during runs with isothermal volume
increasing (lines with arrows 1 to 5) and change of solution composition (P–X1) or
quantity of salt (P–X2). Corresponding experimental P–X (P–X1, P–X2) and P–V
(1 to 5) curves are also shown. (b) P–T curves (1, 2) plotted on a P–T projection of
three-phase solubility curve with pressure maximum and another experimental
curves (3, 4) corresponding to transition of cooling system from homogeneous to
heterogeneous state. The intersection of the P–X path followed during cooling with
solubility isotherm is shown in the P–X diagram. (c) T–V curves. Isobaric sections of
phase diagram and T–X path followed during the runs with isobaric volume increas-
ing and heating (lines with arrows 1, 2, 3) and corresponding experimental T–V
curves (1, 2, 3)

3

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High pressure DTA measurements (by K.G. Kravchuk)

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Figure 34 Pressure vessel and DTA cell (enlarged scale) [146]. 1, Metallic cell; 2,
lid; 3, bottom-side Bridgman closure; 4, quartz glass disk; 5, crucibles for sample
and reference
,

F

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31
Differential temperature / ∝v
390 80
Temperature / milivolt
380 60
30
pressure (bar)
40
370
20
29 360
0
350
20
28
340 40
330 60
27
320 pressure 80
26 310 100
14300 14500 14700 14900 15100 15300 15500 15700 15900
Time/sec
Figure 35 DTA scan for determination of P–T coordinates of the solid–liquid–vapor

equilibria in the system NaCl-H2 O [146]. Temperature interval 650–750 ºC

)
(0 $

A#-* " 1 AF-* " 1 A " 1 9-* " 1

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Acknowledgements
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4 REFERENCES
#( ( % ' (
7 KHRU\ RI 0 ROHFXODU )OXLGV ; 1 M

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6 SHFLDOLVW 3HULRGLFDO 5 HSRUWV &KHPLFDO 7 KHUPRG\QDPLFV ; "
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CHAPTER 4.4
Solubility of Metals and

Non-metallic Substances in
Liquid Metals
Cezary Guminski
Department of Chemistry, University of Warsaw, Poland,
and
Hans U. Borgstedt
Forschungszentrum Karlsruhe GmbH, Karlsruhe, Germany

1 METHODS BASED ON PHASE SEPARATION

1.1 Weight Loss of an Integrated Solute Sample after Equilibration

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1.2 Analysis of the Solution after Filtration, Centrifuging, Sampling

or Drawing out the Dipped Solute
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Solubility of Metals and Non-metallic Substances in Liquid Metals 439

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OUTER CAPSULE OF STEEL

Ta CRUCIBLE
HEATER
THERMAL INSULATION
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Na SOLVENT
Me SOLUTE
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THERMOCOUPLE COUPLING
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CRUCIBLE HOLDER
Ni CRUCIBLE
Figure 3 Glass vessel for the analytical vacuum distillation of Na and heavier alkali
metals after [20]
1.5 Precipitation of Less Soluble Intermetallic Compounds by Means

of Addition of a Third Metal, Monitored by Slow Scan Rate
Voltammetry or Cyclic Chronopotentiometry

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−0.9V −0.9V
−E
Figure 4 Voltammetric reduction curves of Zn(II) from 1 × 10–2 mol dm –3 ZnCl2 in

4 mol dm-3 KCl on the saturated palladium amalgam (curve A) and pure mercury
(curve B) electrodes. Radius of electrode 0.43 mm; scan rate 0:16 mV s –1
60
50
40
Q /mC
30
20
10
0.1 0.2 0.1

XAu (mol %)
Figure 5 Dependence of the pre-peak charge Q on the initial content of gold in its
amalgam. Solution, 1 × 10 –2 mol dm–3 ZnCl2 in 4 mol dm–3 KCl; radius of electrode,
0.43 mm; scan rate 0.8 mV s–1

% %

< H %

<
>
*

7

4

4

<
@

7

9

<
@

7

4

41

%

<
>

ts
τo
3s
100 mV
−E
Figure 6 One-cycle chronopotentiometric curves of Zn on the saturated Pt amal-

gam hanging drop electrode. Current density 86.4 mA cm –2 ; radius of electrode
0.43 mm; solution: 0.01 mol dm–3 ZnCl2 in 1 mol dm –3 KCl; (-----) processes on the
mercury electrodes

%

CC 3

/'

%

/'–2 / 3

& 3

80
A
70 B
60
50
t0 (s)
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90
tr (s)
Figure 7 Chronopotentiometric dependence of t0 on tr . Curves A and B were

obtained with Hg and saturated Pt amalgam electrodes, respectively. Solution:
1.0 × 10–3 mol dm–3 Zn(II) in 0.1 mol dm– 3 KCl; current density 216 mA cm–2. (+)
Results obtained with the amalgam, conditioned for one week. ( ) Results obtained
after half a year of conditioning
2 METHODS WITHOUT SEPARATION OF THE SOLUTE FROM THE

SATURATED SOLUTION
2.1 Galvanic Cells
!

!5? | ? +

| ?

?
D?

DI? (
A
E (RT=nF ) ln [a(Na)=a*(Na)] A

6 + + Q – ↔ 6

/'

,
7

7

1

(

DIGITAL
RECORDER
DIGITAL
VOLTMETER
Ni Ni
RUBBER
GASKETS
Na Na−Hg
b -ALUMINA
DRY BOX
Figure 8 Set-up for EMF measurements of Na//Na–Hg cells with b00-alumina as

the electrolyte (after [22])

7 " 9
.&&0

&( :

? -

9

Table 1 Galvanic cells for the study of alloys or solutions in alkali metals
Electrolyte State Conduction of System to be studied
ThO2 =Y2 O3 Solid O 2
Oxygen in alkali metals
ZrO2 =CaO Solid O2 Oxygen in alkali metals
Na glass Solid Na Na alloys (with Cd, Ga, Hg, etc.)
K glass Solid K K alloys (with Cd, Ga, Hg, etc.)
b00 -alumina Solid Na (Li ) Na (Li) alloys (with Pb, Sn, etc.)
CaF2 Solid Na (Li , K ) Na (Li, K) alloys (with Sn, etc.)
Li2 CO3 =Na2 CO3 Liquid C(ionic specia) C in alkali metals
CaCl2 =CaH2 Liquid H H in alkali metals
NaI in ethylamine Liquid Na Na alloys (with Ga, etc.)
CdCl2 in water Liquid Cd2 Cd in amalgam (with Hg)
.&20

%

;< & .&>0

%

'

>A( ± / :

%

: + : & D
7 7

5

7

7

: + : & D

7 6

7

<
C

" H
?

7

'./@ ± ':'& 3 D

.&'0

?

.&A0 -

.&B0
7

; "

,

DIGITAL VOLTMETER
E
DIGITAL AMMETER
A V
POTENTIOSTAT
THERMOCOUPLE
In+In2O3
LIQUID K
NICKEL CRUCIBLE
K+K2O (dissolved)
TEMPERATURE CONTROLLER
Figure 9 Experimental set-up for the determination of oxygen in potassium after

[26].
<

%

?

%

.&C0

# .('0

<
/' .(/0 ,

%

9

?

<
/'

0.8
15 C
25
Er (V) 40
0.75
65
90
0.7
−1.6 −1.4 −1.2 −1.0

Log X Na
Figure 10 Equilibrium potentials Er , as a function of the sodium concentration (log

xNa ) in concentration cells Na=Na =Na(Hg) at various temperatures after [31]

'/ 3

4

' F
7

/' –> 3

2.2 Differential Thermal Analysis

; 2/

7 '/ 3 =

=

=

.(&0 =

2'' 8; ('' A'' 8; @'' /&'' 8;


D7

7

=

7

7

;

=

5

.((0
5$ .(20
,

=

%

;5
.(>0
2.3 Measurement of the Density of Solutions

=

7 %

'( 3 .(@(A0

g

,

g

g

<
//

5;
.(B0 g
/(A ;
=

7

7

%

<
//
5.0
4.0
d /g cm −3
3.0 B
2.0
610 650 690 730 770

t / C
Figure 11 Temperature dependence of the density, d, of In–Cs alloys as measured

by g-rays: A, 42 mol-% Cs; B, 67 mol-% Cs [38]
2.4 Measurement of the Magnetic Susceptibility

$

=

<

/' & $

<
/& %

$

:
7

2'

+ 4 + 4 /[ &./'@ & / ( "

,
AB B'' : .(C0 )7

w&

+ 4 + 4 /[

F m0 V (w2 w1 )Hz dHz =dx B

MICROMETER
SCREW
VACUUM SEAL
VACUUM TORSION
BALANCE
K
RECORDER TO VACUUM
SYSTEM
BALANCE POWER
SUPPLY AND P
MEASURING CIRCUITS
TH
COILS COILS
MAGNET
Figure 12 Automatic vacuum torsion balance for the measurement of the mag-
netic susceptibility of a sample according to the Faraday method (after [39])
9
m'

K% HW DO .2'0 7

/'A( :

(5> :

2.5 Measurement of the Electrical Resistivity

TO VACUUM PUMP
RESERVOIR
THERMOCOUPLES
PUMP
POTENTIOMETER
PUMP
Figure 13 Apparatus employing two liquid metal loops with the capillary tube R in
which the resistivity is measured

.2/0 7

# .2/0

<
/(
*

40
38
r (Ωm 10−8)
36
34
32
30
0.0 0.4 0.8 1.2 1.6
X (mol-% N,H or D)
Figure 14 Resistivity–mole fraction isotherms at 673 K for solutions of nitride (solid

circles), hydride (open circles), and deuteride (+ ) in liquid lithium (after [41])

>&( :

?

r

rs =rNa Rs =RNa .

5

<
/2

.2/0

%

7

%

5

.2&0

'> 3

.2/0
2.6 Measurement of the Heat of Dilution

7

<
−Q (Jmol-1) 200
400
600
6 8 10 12
C Cd (mol - %)
Figure 15 Calorimetric titration curve of heterogeneous Cd amalgam at 298 K;

initial concentration of Cd at 12.45 mol-%

,

7

;

7 ;5"

"

<
/>

4

; F; %

7

K
HW DO .2(0

'> 3

/'– & 3


2.7 Measurements of the Kinetics of Decomposition or Formation

7

4

7

L D

.220

; $ ?

7

/22 ; /2( $ /2A ?

%

<
/@

;
"

/' 3

100
80
60
(min)
40
τ
20
0.02 0.04 0.06 0.08

C Ce (mol dm− 3 )
Figure 16 Dependence of the half-decomposition time of Ce amalgams on the

initial Ce concentration
; % # 4 .2>0 %

-
D

:

D

-

%

D

-
& D

,

2.8 Measurements of the Diffusion Coefficient

'/ 3

,

%

K% HW DO .2@0

;
"

;

7

7

.2@0

;

%

<
/A
(' 3

1.2
1.0
105 D (Cu) / cm 2 s −1
0.8
0.6
0.4
6 8 10 12 14 16
C (Cu) / mmol dm−3
Figure 17 Dependence of diffusion coefficients of Cu in its amalgam on the initial

concentration of Cu in Hg

> 3

2.9 Measurement of the Vapour Pressure

<
> /(

7

7

# .2A2B0

: .2C0
2.10 Neutron Transmission Measurements

7

! "

.>'0 =

>' >'

2.11 X-ray Absorption Spectrometry

9%

HW DO .>/0

%

9 8

" 8
7

4 ,

:

[ 6
xM [mi1 mi2 (1 p)] 1

ln [(I2 )1 p (I1 ) 1 I10 (I20 )p 1 ] C
S (mi1 mi2 )=mi2

# .>/0 m
/ m
&

8

/ & , /' , &' , / , &

8

8
-

8

/' –2 3

2.12 Electrochemical Oxidation (Chronoamperometry,

Chronopotentiometry, Amalgam Polarography, Voltammetry)

/&

5

5
5

7

7
7

;

;
" .>&0

<
/B
30
A
B
20
i (mA)
C
10
20 40 60 80
t (min)
Figure 18 Current–time curve of the anodic oxidation of Ce amalgam at – 0.1 V

versus SCE at 298 K; volume of amalgam 5.5 cm3 , surface of amalgam 9 cm2 , total
concentration of Ce 4.66 × 10–2 mol dm–3 (the determined solubility 6 × 10 –3 mol
dm–3 )

(0

%

1

7

7

< 7

4

> 3

/' –(
/ 3
3
40
30 2
i (mA)
20 1
10
0 0.4 0.8 1.2 1.6

w (Ba)/ %
Figure 19 Relationship of limiting currents of the Ba oxidation versus Ba concen-

tration at 293 K (curve 1), 313 K (curve 2), and 333 K (curve 3); the polarization scan
rate is 24 mV min –1, the amalgam volume 0.8 cm3 , the surface of the amalgam
1.0 cm2 , and the rate of mixing 400 s –1
2.13 Measurement of the Decay of Radioactivity

of the Activated Solute

,

7

K
?

- ; .>20

$ 7® K

@> K

" K

?

6 ?

K

?

? 7

# .>>0
2.14 Spot-light Technique

! .>@0

4

3.0
1
2.5 2
3
2.0 4
Ratio
5
6
1.5
1.0
308 C 337 C 378 C 385 C 397 C 418 C

0.5
350 400
t ( C)
Figure 20 Temperature dependence of the ratio of the vibrational attenuation dec-

rements of Na–K alloy with various H concentrations: curves 1 to 6 for (1.5; 9.9; 3.4;
15.2; 6.8; 17.2) × 10 –3 mass-% H, respectively
2.15 Viscosity Measurements

=

4

,

: $
4 .>A0

?5:

'> :E

4

"

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? 5: <
&'

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: $
4 .>A0

4

3 INDIRECT METHODS
3.1 Electroreduction of Solute Ions on an Electrode made of Solvent
Metal with Subsequent Crystallization of the Solute

%

,


/'' F

4

,
/&

4

G

.>B0
K
9 ; .>C0

?
7

?

?

7

?

?

?

?

?
.@'0 9%
D .@/0

7

! : ,
.@&0

!

!

"

4

3.2 Electrooxidation of a Metal Covered by a Film

of Liquid Metal
,% % .@(@20 7

"

"
% K
7

L

/'
nFA=is 1=kcM h=DM CM /'
Q

7

)
<
H $ N

' 6

" F6

"
;

%

Q)$ / L
K

%

;
,
"

; ,

7

%

3.3 Calculation of the Solubility of Metals in Liquid Metals from

Corrosion Rates in Dynamic Corrosion Rigs

.@>0

4

U

F6

F6
%

.
//0
r b(cMs cMb ) //

4

F6

F6

F6 b

/&
b Sh DM =d /&
<

.@@0

Sh 0:037(Re0:75 180) Sc0:42 [1 (d=L)2=3 ] /(

Sh bd=DM , Re vd=n, and Sc n=DM ;d

' 6

& –/

–/ n %

& –/ /

7

$5/A-

.@A0

%

.@B0

/' –B
/' –& 3

b

/' 3

3.4 Motion of Liquid Macroscopic Inclusions in Ionic Crystals

in a Temperature Gradient

! 4
,
6
.@C0

/& CA( :

/''' :E

-
<

4
-
<

D

/2

# .@C0
cF s RT 2 u=DHF DF DT /2
5
7 u

D+ <

-
<

' <

<

D7

/' –& 3 <

CA( :
7


(' A' m

/2 D+ < ' <
7

/' 3

%

'/ 3

4

4 SOLUBILITY DETERMINATIONS OF METALS AND NON-METALS

IN SOLID METALS

& 6

&

*

5

5

5 REFERENCES
/ = : 4 #

3K' 7 KHVLV L

6 N ! /C@2
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TABLE 2 Methods for determining the solubility of metals in solid metals 470
Composition
Method Route of determination Remarks range (mol-%) Example Reference
X-ray diffraction Break point of the relation Supersaturated samples 0.1–100 U in Pd [70]
of lattice parameters versus have constant
composition parameters
Electron diffraction Break point of the relation Thin films are analyzed 0.1–100 Au in Ni [71]
of lattice parameters versus
composition
Electron microprobe Fluorescence intensity of Homogeneity of the sample 0.01–100 Sc in B [72]
X-rays of the saturated should be assured
phase
Metallography (micro Observation of the Electron microscope might 0.01–100 Zn in Mn; [73]
structure) formation of a new phase of be necessary additional V in U [74]
the solvent after addition of to optical
the solute
Electrical resistance Break point of the relation 10–4 –100 Pt in Pb [75]
of the residual electric
resistance versus logarithm
of solute concentration
Electromotive force Break point of the relation Solute has to be 10–4 –100 Hg in Sn [76]
of the cell potential versus electrochemically more
logarithm of solute active than solvent
concentration
Chemical equilibrium Chemical analysis of solid For example: Au foil 10–4 –100 C in Au [77]
equilibrated with gaseous equilibrated with
solute and the related CO/ CO2 gas mixture
constant pressure points at
saturation
Mechanical Break point of the relation of 10 –2 –100 Te in Au [78]
properties rolling properties versus
composition
Hardness Break point of the relation of 0.1–100 P in Fe [79]
hardness versus
composition
Vapor pressure Break point of the relation of 0.1–100 Hg in Au [80]
vapor pressure versus
composition
Dilatometry Break point of the relation of 10–2 –100 Hg in Cd [81]
the thermal expansion
coefficient versus
composition
Thermal analysis Break points of cooling and 0.1–100 Hg in Au [82]
heating curves
Calorimetry Break point of the relation of Dissolution process 0.1–100 Hg in Cd [81]
the enthalpy or heat
capacity versus composition
Electrochemical Abrupt change of current Solute has to be 10–3 –1 Zn in Hg [83]
polarization versus potential electrochemically more
dependence of the oxidation active than solvent
of the solute
Magnetic Break point of the relation of The susceptibility of 10–6 –10–2 P in Fe [84]
susceptibility the susceptibility versus homogeneous and
composition heterogeneous alloys
has to be different
(continues)
471
472
TABLE 2 (continued)
Method Route of determination Remarks Composition Example Reference
range (mol-%)
Mössbauer effect Break point of the relation of 0.1–100 Au in Ni [85]
isomer shift or Curie
temperature versus
composition
Superconductivity Abrupt change of the 0.1–100 Hg in Cd [86]
superconductivity transition
temperature due to change
of the composition
Hall effect Content of charge carriers Thin films; samples have to 10– 6 –10–2 Au in Ge [87]
calculated from Hall be absolutely pure
electromotive force
Activation analysis Measurement of the Detection level may be 10–9 –10–1 Au in Ge [88]
characteristic radiation of different for various
the solute after activation of solutes
the sample
Diffusion process Saturation is indicated by 10–6 –100 Au in Na [89]
constancy of composition
within a part of the sample
Remelting under Measurement of the amount of The gaseous element must 10 –4 –1 N in steels [90]
vacuum or an inert gas isolated during the be weakly bound to the
gas atmosphere remelting of the metal, if it is metal in order to release
saturated with a gaseous practically the whole
element amount
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CHAPTER 4.5
Solubility of Solids in Solids

James Sangster
Sangster Research Laboratories, Montreal, Canada
1 INTRODUCTION
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Solubility of Solids in Solids 479
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9 REFERENCES
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PART 5
Special Systems

2 3
© ** 4 5 6 / 7. ISBN: 0-471-49708-8 .
CHAPTER 5.1
Solubility of Solids and Liquids

in Supercritical Fluids
Karel Aim
Czech Academy of Sciences, Prague, Czech Republic
and
Maurizio Fermeglia
University of Trieste Trieste, Italy
1 INTRODUCTION
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Solubility of Solids and Liquids in Supercritical Fluids 495
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Figure 6 Principle of phase-boundary methods (illustrating the determination of

dew- and bubble-points): The P–X, Y diagram (on the left) may be constructed of
the pairs of dew- and bubble-points (designated for the arrow-pointed overall com-
position by W and L, respectively), which are identified with the corresponding
breaks on the P–V diagram for that overall composition (on the right). P, pressure;
V, volume; x, liquid phase mole fraction; y, vapor phase mole fraction
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CHAPTER 5.2
Solubility of Solids and Liquids

in Cryogenic Liquids
Elzbieta Szczepaniec-Cieciak
Jagiellonian University, Cracow, Poland
1 INTRODUCTION
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TABLE 1 Selected physical properties of pure fluids of cryogenic interest [2,131±133]
Molecular Triple point Normal boiling Critical point Critical point
weight temperature (Ttp =K) point (Tb =K) temperature (Tc =K) pressure (105 P c =Pa)
Inorganic
o-H2 2.016 14.05 20.45 Ð Ð
p-H2 2.016 13.804 20.268 32.976 12.928
n-H2 2.016 13.96 20.39 33.19 13.15
3
He 3.016 Ð 3.191 3.324 1.163
HD 3.022 16.60 22.14 35.91 14.83
He(4 He) 4.003 Ð 4.224 5.201 2.275
n-D2 4.028 18.73 23.67 38.34 16.639
NH3 17.031 195.4 239.7 405.6 112.8
H2 O 18.015 273.16 373.15 647.1 220.5
Ne 20.179 24.54 27.09 44.40 26.54
CO 28.010 68.13 81.64 132.91 34.99
N2 28.013 63.15 77.35 126.20 34.00
O2 31.999 54.351 90.180 154.576 50.43
H2 S 34.076 187.7 212.9 373.5 90.08
F2 37.997 53.48 84.950 144.31 52.15
Ar 39.948 83.80 87.28 150.86 48.98
CO2 44.010 216.55 194.69 (subl.) 304.2 73.76
Kr 83.80 115.76 119.79 209.4 55.0
Xe 131.29 161.37 165.02 289.73 58.40
Hydrocarbons
CH4 16.043 90.680 111.63 190.555 45.988
C2 H2 26.038 192.4 189.13 (subl.) 308.33 61.39
C2 H4 28.054 103.986 169.409 282.343 50.40
C2 H6 30.070 90.348 184.547 305.33 48.714
(continues)
559
TABLE 1 (continued ) 560
Molecular Triple point Normal boiling Critical point Critical point

weight temperature (Ttp =K) point (Tb =K) temperature (Tc =K) pressure (105 P c =Pa)
C3 H4 (propyne) 40.065 170.5 (1 atm) 250.0 402.38 56.28
C3 H4 (propadiene) 40.065 136.9 (1 atm) 238.7 393.0 54.7
C3 H6 (propene) 42.081 87.9 (1 atm) 225.4 365.0 46.2
C3 H6 (cyclopropane) 42.081 145.7 (1 atm) 240.4 397.80 54.95
C3 H8 44.097 85.47 231.071 369.80 42.420
iso-C4 H10 (2-methylpropane) 58.124 113.55 261.359 408.00 36.549
C4 H10 58.124 134.86 272.638 425.16 37.961
neo-C5 H12 (2,2-dimethylpropane) 72.151 256.6 282.628 433.75 31.96
iso-C5 H12 (2-methylbutane) 72.151 113.25 301.025 460.39 33.81
C5 H12 72.151 143.429 309.19 469.65 33.69
Some fully halogenated hydrocarbons
CCl3 F R11 137.368 162.67 296.780 471.2 44.1
CCl2 F2 R12 120.914 115.0 243.38 385.0 41.25
CClF3 R13 104.459 84.2 191.71 301.88 40.07
C2 Cl5 F R111 220.31 374.5 411.1
C2 Cl4 F2 R112 203.831 299.70 366.0 551 34
C2 Cl3 F3 R113 187.376 236.8 320.783 487.5 34.11
C2 Cl2 F4 R114 170.922 180.62 276.92 418.9 32.6
C2 ClF5 R115 154.467 167 234.04 353.1 31.57
C3 Cl3 F5 R125 237.38 346.0 505.0 30.8
C3 Cl2 F6 R216 220.93 137 307.5 449 29.3
C3 ClF7 R217 204.47 274±275 395 27.8
CBrClF2 R12B1 165.4 193 269.27 427 43.10
CBrF3 R13B1 148.910 105 215.3 340.1 40.99
C2 Br2 F4 R114B2 259.824 162.7 320.41 487.80 33.93
CCl4 R10 153.825 250.33 349.788 556.6 45.16
Some CFC alternatives
CHCl2 F R21 102.923 138 282.05 451.6 51.97
CHClF2 R22 86.468 113 232.3 369.30 49.88
CHF3 R23 70.013 117.97 191.1 298.98 48.20
CH2 ClF R31 68.48 140 264.1
CH2 F2 R32 52.024 137 221.4 351.56 58.30
C2 HCl4 F R121 185.84 190.5 389.7
C2 HCl3 F2 R122 169.39 344.9
C2 HCl2 F3 R123 152.930 166 301.0 456.94 36.74
C2 HClF4 R124 136.475 74 261.1 395.65 36.34
C2 HClF4 R124a 136.475 156 262.9
C2 HF5 R125 120.020 170 224.6 339.4 36.31
C2 H2 Cl2 F2 R132 134.94 236
C2 H2 Cl2 F2 R132a 134.94 171.9 319.9
C2 H2 F4 R134a 102.030 172 247.0 374.21 40.56
C2 H3 ClF2 R142b 100.495 142 263.9 410.25 42.46
C2 H3 F3 R143a 84.040 161.82 225.8 346.25 38.11
C2 H4 F2 R152a 66.060 156 249.0 386.44 45.20
C3 H4 Cl3 F R251 165.38 391.6
C3 H4 Cl2 F2 R252 148.92 353.6
C3 H4 ClF3 R253 132.46 166.9 318.2
561
TABLE 2 Some solubility ranges of solids in cryogenic liquids 562
Temperature Ranges of experimentally determined or estimated ( ) solubilities (in mole fractions) and examples of
Solvent T/K substances possessing a given level of solubility
LHe 4.2 < 10 11 H2 [134]
LH2 20 10 0 10 1 D2 [135]
10 1 10 2 Ne [15]
< 5 10 7 O2 (30 K)[117]
10 8 N2 [117]
10 11 10 12 CO [15], Ar [15]
LNe 27 10 2 10 3 N2 [15]
10 3 10 4 CO [15], F2 [15], Ar [15], O2 [15], CH4 [15]
10 7 10 8 CF4 [15], Kr [15]
LN2 77 100 10 1 CH4 [27,45], Ar[44], Kr[23]
10 2 10 3 C2 H6 [26,91], C3 H8 [91], C2 H4 [51,90]
10 3 10 4 C3 H6 [90], iso-C4 H10 [91], C4 H8 [90], CF4 [67]
10 4 10 5 N2 O[16], C4 H10 [91], CHF3 [67]
10 5 10 6 CO2 [16,48,49,69], N2 O[71], C2 H2 [48,49], dimethyl ether[16]
10 6 10 7 H2 S[70], Cl2 [70], 2-methylbutane[63], 1-pentene[64], CF2 Cl2 [67], CCl4 [58],
C2 H5 Br[59]
< 10 7 CH3 OH(115 K)[16], C2 H5 OH(115 K) [16], CH3 I(125 K)[89]
8
10 7 10 CS2 (90 K)[89], C5 H12 [63], cyclopentane[63], 2-methylpentane[75],
1-hexyne[76], toluene[61,89], CH2 Cl2 [68], C2 HCl3 [58], diethyl ether[16]
< 10 8 H2 O[16]
10 8 10 9 C6 H14 [62], 1- hexene[765], cyclohexane[62], CHCl3 [58]
< 10 10 NH3 [70], SO2 [70], N2 O4 [60]
10 10 10 11 C6 H5 Cl[67]
LO2 90 100 10 1 Kr[25], Xe[25], CH4 [17,18,27], C2 H6 [18]
10 1 10 2 C2 H4 [18,26,51,81], C3 H8 [18]
10 2 10 3 SF6 [80], C3 H6 [18,26], iso-C4 H10 [18,52]
10 3 10 4 C4 H10 [18,52], 2,2- dimethylpropane[18], COS[81], CHF3 [20]
10 4 10 5 N2 O[16,17], C5 H12 [18], 2-methylpropene[18,80]
5 6
10 10 CO2 [16,18,48,49,81], C6 H14 [18,52], C2 H2 [18,48–50,52,80,83], CH3 Cl[80], diethyl
ether[16,80], dipropyl ether[16,80], (CH3 )3 N[80]
10 6 10 7 CS2 [80], H2 CO[80], CCl4 [80], dimethyl ether[80], diisopropyl ether[16,80]
10 7 10 8 NH3 [52], CH2 Cl2 [80], CHCl3 [80], C2 H4 Cl2 [80]
< 10 8 H2 O[16]
LAr 90 100 10 1 Kr[23], CH4 [47]
10 1 10 2 Xe[138]
10 2 10 3 CF3 Cl[88]
10 3 10 4 2,3-dimethylbutane[79], CHF3 [20], CF2 Cl2 [88]
10 4 10 5 HCl[20], N2 O[16], C5 H12 [79], 2,2-dimethylpropane[79], 2-methylpentane[75],
4-methyl-2-pentene[87], 2-hexene[87], cyclopentene[87], dimethyl ether[16],
CFCl3 [88]
5 6
10 10 CO2 [79], 1,3- butadiene[79], 2-methylbutane[65], C6 H14 [87], isooctane[87],
2-methyl-1-pentene[87], 1-hexene[87], 2-heptene[87], 1-octene[87],
cyclohexane[87], methylcyclopentene[87], methylacetylene[86],
ethylacetylene[86], diethyl ether[16], dipropyl ether[16], CH3 I(125 K)[89]
6 7
LAr 90 10 10 NH3 (125 K)[89], CS2 [81], C5 H12 [65], 1-pentene[64], 1-hexene[75],
1,2-dimethycyclopentene[87], 2-octene[87], vinylacetylene[86], diacetylene[86],
toluene (90 K)[20], 1,3-dimethylbenzene (135 K)[20], isopropylbenzene
(135 K)[20], diisopropyl ether[16]
< 10 7 methanol (128 K)[16], ethanol (128 K)[16]
10 7 10 8 1-hexyne[76], cyclopentane[65]
10 8 10 9 benzene[20,89], anisole (125 K)[20]
< 10 8 H2 O[16]
< 7 10 9 pyridine (135 K)[20]
< 6 10 9 pyrazine (135 K)[20]
LCH4 110 100 10 1 C4 H10 [21,97]
10 1 10 2 2,2-dimethylpropane[79], cyclopentane[79]
10 2 10 3 H2 S[139], C5 H12 [79], 2,3-dimethylbutane[79]
10 3 10 4 CO2 [79,139], C6 H14 [24,55], cyclohexane[55], 1,3-butadiene[79], C2 H2 [54]
10 4 10 5 H2 O[85], C7 H16 [24,55], toluene[24]
(continues)
563
TABLE 2 (continued) 564
Temperature Ranges of experimentally determined or estimated ( ) solubilities (in mole fractions) and examples of
Solvent T/K substances possessing a given level of solubility
10 5 10 6 benzne[24,55,56], methanol[55]
LKr 125 100 10 1 Xe[23]
10 2 10 3 CO2 (140 K)[92]
10 3 10 4 MoF6 (140 K)[92], H2 CO (140 K)[92]
10 4 10 5 C2 H2 [20]
10 5 10 6 benzene[89], acetone[89], HN3 (140 K)[92]
10 6 10 7 NH3 [89], anisole (140 K)[20], pyridine (140 K)[89]
10 8 10 9 pyrimidine[89]
10 9 10 10 pyrazine[89]
Solubility of Solids and Liquids in Cryogenic Liquids 565
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Krzeczkowska [62,64] to determine the solubility of solid C5-C 6 hydrocarbons in
liquid nitrogen and argon. (a) Unit for obtaining solidified hydrocarbon. (b) Unit for
obtaining saturated solution of a hydrocarbon in cryogenic liquid. (c) Unit for evapor-
ating the saturated solution
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of the solubility of hydrocarbons in liquid oxygen
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Figure 6 Single-pass, continuous-flow, solubility apparatus constructed by Kuebler

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Figure 7 Flow diagram of the apparatus used by Sterner [77] to study phase
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Figure 8 Scheme of the apparatus used by Preston, Funk and Prausnitz [79] for
the determination of the solubilities of hydrocarbons and carbon dioxide in liquid
methane and in liquid argon: (a) cryostat (b) solid–liquid equilibrium cell; (c) liquid-
sampling valve
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Figure 9 Schematic diagram of the apparatus built in the Institute of Physics,

Leningrad University (now St Petersburg University) for the study of cryogenic solu-
tions by the infrared spectroscopy method [91]. The sample chamber with two per-
pendicular optical layers: 1.7 cm and 10 cm long has BaF2 windows
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Figure 12 Flow diagram of apparatus designed by Kurata and Kohn [95] for study-
ing fluids under high pressures and low temperatures (p–V–T measurements,
vapor–liquid equilibria, solid–liquid equilibria, solid–vapor equilibria, solid–liquid–
vapor equilibria, partial miscibility in a binary system, viscosity relationships, solid
solubility)
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Figure 13 Schematic and detailed diagrams of the apparatus designed by Omar

and Dokoupil [117] for determining the solubilities of nitrogen and oxygen in liquid
hydrogen
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Figure 14 Scheme of the apparatus used by Omar, Dokoupil and Schroten [45] for
the determination of solid–liquid equilibrium for the N2 CH4 system
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Figure 15 Schematic of sample cell used by Souers et al. [130] for three-phase
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CHAPTER 5.3
Solubility of Polymers in Liquids

Sonja Krause
Rensselaer Polytechnic Institute, New York
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Figure 5 Simplified version of pulse induced critical scattering apparatus. A, bath;

B, immersion heater; C, refrigeration unit; D, heat transfer fluid; E, flow system; F,
data handling system; G, light guide; H, heater; I, He–Ne laser; J, scattering cell; K,
thermistor; L, pump. Reprinted from Reference [16] by permission of Butterworth/
Heinemann
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Figure 6 Typical extrapolation procedure to locate spinodal points for four different
solutions of polystyrene in cyclohexane. This Figure is a plot of scattered intensity at
a scattering angle of 30º against temperatures. Data at the lower temperatures are
extrapolated in a linear fashion. The letter ‘y’ marks the lowest temperature at which
acceptable data could be obtained for each sample. At lower temperatures, phase
separation by nucleation and growth invalidated the data for this procedure. The
solid circles in plot A are an attempt to linearize the data. Reprinted from Reference
[16] with permission of Pure Appl. Chem. and Butterworth/Heinemann, Oxford
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P.G.T. Fogg (Eds.) - The Experimental Determination of Solubilities, Volume 6 (2003)

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P.G.T. Fogg (Eds.) - The Experimental Determination of Solubilities, Volume 6 (2003)

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The Experimental

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Wiley Series in Solution Chemistry

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1 FUNDAMENTALS OF SOLUBILITY <A

Chapter 1.1 Thermodynamics of Solubility <=

Chapter 1.2 Kinetics and Mechanisms of Crystal

Chapter 2.1 Solubility of Gases in Liquids <9<

Chapter 2.2 Solubility of Gases in Polymers <K<

Chapter 2.4 Solubility of Gases in Solid Metals 8<=

Chapter 3 Liquid–Liquid Solubilities 8:A

Chapter 4.1 Solubility of Solids in Liquids 8K=

Chapter 4.2 Solubility of Sparingly Soluble Ionic Solids in Liquids :<K

Chapter 4.3 Solubility of Salt–Water Systems at High

Chapter 4.4 Solubility of Metals and Non-metallic Substances

Chapter 4.5 Solubility of Solids in Solids @AA

5 SPECIAL SYSTEMS @=<

Chapter 5.1 Solubility of Solids and Liquids in Supercritical Fluids @=:

Chapter 5.2 Solubility of Solids and Liquids in Cryogenic Liquids KKA

Chapter 5.3 Solubility of Polymers in Liquids K=K

Reginald P.T. Tomkins

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Table 2 Quantities used to describe solubilities : Based on mass

Table 5 (Quantities used to describe solubilities : Based on volume alone, or on

relative (mass) density d d  r=r0 1 4

2 QUANTITIES AND UNITS USED TO DESCRIBE SOLUBILITIES

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2.2 Relation of Special Quantities to Amount Fraction, Molality

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2.4 Sechenov Parameters for Salt Effects on Solubility of Gases

Bunsen coefficient (quantities at standard partial pressure p 0 and

Table 10 Approximate relations connecting Ostwald, Bunsen

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2 BASIC DEFINITIONS IN THERMODYNAMICS OF SOLUBILITY

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