IUPAC-NIST Solubility Data Series. 79. Alkali and Alkaline Earth Metal Pseudohalides

176 Pages·2004·1.59 MB·English

IUPAC-NIST Solubility Data Series. 79. Alkali and Alkaline Earth Metal
Pseudohalides
Jiri Ha´laa(cid:133)
DepartmentofInorganicChemistry,MasarykUniversity,Brno,CzechRepublic
Contributors *Evaluator
(cid:132) (cid:133)
Jiri Ha´la*
MasarykUniversity,CzechRepublic
H. Akaiwa
GunmaUniversity,Japan
~Received23August2002;accepted4November2002;publishedonline13February2004!
Thisvolumepresentssolubilitydataofazides,cyanides,cyanates,andthiocyanatesof
alkali metals, alkaline earth metals, and ammonium. Covered are binary and ternary
systemsinallsolvents.Nosolubilitydatahavebeenfoundforsomeofthecompoundsof
alkali metals, alkaline metals, and ammonium. These include beryllium and magnesium
azides, lithium, rubidium cesium, ammonium, and alkaline earth cyanates and cyanides,
and beryllium thiocyanate. Likewise, no solubility data seem to exist for selenocyanates
ofthementionedmetalsandammonium.Theliteraturehasbeencovereduptothemiddle
of2001,andtherewasagreatefforttohavetheliteraturesurveyascompleteaspossible.
The few documents which remained unavailable to the editor, and could not be included
in the volume, are listed in the Appendix. For some compounds it was not possible to
show the Chemical Abstracts registry numbers since these have not been assigned. For
this reason, the registry number index is incomplete. © 2004 American Institute of
Physics. @DOI:10.1063/1.1563591#
Keywords: alkali metals; alkaline earth metals; ammonia; azides; cyanides; cyanates; organic solvents;
thiocyanates;solid-liquieequilibrium;solubility;water.
Contents 3.3.1. Evaluation of the KN –H O
3 2
System........................... 15
3.4.RubidiumAzide........................ 17
1. Preface................................... 3
3.5.CesiumAzide.......................... 18
2. Introduction to the Solubility Data Series:
3.6.AmmoniumAzide....................... 18
Solubility of Solids in Liquids................. 3
3.7.CalciumAzide.......................... 20
2.1.The Nature of the Project................. 3
3.8.StrontiumAzide........................ 21
2.2.Compilations and Evaluations............. 3 3.8.1. Evaluation of the Sr~N ) –H O
3 2 2
2.2.1. Compilations...................... 3
System........................... 21
2.2.2. Evaluations....................... 3
3.9.BariumAzide.......................... 24
2.3.Quantities and Units Used in Compilation 3.9.1. Evaluation of the Ba~N ) –H O
3 2 2
and Evaluation of Solubility Data.......... 5 System........................... 24
2.3.1. Mixtures, Solutions, and Solubilities... 5 4. The Solubility of Cyanides................... 25
2.3.2. Physicochemical Quantities and 4.1.Lithium Cyanide........................ 25
Units............................ 5 4.2.Sodium Cyanide........................ 26
2.4.References for the Introduction............ 7 4.2.1. Evaluation of the NaCN–H O
2
3. The Solubility ofAzides..................... 8 System........................... 26
3.1.LithiumAzide.......................... 8 4.2.2. Evaluation of the NaCN–NaOH–H O
2
3.2.SodiumAzide.......................... 9 System........................... 29
3.3.PotassiumAzide........................ 15 4.3.Potassium Cyanide...................... 33
4.3.1. Evaluation of the KCN–NH
3
a!Electronicmail:[email protected] System........................... 36
© 2004AmericanInstituteofPhysics. 4.3.2. Evaluation of the KCN–Ethanol
0047-2689(cid:213)2004(cid:213)331(cid:213)1(cid:213)176(cid:213)$39.00 1 J.Phys.Chem.Ref.Data,Vol.33,No.1,2004
(cid:132) (cid:133)
22 IUPAC-NIST SOLUBILITY DATASERIES
System........................... 37 6. Sodium cyanate–ammonia system............. 46
5. The Solubility of Cyanates................... 46 7. Sodium cyanate–diethylether–methanol
5.1.Sodium Cyanate........................ 46 system.................................... 49
5.1.1. Evaluation of the NaOCN–NH3 8. Lithium thiocyanate–water system............. 52
System........................... 46 9. Sodium thiocyanate–water system............. 60
5.2.Potassium Cyanate...................... 50 10. Sodium thiocyanate–ammonia system.......... 64
6. The Solubility of Thiocyanates................ 52
11. Sodium thiocyanate–acetone system............ 67
6.1.Lithium Thiocyanate..................... 52
12. Sodium thiocyanate–methylthiocyanate–water
6.1.1. Evaluation of the LiSCN–H O
2 system.................................... 80
System........................... 52
13. Potassium thiocyanate–water system........... 82
6.2.Sodium Thiocyanate..................... 59
14. Potassium thiocyanate–water system........... 85
6.2.1. Evaluation of the NaSCN–H O
2 15. Potassium thiocyanate–ammonia system........ 88
System........................... 59
16. Potassium thiocyanate–potassium carbonate–
6.2.2. Evaluation of the NaSCN–Ethanol
water system............................... 107
System........................... 65
17. Potassium thiocyanate–urea–water system....... 111
6.2.3. Evaluation of the NaSCN–Acetone
18. Potassium thiocyanate–water–acetone system.... 113
System........................... 67
6.3.Potassium Thiocyanate................... 82 19. Potassium thiocyanate–polyethylene~1500!–
6.3.1. Evaluation of the KSCN–H O water system............................... 115
2
System........................... 82 20. Potassium thiocyanate–polyethylene~6000!–
6.3.2. Evaluation of the KSCN–Ethanol water system............................... 116
System........................... 90 21. Potassium thiocyanate–methylthiocyanate–water
6.3.3. Evaluation of the KSCN–Acetone system.................................... 116
System........................... 91 22. Potassium thiocyanate–ethylthiocyanate–water
6.3.4. Evaluation of the KSCN–2-Butanone system.................................... 117
System........................... 93 23. Ammonium thiocyanate–water system.......... 122
6.3.5. Evaluation of the KSCN–1-Butanol 24. Ammonium thiocyanate–water system.......... 124
System........................... 94 25. Ammonium thiocyanate–ammonia system....... 127
6.3.6. Evaluation of the KSCN–Pyridine
26. Ammonium thiocyanate–ammonium nitrate–
System........................... 95
water system............................... 132
6.4.Rubidium Thiocyanate................... 119
27. Ammonium thiocyanate–potassium thiocyanate–
6.5.Cesium Thiocyanate..................... 121
water system............................... 134
6.6.Ammonium Thiocyanate.................. 122
28. Ammonium thiocyanate–potassium thiocyanate–
6.6.1. Evaluation of the NH SCN–H O
4 2 water system............................... 136
System........................... 122
29. Ammonium thiocyanate–ammonium sulfate–
6.7.Magnesium Thiocyanate.................. 146
water system............................... 139
6.8.Calcium Thiocyanate..................... 148
30. Ammonium thiocyanate–triethylamine–water
6.9.Strontium Thiocyanate................... 154
system.................................... 141
6.10. Barium Thiocyanate.................... 155
6.10.1. Evaluation of the Ba~SCN) –H O 31. Ammonium thiocyanate–urea–water system..... 142
2 2
32. Ammonium thiocyanate–methylthiocyanate–
System.......................... 155
water system............................... 143
7. Appendix.................................. 162
8. System Index.............................. 164 33. Ammonium thiocyanate–aniline–water system... 144
9. Registry Number Index...................... 168 34. Calcium thiocyanate–sodium thiocyanate–water
10. Author Index............................... 170 system.................................... 150
35. Calcium thiocyanate–potassium thiocyanate–
List of Tables water system............................... 151
1. Interconversions between quanties used as 36. Calcium thiocyanate–ammonium thiocyanate–
measures of solubilities...................... 7 water system............................... 152
37. Calcium thiocyanate–methylthiocyanate–water
system.................................... 152
List of Figures
38. Barium thiocyanate–sodium thiocyanate–water
1. Lithium azide–water system.................. 8
2. Sodium azide–water system.................. 10 system.................................... 156
3. Potassium azide–water system................ 16 39. Barium thiocyanate–potassium thiocyanate–
4. Ammonium azide–ammonia system............ 19 water system............................... 157
5. Sodium cyanide–sodium hydroxide–water 40. Barium thiocyanate–methylthiocyanate–water
system.................................... 31 system.................................... 159
J.Phys.Chem.Ref.Data,Vol.33,No.1,2004
JIRI HA´LA 33
1. Preface Dr.H.J.M.Gru¨nbauer,Amsterdam,TheNetherlands;Dr.A.
Maczynski, Warsaw, Poland; Professor P. Paoletti, Florence,
Italy; Professor V. M. Valyashko, Moscow, Russia; and Pro-
This volume presents solubility data of azides, cyanides,
fessor B. A. Wolf, Mainz, Germany. Without their help the
cyanates, and thiocyanates of alkali metals, alkaline earth
volume would not be complete.
metals, and ammonium. Covered are binary and ternary sys-
tems in all solvents. No solubility data have been found for
2. Introduction to the Solubility Data Series:
someofthecompoundsofalkalimetals,alkalinemetals,and
Solubility of Solids in Liquids
ammonium.Theseincludeberylliumandmagnesiumazides,
lithium,rubidiumcesium,ammonium,andalkalineearthcy-
2.1. The Nature of the Project
anatesandcyanides,andberylliumthiocyanate.Likewise,no
solubility data seem to exist for selenocyanates of the men- The Solubility Data project ~SDP! has as its aim a com-
tioned metals and ammonium. The literature has been cov-
prehensivereviewofpublisheddataforsolubilitiesofgases,
ereduptothemiddleof2001,andtherewasagreateffortto
liquids, and solids in liquids or solids. Data of suitable pre-
have the literature survey as complete as possible. The few
cision are compiled for each publication on data sheets in a
documents which remained unavailable to the compiler, and
uniform format.The data for each system are evaluated and,
could not be included in the volume are listed in the Appen-
where data from independent sources agree sufficiently, rec-
dix. For some compounds it was not possible to show the
ommended values are proposed. The evaluation sheets, rec-
Chemical Abstracts registry numbers since these have not
ommended values, and compiled data sheets are published
been assigned. For this reason, the registry number index is
on consecutive pages.
incomplete.
In addition to documents that published numerical data,
2.2. Compilations and Evaluations
some papers that presented data in graphical form only were
includedaswell.Theywereconsideredforthevolumeeither The formats for the compilations and critical evaluations
if no other data were available for the system, or if the data have been standardized for all volumes. A description of
were published in difficult to obtain older literature. These these formats follows.
criteria led the compiler to include sometimes papers in
which the authors failed to specify conditions such as tem- 2.2.1. Compilations
perature, equilibrium time, or methods of analysis. Phase
diagrams have been included for some of the ternary sys- Theformatusedforthecompilationsis,forthemostpart,
tems. For binary eutonic systems, phase diagrams were in- self-explanatory. Normally, a compilation sheet is divided
cluded only if no numerical data were reported in the origi- into boxes, with detailed contents described below.
nal documents and the diagrams were the sole source of
Components
information. Of the many systems covered by the volume,
relatively few were studied by more than one laboratory. Each component is listed according to IUPAC name, for-
Thus the opportunity to carry out evaluations has been lim- mula, and Chemical Abstracts ~CA! Registry Number. The
ited, and only 20 systems have been evaluated. However, ChemicalAbstractsnameisalsoincludedifthisdiffersfrom
because of some uncertainty in most of the evaluated sys- the IUPAC name, as are trivial names if appropriate. IUPAC
tems, only tentative solubility values could usually be rec- and common names are cross-referenced to Chemical Ab-
ommended. stracts names in the System Index.
Only those published results that report meaningful data TheformulaisgiveneitherintermsoftheIUPACorHill1
were considered for the volume. Papers that reported quali- system and the choice of formula is governed by what is
tativeresultswithstatementslike‘‘sparinglysoluble’’or‘‘in- usual for most current users: i.e., IUPAC for inorganic com-
soluble,’’ etc., were not considered. However, some docu- pounds, and Hill system for organic compounds. Compo-
ments reported solubility data which, although not included nents are ordered on a given compilation sheet according to:
in the volume for one reason or other ~e.g., single values of ~a! saturating components;
uncertain quality without any supporting information, ~b! non-saturating components;
sketches of phase diagrams!, may nevertheless be of some ~c! solvents.
informativevaluetothepotentialuserofthisvolumeincase In each of ~a!, ~b! or ~c!, the components are arranged in
theyrepresenttheonlyinformationavailableforagivensys- orderaccordingtotheIUPAC18-columnperiodictablewith
tem. For this reason, a list of systems for which only such two additional rows:
data exist has been included in theAppendix. Columns1and2: H,alkalielements,ammonium,alkaline
The editor wishes to express his thanks to the following earth elements
colleagues from IUPAC for their effort in proving copies of Columns 3 to 12: transition elements
publications,whichwouldotherwisenotbeavailabletohim: Columns 13 to 17: boron, carbon, nitrogen groups; chal-
Professor H.Akaiwa, Gunma, Japan ~also for translating the cogenides, halogens
Japanese papers!; D. J. J. Counioux, Lyon, France; Dr. P. G. Column 18: noble gases
T. Fogg, London, U.K.; Professor Fu Jufu, Beijing, China; Row 1: Ce to Lu
J.Phys.Chem.Ref.Data,Vol.33,No.1,2004
44 IUPAC-NIST SOLUBILITY DATASERIES
Row 2: Th to the end of the known elements, in order of originalgraphandthelimitationsofthedigitizingtechnique.
atomic number. In some cases graphs have been included, either to illustrate
The same order is followed in arranging the compilation data more clearly, or if this is the only information in the
sheets within a given volume. original. Full grids are not usually inserted as it is not in-
tended that users should read data from the graphs.
OriginalMeasurements
References are abbreviated in the forms given by Chemi- Method
cal Abstracts Service Source Index ~CASSI!. Names origi-
Theapparatusandprocedurearementionedbriefly.Abbre-
nally in other than Roman alphabets are given as transliter-
viations used in Chemical Abstracts are often used here to
ated by Chemical Abstracts. In the case of multiple entries
savespace,referencebeingmadetosourcesoffurtherdetail
~for example, translations! an asterisk indicates the publica-
if these are cited in the original paper.
tion used for compilation of the data.
Variables SourceandPurityofMaterials
Ranges of temperature, pressure, etc., are indicated here. For each component, referred to as ~1!, ~2!, etc., the fol-
lowinginformation~inthisorderandinabbreviatedform!is
Preparedby provided if available in the original paper: source and speci-
fied method of preparation; properties; degree of purity.
The names of all compilers are given here.
ExperimentalData EstimatedError
Components are described as ~1!, ~2!, etc., as defined in If estimated errors were omitted by the original authors,
the ‘‘Components’’box. Data are reported in the units used and if relevant information is available, the compilers have
in the original publication, with the exception that modern attemptedtoestimateerrors~identifiedby‘‘compiler’’orthe
names for units and quantities are used; e.g., mass percent compiler’s name in parentheses or in a footnote! from the
for weight percent; moldm23 for molar; etc. Usually, only internal consistency of data and type of apparatus used.
onetypeofvalue~e.g.,masspercent!isfoundintheoriginal Methods used by the compilers for estimating and reporting
paper, and the compiler has added the other type of value errors are based on Ku and Eisenhart.4
~e.g., mole percent! from computer calculations based on
1989 atomic weights.2 Temperatures are expressed as t/°C,
Commentsand(cid:213)orAdditionalData
t/°F or T/K as in the original; if necessary, conversions to
T/K are made, sometimes in the compilations and always in Many compilations include this section which provides
the critical evaluation. However, the author’s units are ex- shortcommentsrelevanttothegeneralnatureoftheworkor
pressedaccordingtoIUPACrecommendations3asfaraspos- additional experimental and thermodynamic data which are
sible. judged by the compiler to be of value to the reader.
Errorsincalculations,fittingequations,etc.,arenoted,and
where possible corrected. Material inserted by the compiler
References
is identified by the word ‘‘compiler’’ or by the compiler’s
name in parentheses or in a footnote. In addition, compiler- The format for these follows the format for the Original
calculated values of mole or mass fractions are included if Measurements box, except that final page numbers are omit-
the original data do not use these units. If densities are re- ted.References~usuallycitedintheoriginalpaper!aregiven
portedintheoriginalpaper,conversionsfromconcentrations whererelevanttointerpretationofthecompiledata,orwhere
to mole fractions are included, but otherwise this is done in cross-reference can be made to other compilations.
the evaluation, with the values and sources of the densities
being quoted and referenced.
Details of smoothing equations ~with limits! are included 2.2.2. Evaluations
if they are present in the original publication and if the tem-
The evaluator’s task is to assess the reliability and quality
perature or pressure ranges are wide enough to justify this
of the data, to estimate errors where necessary, and to rec-
procedure and if the compiler finds that the equations are
ommend ‘‘best’’ values. The evaluation takes the form of a
consistent with the data.
summaryinwhichallthedatasuppliedbythecompilerhave
The precision of the original data is preserved when de-
been critically reviewed. There are only three boxes on a
rived quantities are calculated, if necessary by the inclusion
typical evaluation sheet, and these are described below.
ofoneadditionalsignificantfigure.Insomecases,compilers
note that numerical data have been obtained from published
Components
graphs using digitizing techniques. In these cases, the preci-
sion of the data can be determined by the quality of the The format is the same as on the Compilation sheets.
J.Phys.Chem.Ref.Data,Vol.33,No.1,2004
JIRI HA´LA 55
Evaluator ~f! Units. While the original data may be reported in the
unitsusedbytheinvestigators,thefinalrecommendedvalues
Thenameandaffiliationoftheevaluator~s!anddateupto
are reported in SI units3 when the data can be accurately
which the literature was checked.
converted.
CriticalEvaluation 2.3. Quantities and Units Used in Compilation and
~a! Critical text. The evaluator checks that the compiled Evaluation of Solubility Data
data are correct, assesses their reliability and quality, esti-
2.3.1.Mixtures,SolutionsandSolubilities
mates errors where necessary, and recommends numerical
valuesbasedonallthepublisheddata~includingtheses,pat- Amixture5 describes a gaseous, liquid or solid phase con-
ents and reports! for each given system. Thus, the evaluator tainingmorethanonesubstance,wherethesubstancesareall
reviewsthemeritsorshortcomingsofthevariousdata.Only treated in the same way.
published data are considered. Documented rejection of A solution5 describes a liquid or solid phase containing
some published data may occur at this stage, and the corre- more than one substance, when for convenience one of the
sponding compilations may be removed. substances, which is called the solvent, and may itself be a
The solubility of comparatively few systems is known mixture, is treated differently than the other substances,
withsufficientaccuracytoenableasetofrecommendedval- which are called solutes. If the sum of the mole fractions of
uestobepresented.Althoughmanysystemshavebeenstud- the solutes is small compared to unity, the solution is called
ied by at least two workers, the range of temperatures is a dilute solution.
often sufficiently different to make meaningful comparison The solubility of a solute 1 ~solid, liquid or gas! is the
impossible. analytical composition of a saturated solution, expressed in
Occasionally, it is not clear why two groups of workers terms of the proportion of the designated solute in a desig-
obtained very different but internally consistent sets of re- nated solvent.6
sults at the same temperature, although both sets of results ‘‘Saturated’’ implies equilibrium with respect to the pro-
wereobtainedbyreliablemethods.Insuchcases,adefinitive cesses of dissolution and precipitation; the equilibrium may
assessmentmaynotbepossible.Insomecases,twoormore be stable or metastable. The solubility of a substance in
setsofdatahavebeenclassifiedastentativeeventhoughthe metastable equilibrium is usually greater than that of the
sets are mutually inconsistent. samesubstanceinstableequilibrium.~Strictlyspeaking,itis
~b! Fitting equations. If the use of a smoothing equation is theactivityofthesubstanceinmetastableequilibriumthatis
justifiable the evaluator may provide an equation represent- greater.! Care must be taken to distinguish true metastability
ing the solubility as a function of the variables reported on from supersaturation, where equilibrium does not exist.
all the compilation sheets, stating the limits within which it Either point of view, mixture or solution, may be taken in
should be used. describing solubility. The two points of view find their ex-
pression in the reference states used for definition of activi-
~c! Graphical summary. In addition to ~b! above, graphical
ties, activity coefficients and osmotic coefficients.
summaries are often given.
Note that the composition of a saturated mixture ~or solu-
~d! Recommendedvalues.Dataarerecommendedifthere- tion!canbedescribedintermsofanysuitablesetofthermo-
sults of at least two independent groups are available and dynamiccomponents.Thus,thesolubilityofasalthydratein
theyareingoodagreement,andiftheevaluatorhasnodoubt water is usually given as the relative proportions of anhy-
astotheadequacyandreliabilityoftheappliedexperimental drous salt in solution, rather then the relative proportions of
andcomputationalprocedures.Dataarereportedastentative hydrated salt and water.
if only one set of measurements is available, or if the evalu-
ator considers some aspect of the computational or experi- 2.3.2.PhysicochemicalQuantitiesandUnits
mental method as mildly undesirable but estimates that it
Solubilities of solids have been the subject of research for
shouldcauseonlyminorerror.Dataareconsideredasdoubt-
a long time, and have been expressed in a great many ways,
ful if the evaluator considers some aspect of the computa-
as described below. In each case, specification of the tem-
tionalorexperimentalmethodasundesirablebutstillconsid-
perature and either partial or total pressure of the saturating
ersthedatatohavesomevaluewheretheorderofmagnitude
gaseouscomponentisnecessary.Thenomenclatureandunits
ofthesolubilityisneeded.Datadeterminedbyaninadequate
follow, where possible, IUPAC Green Book.3Afew quanti-
method or under ill-defined conditions are rejected. How-
tiesfollowtheISOstandards7ortheGermanstandard;8seea
ever, references to these data are included in the evaluation
review by Cvitasˇ9 for details.
togetherwithacommentbytheevaluatorastothereasonfor
their rejection.
ANoteonNomenclature
~e! References.All pertinent references are given here, in-
cludingallthosepublicationsappearingintheaccompanying The nomenclature of the IUPAC Green Book3 calls the
compilation sheets and those which, by virtue of their poor solute component B and the solvent component A. In com-
precision, have been rejected and not compiled. pilations and evaluations, the first-named component ~com-
J.Phys.Chem.Ref.Data,Vol.33,No.1,2004
66 IUPAC-NIST SOLUBILITY DATASERIES
ponent 1! is the solute, and the second ~component 2 for a 5. Solvent mole fraction of sYubstance 1, xv,1:
two-component system! is the solvent. The reader should p
(
bear these distinctions in nomenclature in mind when com- xv,15x1 xs. ~8!
s51
paring equations given here with those in the Green Book.
1. Mole fraction of substance 1, x or x~1! ~condensed Here, p is the number of solvent components in the mixture.
1
phases!, y ~gases!: Y Solvent mass fraction of substance 1, wv,1, is defined analo-
1
c gously.
(
x 5n n ~1!
1 1 s 6. Molality of solute 1 in a solvent 2, m :
s51 1
m 5n /n M ~9!
wheren istheamountofsubstanceofs,andcisthenumber 1 1 2 2
s
of distinct substances present ~often the number of thermo- SI base units: molkg21. Here, M is the molar mass of the
2
dynamic components in the system!. Mole percent of sub- solvent.
stance 1 is 100 x .
1 7. Aquamolality, Solvomolality of substance 1 in a mixed
2. Ionic mole fractions of salt i, xi1, xi2: For mixture of solvent with components 2, 3,13 m1(3):
s binary salts i, each of which ionizes completely into ni1 m~3!5m M¯ /M ~10!
cations and vi2 anions, with vi5vi11vi2 and a mixture of 1 1 3
p nonelectrolytes k, of which some may be considered as SIbaseunits:molkg21.Here,theaveragemolarmassofthe
solvent components, a generalization of the definition in solvent is
Robinson and Stokes10 gives: M¯ 5x M 1~12v !M ~11!
v,2 2 v,2 3
x1i5 (sv1ix1i , x2i5v2vi1xi1i i51...s ~2! atenrdmxivs,uissedthmeossotlfvreenqtuemnotllyeifnradcitsicounssoifngcocmompopnaeranttiv2e.sTohluis-
11 ~v 21!x
j51 j j bilities in water ~component 2! and heavy water ~component
3! and in their mixtures.
x
x 5 j , k5~s11!...c. ~3! 8. Amount concentration of solute 1 in a solution of vol-
ok s
( ume V, c :
11 ~v 21!x 1
j51 j j c15@formula of solute#5n1/V ~12!
The sum of these mole fractions is unity, so that, with c5s SI base units: molcm23. The symbol c1 is preferred to @for-
1p, mula of solute#, but both are used. The old terms molarity,
(s (c molar and moles per unit volume are no longer used.
i51 ~x1i1x2i!1i5s11 xoi51. ~4! 9. Mass concentration of solute 1 in a solution of volume
V, r:
General conversions to other units in multicomponent sys- 1 r5g /V5c M /V ~13!
tems are complicated. For a three-component system con- 1 1 1 1
taining nonelectrolyte 1, electrolyte 2, and solvent 3, SI base units: kgm23.
10. Mole ratio, r ~dimensionless!:9
x15v122v~1v22x2o11!x12 x25v122~xv1222 1!x12. ~5! A,B rn,125n1/n2. ~14!
Mass ratio, symbol z , may be defined analogously.9
Theserelationsareusedinsolubilityequationsforsalts,and A,B
for tabulation of salt effects on solubilities of gases. 11.Ionicstrength,I ~molalitybasis!,orI ~concentration
m c
3. Mass fraction of substance 1, w or w~1!: basis!:
Y 1 1( 1(
w 5g (c g ~6! Im52 i mizi2, Ic52 i cizi2 ~15!
1 1 s
s51 wherez isthechargenumberofioni.Whilethesequantities
i
where g is the mass of substance s. Mass percent of sub- arenotusedgenerallytoexpresssolubilities,theyareusedto
s
stance 1 is 100 w . The equivalent terms weight fraction, expressthecompositionsofnonsaturatingcomponents.Fora
1
weight percent and g(1)/100g solution are no longer used. single salt i with ions of charge numbers z1 and z2,
4. Solute mole fraction of substance 1, x : Im5uz1z2uvmi, Ic5uz1z2uvci. ~16!
Y Y v,1
c8 c8 Moleandmassfractionsandmoleratiosareappropriateto
( (
xs,15m1 ms5x1 xs ~7! either the mixture of the solution point of view. The other
s51 s51
quantities are appropriate to the solution point of view only.
where c8 is the number of solutes in the mixture. These Conversions between pairs of these quantities can be carried
quantities are sometimes called Ja¨necke mole ~mass! out using the equation given in Table 1 at the end of this
fractions.11,12 Solute mass fraction of substance 1, w , is Introduction. Other useful quantities will be defined in the
s,1
defined analogously. prefaces to individual volumes or on specific data sheets.
J.Phys.Chem.Ref.Data,Vol.33,No.1,2004
JIRI HA´LA 77
TABLE1. Interconversionsbetweenquantitiesusedasmeasuresofsolubilitiesc-componentsystemscontainingc-1solutesiandsinglesolventc~r—density
ofsolution;M—molarmassesofi.Forrelationsfortwo-componentsystems,setsummationsto0.!
i
x w m c
i i i i
H 1 J 1 1
S D S D S D
xi5 xi M 1 (c21 M w 1 (c21 m 1 r (c21c M
11 i 211 c21 j 11 1 j 11 2M 1 j 12 j
Mc wi j(cid:222)1 Mj wi miMc j(cid:222)i mi Mc ci i j(cid:222)i ci Mc
H 1 S D J S 1 D ciMi
wi5 M 1 (c21 M x wi 1 (c21 r
11 c 211 j21 j 11 11 mM
Mi xi j(cid:222)i Mc xi miMi j(cid:222)i j j
S 1 D S 1 D S 1 D
mi5 1 (c21x 1 (c21w mi 1 (c21
M 212 j M 212 j r2 cM 2M
c xi j(cid:222)i xi i wi j(cid:222)i wi ci j(cid:222)i j j i
H r S D J rwi S r D
ci5 M1M 1211(c21 Mj21 xj Mi 1 11(c21mM 1M ci
i c xi j(cid:222)i Mc xi mi j(cid:222)i j j j
Salt hydrates are generally not considered to be saturating based on established thermodynamic methods. Specific pro-
componentssincemostsolubilitiesareexpressedintermsof cedures used in a particular volume will be described in the
the anhydrous salt. The existence of hydrates or solvates is Preface to this volume.
noted carefully in the critical evaluation.
Mineralogical names are also quoted, along with their CA
RegistryNumbers,againusuallyinthetextandCARegistry 2.4 References for the Introduction
Numbers ~where available! are given usually in the critical
evaluation. 1E.A.Hill,J.Am.Chem.Soc.22,478~1900!.
In addition to the quantities defined above, the following 2IUPAC Commission onAtomic Weights and IsotopicAbundances, Pure
Appl.Chem.63,975~1989!.
are useful in conversions between concentrations and other
3I.Millsetal.,eds.Quantities,UnitsandSymbolsinPhysicalChemistry
quantities. ~theGreenBook!~BlackwellScientificPublications,Oxford,U.K.,1993!.
12. Density, r: 4H.H.Ku,p.73;C.Eisenhart,p.69;inH.H.Ku,ed.,PrecisionMeasure-
(c ment and Calibration, NBS Special Publication 300 ~NBS,Washington,
r5g/V5 r ~17! 1969!,Vol.1.
s
s51 5V. Gold etal., eds., Compendium ofAnalytical Nomenclature ~the Gold
Book!~BlackwellScientificPublications,Oxford,U.K.,1987!.
SIbaseunits:kgm23.Heregisthetotalmassofthesystem. 6H.FreiserandG.H.Nancollas,eds.,CompendiumofAnalyticalNomen-
13.Relativedensity,d5r/r°: theratioofthedensityofa clature ~the Orange Book! ~Blackwell Scientific Publications, Oxford,
U.K.,1987!,Sect.9.1.8.
mixture at temperature t, pressure p to the density of a ref- 7ISO Standards Handbook, Quantities and Units ~International Standards
erence substance at temperature t8, pressure p8. For liquid Organization,Geneva,1993!.
solutions, the reference substance is often water at 4°~C!, 1 8GermanStandard,DIN1310,ZusammensetzungvonMischphasen~Beuth
bar.~Insomecases1atmisusedinsteadof1bar.!Theterm Verlag,Berlin,1984!.
9T.Cvitasˇ,Chem.International17,123~1995!.
specific gravity is no longer used. 10R.A.RobinsonandR.H.Stokes,ElectrolyteSolutions,2nded.~Butter-
worths,London,1959!.
ThermodynamicsofSolubility 11E.Ja¨necke,Z.Anorg.Chem.51,132~1906!.
12H.L.Friedman,J.Chem.Phys.32,1351~1960!.
Thermodynamic analysis of solubility phenomena pro- 13J. W. Lorimer, in Alkali Metal and Ammonium Chlorides in Water and
vides a rational basis for the construction of functions to Heavy Water (Binary Systems), edited by R. Cohen-Adad, and J. W.
represent solubility data, and thus aids in evaluation, and Lorimer,IUPACSolubilityDataSeries,Vol.47~Pergamon,Oxford,U.K.,
1991!,p.495.
sometimesenablesthermodynamicquantitiestobeextracted.
Both these aims are often difficult to achieve because of a Thissectionwaswrittenby:
lack of experimental or theoretical activity coefficients. R.Cohen-Adad J.W.Lorimer
Where thermodynamic quantities can be found, they are not Villeurbanne,France London,Ontario,Canada
M.Salomon M.-T.Saugier-CohenAdad
evaluated critically, since this task would involve examina-
SeaBright,N.J.,USA Villeurbanne,France
tion of a large body of data that is not directly relevant to
December,1995
solubility. Where possible, procedures for evaluation are
J.Phys.Chem.Ref.Data,Vol.33,No.1,2004
88 IUPAC-NIST SOLUBILITY DATASERIES
Components:OriginalMeasurements:@#~!A.P.RolletandJ.Wohlgemuth,Compt.Rend.199,1772–4;19597-69-41Lithiumazide;LiN3@#~!~!O;7732-18-51934.2Water;H2 Variables:PreparedBy:´Temperatureandcomposition.J.Hala ExperimentalDataaPhasediagramoftheLiN–HOsystem32 LiNSignificantTemperatureLiN332bc1(100w/mass%)(m/molkg)Solidphasepoint(t/°C)11 2661E47.50.526.00.47.176AB266131.00.533.50.310.29BCT166168.20.148.00.318.85CDT2 a~!ResultswerepresentedingraphicalformFig.1.Numericalvalueswerereportedforthreesignificantpointsinthephasediagram.bCalculatedbycompiler.c@#@#@#@#A:Ice;HO;7732-18-5;B:LiN4HO;;C:LiNHO;34204-05-2;D:LiN;19597-69-4.232323(cid:149)(cid:149) @~!~!F.1.PhasediagramoftheLiN–HOsystemfullcirclespolythermalmeasurements,opencirclesisothermalmeasurements,IG321#~!includedbyauthors.trianglesdatafromCurtiusandRissom,
3.TheSolubilityofAzides 3.1.LithiumAzide Components:OriginalMeasurements:@#~!~!;19597-69-4T.CurtiusandJ.Rissom,J.Prakt.Chem.58,261–3091898.1Lithiumazide;LiN3~!2Solvents Variables:PreparedBy:´T/K:283–289J.Hala ExperimentalDataainwaterorethanolatdifferenttemperaturesSolubilityofLiN3 TemperatureLiNLiN332b!1Solvent(t/°C)(g/100gsolvent(m/molkg)1 @#Water;HO;7732-18-51036.127.377215.562.0712.681666.4113.56@#HO;64-17-51620.264.14Ethanol;C26 aSolidphaseswerenotinvestigated.bCalculatedbycompiler. inwatershowedalkalinereaction.Additionalinformation:SaturatedsolutionsofLiN3 AuxiliaryInformation MethodApparatusProcedure:SourceandPurityofMaterials:(cid:213)(cid:213)~waspreparedfromLiSOandBaN)ascolorlessLiNAnisothermalmethodwasused.Excesssaltwaskeptin32432hygroscopiccrystals.Theproductwasrecrystallizedfromwater,contactwiththesolventforseveralweeksunderoccasionalSOinandanalyzedafterprolongeddryingoverconcentratedHstirringinaroomwithconstanttemperature.Equilibrium24avacuumdesiccator.Found/calculatedforLiN(%):N85.67–temperaturewasmeasuredinthesaturatedsolutionsprior386.02/85.71,Li14.09–14.18/14.29.Thebariumazideusedwaswithdrawalofthesamples.Aweighedamountofthesaturated~in8%aqueoussolutionofpreparedbydissolvingBaOH)solutionwasthenevaporatedinaplatinumdish,anddriedina2.ThelatterwasobtainedbydistillationwithdiluteHSOHNdessicatoruntilconstantweightwasattained.3241~ofeitherPbN)orNHNaccordingtoCurtius.Purityof3243waternotspecified.Absoluteethanolwasused. EstimatedError:Temperature:notreported.Solubility:insufficientdatagiventoallowforerrorestimate. References:1~!T.Curtius,Ber.24,33411891.
J.Phys.Chem.Ref.Data,Vol.33,No.1,2004
JIRI HA´LA 99
3.2.SodiumAzide Components:OriginalMeasurements:@#~!~!;26628-22-8T.CurtiusandJ.Rissom,J.Prakt.Chem.58,261–3091898.1Sodiumazide;NaN3~!2Solvents Variables:PreparedBy:´T/K:283–290J.Hala ExperimentalDataainwaterorethanolatdifferenttemperaturesSolubilityofNaN3 TemperatureNaNNaN332b!1(t/°C)Solvent(g/100gsolvent(m/molkg)1 @#Water;HO;7732-18-51040.166.178215.240.76.2611741.76.414@#HO;64-17-5160.31530.0485Ethanol;C26 aSolidphaseswerenotinvestigated.bCalculatedbycompiler. inwatershowedalkalinereaction.Additionalinformation:SaturatedsolutionsofNaN3 AuxiliaryInformation MethodApparatusProcedure:SourceandPurityofMaterials:(cid:213)(cid:213)waspreparedbyneutralizing8%aqueoussolutionofHNNaNAnisothermalmethodwasused.Excesssaltwaskeptin33withNaOH.Thesolutionoftheacidwasobtainedbydistillationcontactwiththesolventforseveralweeksunderoccasional~SOofeitherPbN)orNHNaccordingtowithdiluteHstirringinaroomwithconstanttemperature.Equilibrium2432431Curtius.NaNwasrecrystallizedfromwater,anddriedovertemperaturewasmeasuredinthesaturatedsolutionsprior3SOinavacuumdessicator.Analysis,found/concentratedHwithdrawalofthesamples.Aweighedamountofthesaturated24~!calculatedforNaN%:Na35.31–35.35/35.38.Purityofwatersolutionwasthenevaporatedinaplatinumdish,anddriedina3notspecified.Absoluteethanolwasused.desiccatoruntilconstantweightwasattained. EstimatedError:Temperature:notreported.Solubility:insufficientdatagiventoallowforerrorestimate. References:1~!T.Curtius,Ber.24,33411891.
~!1898.
261
nformation SourceandPurityofMaterials:Nodetailsreported. EstimatedError:6~!Temperature:0.1–0.5Kauthors.6~!Solubility:100w:0.3%–0.4%authors.1 References:1T.CurtiusandJ.Rissom,J.Prakt.Chem.58,
I
Auxiliary MethodApparatusProcedure:(cid:213)(cid:213)Freezingcurvewasobtainedbypolythermalmethod.Thesolubilitycurvewasobtainedbyisothermalmethod.Excesssaltwasequilibratedwithwaterinathermostatfor1dayinclosedvessels.Inthesaturatedsolutions,azidewas,andsubsequentlydeterminedprecipitatedwithAgNO3gravimetricallyasAgCl,lithiumwasdeterminedSO.CoolingcurveswereobtainedbygravimetricallyasLi24polythermalmethod,thetimenecessarytoreachequilibriumwasnotspecified.Itwasstatedthatequilibriumwasattainedveryslowly,andthatthesystemsshowedconsiderabletendencytosupersaturationevenwheninoculated.
J.Phys.Chem.Ref.Data,Vol.33,No.1,2004
1100 IUPAC-NIST SOLUBILITY DATASERIES
estimate. ~!58,2611898.
nformation SourceandPurityofMaterials:Nodetailsreported. EstimatedError:Insufficientdatareportedtoallowforerror References:1T.CurtiusandJ.Rissom,J.Prakt.Chem.
I
Auxiliary MethodApparatusProcedure:(cid:213)(cid:213)Thefreezingcurvewasobtainedbypolythermalmethod.Thesolubilitycurvewasobtainedbyisothermalmethod.Excesssaltwasequilibratedwithwaterinathermostatfor1dayinclosedvessels.Insamplesofthesaturatedsolutions,azidewas,andsubsequentlydeterminedprecipitatedwithAgNO3gravimetricallyasAgCl,sodiumwasdeterminedSO.CoolingcurveswereobtainedbygravimetricallyasNa24polythermalmethod.Equilibriumtimewasnotspecified.
)NaN3 m. ments;
Components:OriginalMeasurements:~!@#~!J.Wohlgemuth,Compt.Rend.198,601–31934.;26628-22-81Sodiumazide;NaN3@#~!O;7732-18-52Water;H2 Variables:PreparedBy:´TemperatureJ.Hala ExperimentalData TemperatureNaNNaN332c1(t/°C)(100w/mass%)(m/molkg)Note11 212026.85.63metastableeutecticpoint(ice215.121.64.24eutecticpoint22.127.85.92transitionpoint0285.9810035.68.50 a~!ResultswerepresentedingraphicalformFig.2.Numericalvalueswerereportedforfivesignificantpointsinthephasediagrab@#22@#2SolidphaseswerereportedtobeNaN3HO,,between15.1°Cand2.1°C,andNaN,26628-22-8,above2.1°C.323(cid:149)cCalculatedbycompiler. @~!~!F.2.PhasediagramoftheNaN–HOsystemfullcirclespolythermalmeasurements;opencirclesisothermalmeasureIG321~!#trianglesdatafromCurtiusandRissom,includedbytheauthor.
J.Phys.Chem.Ref.Data,Vol.33,No.1,2004