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Applications of Solubility Data
Applications of Solubility Data
Solubility data have many interesting and important ap- One of the earliest applications of gas solubilities pertains
plications in science and technology. For example chemical to diving. The affliction is known as “bends”. This occurs when a
engineers involved with the design of systems for chemical diver goes rapidly from deep water (high pressure) to the surface
separation and purification processes rely heavily on solubility (lower pressure). The rapid decompression causes air, dissolved
data for their calculations. Civil engineers require solubility in blood and other body fluids, to bubble out of solution. These
data to design water treatment facilities to remove hazardous bubbles impair blood circulation and affect nerve impulses. As
chemicals from supplies of drinking water. Drug solubility is a helium is much less soluble than nitrogen, to minimize the ef-
vital parameter for controlling solubility in the blood stream and fects of “bends”, mixtures of helium and oxygen are now used in
various body fluids to facilitate drug delivery systems. When se- diving tanks, so that much less gas comes out of solution upon
lecting solvent systems for chemical reactions chemists examine decompression.
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both the reactant and product solubilities. The fate of chemical One important application is in the control and study of
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pollutants in the environment is partially explained by a careful pollution. Solubilities of pollutant gases are of special interest at
analysis of solubility data. the present time. One method of scrubbing effluent gas streams
Also over the past decade or so several models have been is to dissolve noxious gases in a suitable solvent. The variation of
advanced to predict solubility (1–3). Those concerned with solubility with temperature as well as the absolute value of the
solution thermodynamics utilize solubility data to test the ap- solubility is important in such applications if the solvent is to
plications, predictive ability, and limitations of some of these be regenerated by heating. The understanding of the behavior
models. At the undergraduate level students are exposed to of pollutant gases in the atmosphere requires a knowledge of
solubility in a peripheral way in several laboratory experiments solubilities at very low partial pressures in fresh water and in sea
by the need to get materials into solution prior to analysis. Some water, in the presence of other gases.
physical chemistry laboratory courses include an experiment on Many gases have anesthetic properties. These depend, to
solubility as a function of temperature (4) or the determination a large extent, upon solubilities in body fluids. Even xenon has
of a solubility product constant, Ksp. Solubility processes are been shown to cause anesthesia (19, 20). The understanding of
also important for the teaching of analytical chemistry (5). The the behavior of anesthetics in common use and the search for
information discussed in this article could possibly be a useful new anesthetics requires accurate information on the solubilities
resource for instructors of introductory, qualitative, quantitative, in water and in body fat (21, 22). The solubility of a gas in olive
and environmental chemistry courses. Solubility data are used oil is always close to that in animal fat under the same conditions
to create or understand qualitative and quantitative analysis of temperature and pressure. The solubility of a gas in olive oil has
schemes that students use in laboratory classes. been investigated for potential medical interest (23–25). Two new
The American Chemical Society publication ChemMatters inhalation anesthetics introduced in the 1990s that are in current
has included an interesting application of solubility for use in use are desflurane and sevoflurane (26).
teaching at different levels. The example on aquarium chemistry Gas solubilities have also found application in the formula-
focuses on the importance of dissolved oxygen, salinity, and am- tion of artificial blood or blood substitutes. For example using
monia, nitrite, and nitrate concentrations (6). the fact that oxygen has a high solubility in perfluorinated
A recent publication presents a comprehensive treatment hydrocarbons has led to the use of these solvents as blood sub-
on the experimental determination of solubilities and includes stitutes (27–29).
some discussion on applications of solubility data (7). Several A number of gas–solvent systems have now been studied
other publications have focused on experiments involved with to pressures far exceeding barometric pressure. The variation
solubility and thermodynamics, the determination of enthalpies of solubility with pressure of some gases such as ammonia,
of solution from solubility measurements, and an understand- hydrogen sulfide, and sulfur dioxide have been studied below
ing of solubility products (8–12). This article will review some their critical temperatures over much of the possible concentra-
of the applications of solubility data that are important for the tion range. In some cases mole fraction solubility has ranged
practicing engineer and scientist. from zero to one with a variety of non-linear variations of mole
fraction solubility with pressure. A knowledge of the solubility
Gas Solubilities of ammonia at high pressures is important in designing new
integrated ammonia and urea processes (30).
The solubilities of gases in liquids has been studied for As the solubility of a particular gas depends upon both
over a hundred and fifty years and many measurements are temperature and pressure, confusion may arise from the various
recorded in the literature. This topic is of particular inter- ways in which such solubilities are reported. There are, in addi-
est to ecologists and environmentalists. Water quality is tion, sometimes serious discrepancies between measurements
frequently measured by dissolved oxygen (13, 14) and this is by one group of workers and another group because it may be
determined by measuring the quantity of oxygen dissolved in difficult to establish thermodynamic equilibrium between a
natural waters. Dissolved oxygen also plays a role in sewage gas phase and a liquid phase in an apparatus for measuring gas
treatment (15–18). solubilities (7).
310 Journal of Chemical Education • Vol. 85 No. 2 February 2008 • www.JCE.DivCHED.org • © Division of Chemical Education
Research: Science and Education
When apparently reliable gas solubility data are applied dioxide in various aqueous solutions of certain salts or organic
to an industrial problem it must be borne in mind that, in the compounds is essential for the design and operation of flue gas
application under consideration, equilibrium may not exist treating equipment. There has been a dearth of information to
between the gas and liquid phase. A detailed discussion of the indicate which solvents or mixed solvent solutions would effec-
thermodynamic equilibrium of the gas and liquid phases is tively remove the sulfur dioxide pollutant to an acceptably low
presented in a recent text (31). concentration on a cost-effective basis (42). Thus a good deal of
A basic question of concern to environmental scientists as research effort is still involved with the solubility determinations
well as individuals and organizations responsible for environ- of sulfur dioxide in various potential solvents.
mental management is what happens to pollutants once they are Another area of concern to those involved in waste treat-
released. One general approach to answering questions about the ment facilities is that of the possible volatilization of pollutants
fate of pollutants is environmental modeling. For this, box mod- from biological treatment facilities (43). The rate at which a
els (32–35) are often used in which the environment is thought compound volatilizes from the liquid phase is proportional to
of as a collection of boxes or compartments (lake, atmosphere, the difference between (i) the partial pressure of the compound
soil, ocean, etc. as appropriate for the environment being mod- in the gas phase and (ii) the partial pressure that the compound
eled). The boxes are then connected by equations that describe would have in the gas phase if the state of equilibrium existed
the rates of production and destruction of pollutant in each between the two phases. The proportionality constant is de-
box and the rates of pollutant transfer between boxes. A model termined by the mass transfer characteristics of a given instal-
can then be “run” by specifying initial quantities of pollutant in lation.
each box and calculating pollutant distributions at later times. Many of the organic priority pollutants are hydrophobic
Many models, both simple and complex, of this sort have been compounds with large activity coefficients. As a result, these
created and used to predict the fate of pollutants. Obviously, the compounds will attempt to leave the aqueous phase at the first
usefulness of these models is strongly dependent on the accuracy opportunity. If the vapor pressure is sufficient, the compound
of the rate equations that connect the boxes. will volatilize from an aerated reactor. If the vapor pressure is
In assessing the fate of pollutants from marine and aquatic very low, the compound will attach itself to any available surface
oil spills, one of the important transfer processes that must be (e.g., biomass or reactor walls). Aerobic biological treatment
considered is between water and the atmosphere. Such evapora- then becomes a race between the rate of biodegradation and the
tion rates may need to be known for many different pollutants at rate of other removal mechanisms.
a variety of temperature conditions and are difficult to measure
directly. Fortunately, a method has been described for estimating Selective Solvation in Mixed Solvents
the rate of evaporation of slightly soluble contaminants from
water to the atmosphere (36). At any temperature for which Selective solvation of the ions of an electrolyte by the
the aqueous solubility and vapor pressure of a slightly soluble components of a binary mixed solvent profoundly affects (44,
pollutant are known, the ratio of evaporation rates for water 45) its solubility. Most often, when a salt is heteroselectively
and the pollutant from a saturated solution or dispersion can solvated by the constituents of a mixed solvent, its solubility
be calculated. Since considerable solubility data are available will be higher (46) in mixtures of the two solvents than in the
for binary systems of hydrocarbons in water, evaporation rates pure solvent components. In many cases, the solubility has been
for single hydrocarbons from water can be estimated. Extending observed to pass through a maximum value at an intermediate
this approach to multi-component systems such as petroleum in composition of the mixed solvent. Several examples of enhanced
water is also possible since it has been shown that binary system solubility of salts such as Ag2SO4 in water–acetonitrile, Ag2SO4
data can be used to predict multi-component system data with in methanol–dimethylsulfoxide, and AgBrO3 in methanol–
an error of 15% or less (37). acetonitrile have been reported.
Another important application is the removal of toxic, Parker et al. (47) have shown that the solubility of Ag2SO4
sulfur-containing gases from petroleum products and flue gases in water containing 150 g∙L of 3-hydroxy propionitrile and 140
from furnaces and metallurgical processes (38). Even at low g∙L H2SO4 at 25 °C is 0.25 M as compared to 0.07 M in pure
concentrations the sulfur-containing compounds, hydrogen water; that is, Ag2SO4 is much more soluble in acidic aqueous
sulfide and sulfur dioxide, are extremely corrosive to many met- solutions containing organic nitriles and H2SO4. Further, Gibbs
als and alloys (39) and extremely toxic to plant and animal life. transfer energy measurements reveal that the silver ion is pref-
As elsewhere, in North America many tons per day of these gases erentially solvated by the nitrile and SO42− by water and these
are removed by appropriate gas treatment units in an effort to results do not depend upon acidity up to pH 3. These observa-
maintain a clean environment. The sources of hydrogen sulfide tions formed the basis (47) for suggesting an improved method
or other sulfur-containing compounds are the crude oil, natural of electro refining silver over the conventional method. Conven-
gas, or tar sand bitumen that are subsequently processed and tionally, silver is refined from a solution of silver nitrate of low
refined to produce a host of petroleum products. The processes acidity at high current density in a Thum or Moebius Cell. The
for the removal of hydrogen sulfide are relatively well-established silver deposit on the cathode is dendritic, non-adherent, and of
and relatively successful. On the other hand, sulfur dioxide from moderate purity and the electrolysis involves significant energy
processes such as the combustion of coal or roasting of sulfur- consumption. These disadvantages are absent in electrolysis
bearing ores is produced in immense quantities (40). Although involving the new Ag2SO4–H2SO4 bath containing about 45
treatment facilities for flue gases are generally available (41), g∙L of Ag+ as sulfate (which is below the saturation solubility
much more needs to be done to control the incidence of the under these conditions), 140 g∙L of H2SO4, and 150 g∙L of
resulting “acid rain”. A knowledge of the solubilities of sulfur the nitrile.
© Division of Chemical Education • www.JCE.DivCHED.org • Vol. 85 No. 2 February 2008 • Journal of Chemical Education 311
Research: Science and Education
Solubility studies of gypsum (CaSO4⋅2H2O) in the pres- Applications in the Power Industry
ence of different substances such as urea (48) or farmyard ma-
nure (49), which are known to enhance its solubility in water, For nuclear power stations it is necessary to provide infor-
are particularly relevant in the field of agricultural chemistry. mation about the solubility of Ar, Kr, Xe, N2, and H2 in light
The increased solubility of gypsum in urea solutions, which is and heavy water over a wide temperature range (67, 68). This
about five times that in pure water, is attributed to the forma- information is necessary for various reasons: (i) Solubility data
tion of a complex, CaSO4⋅4CO(NH2)2, whereas the chelating for Kr and Xe are needed to optimize the working conditions
ability of Ca2+ ions with the organic materials in farmyard for the early detection of fuel element failure based on degassing
manure leads to an increase in solubility. There is evidence to samples of the coolant to detect the presence of these gaseous fis-
show that the addition of gypsum improves (49) the quality of sion products. (ii) Ar solubility is necessary to evaluate possible
alkaline soils that in turn results in an increase of crop yields. It oxygen in-leakage from air using a mass-balance model (69). (iii)
is noteworthy that urea, which is a nitrogenous fertilizer of the N2 and H2 solubilities are necessary to know precisely that the
highest nitrogen content (46.7%), is of limited utility because coolant and moderator are under reducing conditions according
of its hygroscopic nature whereas the gypsum–urea complex is to specifications. Such problem areas require a careful survey and
more suitable as a fertilizer because of its weaker hygroscopicity subsequent critical evaluation of available literature data.
compared to that of urea. For the steam–water cycle of power plants (70) it is neces-
sary to have data for the solubility of CO2 at different alkaline
pHs to know the local concentration of this species in various
Solubility Data and Phase Diagrams components of the steam–water cycle. A critical literature survey
in Industrial Processes shows data are fairly thorough. This helps to optimize working
Solubility data are used in almost all industrial treatments conditions and to improve the designs of some auxiliary systems
involving separation, extraction, purification, and crystallization. for a new plant.
Useful thermodynamic information can also be derived from Information is also needed for the solubility of CaSO4
solubility data (50). A knowledge of solubility and a reason- at high temperatures, as it relates to scale formation in boilers
able model for its behavior often permit the extrapolation of and in steam generator tubings (71). The available data show a
solubility behavior into pressure and temperature ranges where discrepancy between experimental and recommended values of
solubility data are not available. The different unit operations three orders of magnitude at 573 K. A careful thermodynamic
used in industry such as the addition of reactants, evaporation evaluation of the data and the procedures of calculation elimi-
and dilution, purification to given specifications can be simu- nated this discrepancy and it was possible to recommend a value
lated quantitatively by graphical displacements using solubility of the solubility supported both experimentally and theoreti-
data diagrams. cally. The values of high temperature solubility were of impor-
From solubility data, the mass balance of each operation can tance in preparing specifications for feed water purity starting
often be deduced. Furthermore, if additional data on enthalpies from fresh water available in the plant site, thus minimizing the
of reaction or enthalpies of dilution are available, an energy bal- risk of scale formation.
ance and, in some instances, a cost balance can be derived. Flow
sheets for processes can be constructed and optimized. Process Solubilities of Oxides and Hydroxides
parameters such as amounts of reactants, types of reactors, fluid of Copper, Silver, Gold, Zinc, Cadmium, and Mercury
flow and heat flow behavior, material recycling, and the like can
be calculated (51). Solubility data on oxides and hydroxides are of interest to
In industry, several techniques are closely related to solubil- manufacturers of batteries (72, 73). The oxides of silver, zinc,
ity behavior. A knowledge of such behavior and the use of such cadmium, and to some extent copper are used in several battery
information by means of phase diagrams can often enhance systems. In such systems the oxides are soluble to some extent in
product recovery. Some of the more common techniques are the electrolytes. The degree of solubility is an important factor
in the behavior and understanding of the electrode processes.
• distillation (52, 53) The mechanism of the electrode reactions is interpreted in terms
• fractional crystallization (54, 55) of the solubilities of the oxides and hydroxides. Therefore, the
• zone melting (56) solubility data are of use in the design of battery systems and
their applications in different environments.
Others, less usual, are A second area where oxide and hydroxide data are of value
• supercritical extraction (57–59) is in the practice of the winning of metals from their ores (74).
• zone crystallization (50) Some of the processes that are used involve the leaching of the
oxides of the metals and therefore solubility data are of impor-
• multiphase component partitioning (51) tance in the operation of such processes.
In some cases, the process itself can be improved or redesigned The third area has to do with recent concerns about the
from the knowledge of solubility behavior. For example, such is environment (75). The oxides and hydroxides of many of the
true for processes involving metals cited above are components of throw-away items, for
• lyophilization (60–62) example, small batteries used in hearing aids, watches, and so
forth. The metals are heavy metals and toxic. As components
• hydrothermal synthesis (63, 64) of waste they can enter the environment by means of solubility
• crystal growth (65–66) processes.
312 Journal of Chemical Education • Vol. 85 No. 2 February 2008 • www.JCE.DivCHED.org • © Division of Chemical Education
Research: Science and Education
A large quantity of solubility data for alkaline earth metal current flow 1–100 kA
halates and alkali metal halates has already been published (76,
77). Halate compounds are used widely in pure and applied
á ź
chemistry. Potassium iodate is used as the titrant for iodometric
titrations, and the titration is used to determine the solubilities
of alkali, alkaline earth, transition, and rare earth metal iodates. Cl2 gas H2 gas
Important practical applications of halates include their use in evolved evolved
pyrotechnic production and in the paper pulp industry for the
generation of the bleaching agent chlorine dioxide. The elec- anode cathode
trolysis process for the production of sodium chlorate is due
to Krebs and Co. Before the development of coated titanium solution
anodes the cells employed graphite electrodes. With the intro- NaCl: 70–310 g/L
duction of activated titanium anodes it was possible to improve NaClO3: 0–650 g/L
the efficiency of the process. The essential basic components in a NaOCl: 1–6 g/L
typical chlorate cell system (78) are illustrated in Figure 1. Na2Cr2O7: 0.5–7 g/L
The principal overall chemical reaction in a chlorate cell temperature: 30–90 °C
is given by pH : 5.5–7.0
NaCl 3H2O NaClO3 3H2 (1) Figure 1. Simple chlorate cell (redrawn and used with permission
from ref 78).
Equation 1 is an extremely simplistic expression of a series of
desirable reactions that occur in a chlorate cell and ignores a
number of undesirable reactions. When the purified brine is
electrolyzed, chlorine is formed at the anode and caustic soda
and hydrogen are formed at the cathode (78–81):
Cathode: 2H2O 2e
H2 2OH (2)
The actual formation of chlorate takes place outside the cell ac-
cording to the overall equation (77–80)
Figure 2. Isothermal diagram of solubility for ternary NaClO3–NaCl–
2HClO ClO H2O system (used with permission from ref 84).
3 2H 2Cl
ClO (6)
© Division of Chemical Education • www.JCE.DivCHED.org • Vol. 85 No. 2 February 2008 • Journal of Chemical Education 313
Research: Science and Education
314 Journal of Chemical Education • Vol. 85 No. 2 February 2008 • www.JCE.DivCHED.org • © Division of Chemical Education
Research: Science and Education
Solubility of Bromine 5. Skoog, D.; West, D. M.; Holler, F. J.; Crouch, S. R. Fundamentals
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