Supersaturation

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In physical chemistry, supersaturation occurs with a solution when the concentration of a solute exceeds the concentration specified by the value of solubility at equilibrium. Most commonly the term is applied to a solution of a solid in a liquid, but it can also be applied to liquids and gases dissolved in a liquid. A supersaturated solution is in a metastable state; it may return to equilibrium by separation of the excess of solute from the solution, by dilution of the solution by adding solvent, or by increasing the solubility of the solute in the solvent.

Contents

History

Solubility of Na2SO4 in water as a function of temperature. Na2SO4 solubility.svg
Solubility of Na2SO4 in water as a function of temperature.

Early studies of the phenomenon were conducted with sodium sulfate, also known as Glauber's Salt because, unusually, the solubility of this salt in water may decrease with increasing temperature. Early studies have been summarised by Tomlinson. [1] It was shown that the crystallization of a supersaturated solution does not simply come from its agitation, (the previous belief) but from solid matter entering and acting as a "starting" site for crystals to form, now called "seeds". Expanding upon this, Gay-Lussac brought attention to the kinematics of salt ions and the characteristics of the container having an impact on the supersaturation state. He was also able to expand upon the number of salts with which a supersaturated solution can be obtained. Later Henri Löwel came to the conclusion that both nuclei of the solution and the walls of the container have a catalyzing effect on the solution that cause crystallization. Explaining and providing a model for this phenomenon has been a task taken on by more recent research. Désiré Gernez contributed to this research by discovering that nuclei must be of the same salt that is being crystallized in order to promote crystallization.

Occurrence and examples

Solid precipitate, liquid solvent

Crystallized sugar (rock candy) is made by adding a seed crystal to a supersaturated solution of table sugar and water. The multiple crystals on the right were grown from a sugar cube, while the left was grown from a single seed taken from the right. A red dye was added to the solution for the left crystal, but was insoluble with the solid sugar, and only traces remain while the rest precipitated out. Crystallized sugar, multiple crystals and a single crystal grown from seed.jpg
Crystallized sugar (rock candy) is made by adding a seed crystal to a supersaturated solution of table sugar and water. The multiple crystals on the right were grown from a sugar cube, while the left was grown from a single seed taken from the right. A red dye was added to the solution for the left crystal, but was insoluble with the solid sugar, and only traces remain while the rest precipitated out.

A solution of a chemical compound in a liquid will become supersaturated when the temperature of the saturated solution is changed. In most cases solubility decreases with decreasing temperature; in such cases the excess of solute will rapidly separate from the solution as crystals or an amorphous powder. [2] [3] [4] In a few cases the opposite effect occurs. The example of sodium sulfate in water is well-known and this was why it was used in early studies of solubility.

Recrystallization [5] [6] is a process used to purify chemical compounds. A mixture of the impure compound and solvent is heated until the compound has dissolved. If there is some solid impurity remaining it is removed by filtration. When the temperature of the solution is subsequently lowered it briefly becomes supersaturated and then the compound crystallizes out until chemical equilibrium at the lower temperature is achieved. Impurities remain in the supernatant liquid. In some cases crystals do not form quickly and the solution remains supersaturated after cooling. This is because there is a thermodynamic barrier to the formation of a crystal in a liquid medium. Commonly this is overcome by adding a tiny crystal of the solute compound to the supersaturated solution, a process known as "seeding". Another process in common use is to rub a rod on the side of a glass vessel containing the solution to release microscopic glass particles which can act as nucleation centres. In industry, centrifugation is used to separate the crystals from the supernatant liquid.

Some compounds and mixtures of compounds can form long-living supersaturated solutions. Carbohydrates are a class of such compounds; The thermodynamic barrier to formation of crystals is rather high because of extensive and irregular hydrogen bonding with the solvent, water. For example, although sucrose can be recrystallised easily, its hydrolysis product, known as "invert sugar" or "golden syrup" is a mixture of glucose and fructose that exists as a viscous, supersaturated, liquid. Clear honey contains carbohydrates which may crystallize over a period of weeks.

Supersaturation may be encountered when attempting to crystallize a protein. [7]

Gaseous solute, liquid solvent

The solubility of a gas in a liquid increases with increasing gas pressure. When the external pressure is reduced, the excess gas comes out of solution.

Fizzy drinks are made by subjecting the liquid to carbon dioxide, under pressure. In champagne the CO2 is produced naturally in the final stage of fermentation. When the bottle or can is opened some gas is released in the form of bubbles.

Release of gas from supersaturated tissues can cause an underwater diver to suffer from decompression sickness (a.k.a. the bends) when returning to the surface. This can be fatal if the released gas obstructs critical blood supplies causing ischaemia in vital tissues. [8]

Dissolved gases can be released during oil exploration when a strike is made. This occurs because the oil in oil-bearing rock is under considerable pressure from the over-lying rock, allowing the oil to be supersaturated with respect to dissolved gases.

Liquid formation from a mixture of gases

A cloudburst is an extreme form of production of liquid water from a supersaturated mixture of air and water vapour in the atmosphere. Supersaturation in the vapour phase is related to the surface tension of liquids through the Kelvin equation, the Gibbs–Thomson effect and the Poynting effect. [9]

The International Association for the Properties of Water and Steam (IAPWS) provides a special equation for the Gibbs free energy in the metastable-vapor region of water in its Revised Release on the IAPWS Industrial Formulation 1997 for the Thermodynamic Properties of Water and Steam. All thermodynamic properties for the metastable-vapor region of water can be derived from this equation by means of the appropriate relations of thermodynamic properties to the Gibbs free energy. [10]

Measurement

When measuring the concentration of a solute in a supersaturated gaseous or liquid mixture it is obvious that the pressure inside the cuvette may be greater than the ambient pressure. When this is so a specialized cuvette must be used. The choice of analytical technique to use will depend on the characteristics of the analyte. [11]

Applications

The characteristics of supersaturation have practical applications in terms of pharmaceuticals. By creating a supersaturated solution of a certain drug, it can be ingested in liquid form. The drug can be made driven into a supersaturated state through any normal mechanism and then prevented from precipitating out by adding precipitation inhibitors. [12] Drugs in this state are referred to as "supersaturating drug delivery services," or "SDDS." [13] Oral consumption of a drug in this form is simple and allows for the measurement of very precise dosages. Primarily, it provides a means for drugs with very low solubility to be made into aqueous solutions. [14] [15] In addition, some drugs can undergo supersaturation inside the body despite being ingested in a crystalline form. [16] This phenomenon is known as in vivo supersaturation.

The identification of supersaturated solutions can be used as a tool for marine ecologists to study the activity of organisms and populations. Photosynthetic organisms release O2 gas into the water. Thus, an area of the ocean supersaturated with O2 gas can likely determined to be rich with photosynthetic activity. Though some O2 will naturally be found in the ocean due to simple physical chemical properties, upwards of 70% of all oxygen gas found in supersaturated regions can be attributed to photosynthetic activity. [17]

Supersaturation in vapor phase is usually present in the expansion process through steam nozzles that operate with superheated steam at the inlet, which transitions to saturated state at the outlet. Supersaturation thus becomes an important factor to be taken into account in the design of steam turbines, as this results in an actual mass flow of steam through the nozzle being about 1 to 3% greater than the theoretically calculated value that would be expected if the expanding steam underwent a reversible adiabatic process through equilibrium states. In these cases supersaturation occurs due to the fact that the expansion process develops so rapidly and in such a short time, that the expanding vapor cannot reach its equilibrium state in the process, behaving as if it were superheated. Hence the determination of the expansion ratio, relevant to the calculation of the mass flow through the nozzle, must be done using an adiabatic index of approximately 1.3, like that of the superheated steam, instead of 1.135, which is the value that should have to be used for a quasi-static adiabatic expansion in the saturated region. [18]

The study of supersaturation is also relevant to atmospheric studies. Since the 1940s, the presence of supersaturation in the atmosphere has been known. When water is supersaturated in the troposphere, the formation of ice lattices is frequently observed. In a state of saturation, the water particles will not form ice under tropospheric conditions. It is not enough for molecules of water to form an ice lattice at saturation pressures; they require a surface to condense on to or conglomerations of liquid water molecules of water to freeze. For these reasons, relative humidities over ice in the atmosphere can be found above 100%, meaning supersaturation has occurred. Supersaturation of water is actually very common in the upper troposphere, occurring between 20% and 40% of the time. [19] This can be determined using satellite data from the Atmospheric Infrared Sounder. [20]

Related Research Articles

<span class="mw-page-title-main">Phase (matter)</span> Region of uniform physical properties

In the physical sciences, a phase is a region of material that is chemically uniform, physically distinct, and (often) mechanically separable. In a system consisting of ice and water in a glass jar, the ice cubes are one phase, the water is a second phase, and the humid air is a third phase over the ice and water. The glass of the jar is another separate phase.

<span class="mw-page-title-main">Solution (chemistry)</span> Homogeneous mixture of a solute and a solvent

In chemistry, a solution is a special type of homogeneous mixture composed of two or more substances. In such a mixture, a solute is a substance dissolved in another substance, known as a solvent. If the attractive forces between the solvent and solute particles are greater than the attractive forces holding the solute particles together, the solvent particles pull the solute particles apart and surround them. These surrounded solute particles then move away from the solid solute and out into the solution. The mixing process of a solution happens at a scale where the effects of chemical polarity are involved, resulting in interactions that are specific to solvation. The solution usually has the state of the solvent when the solvent is the larger fraction of the mixture, as is commonly the case. One important parameter of a solution is the concentration, which is a measure of the amount of solute in a given amount of solution or solvent. The term "aqueous solution" is used when one of the solvents is water.

<span class="mw-page-title-main">Vapor pressure</span> Pressure exerted by a vapor in thermodynamic equilibrium

Vapor pressure or equilibrium vapor pressure is the pressure exerted by a vapor in thermodynamic equilibrium with its condensed phases at a given temperature in a closed system. The equilibrium vapor pressure is an indication of a liquid's thermodynamic tendency to evaporate. It relates to the balance of particles escaping from the liquid in equilibrium with those in a coexisting vapor phase. A substance with a high vapor pressure at normal temperatures is often referred to as volatile. The pressure exhibited by vapor present above a liquid surface is known as vapor pressure. As the temperature of a liquid increases, the attractive interactions between liquid molecules become less significant in comparison to the entropy of those molecules in the gas phase, increasing the vapor pressure. Thus, liquids with strong intermolecular interactions are likely to have smaller vapor pressures, with the reverse true for weaker interactions.

<span class="mw-page-title-main">Solubility</span> Capacity of a substance to dissolve in a solvent in a homogeneous way

In chemistry, solubility is the ability of a substance, the solute, to form a solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form such a solution.

Solubility equilibrium is a type of dynamic equilibrium that exists when a chemical compound in the solid state is in chemical equilibrium with a solution of that compound. The solid may dissolve unchanged, with dissociation, or with chemical reaction with another constituent of the solution, such as acid or alkali. Each solubility equilibrium is characterized by a temperature-dependent solubility product which functions like an equilibrium constant. Solubility equilibria are important in pharmaceutical, environmental and many other scenarios.

<span class="mw-page-title-main">Spray drying</span> Method of converting liquid or slurry to powder

Spray drying is a method of forming a dry powder from a liquid or slurry by rapidly drying with a hot gas. This is the preferred method of drying of many thermally-sensitive materials such as foods and pharmaceuticals, or materials which may require extremely consistent, fine particle size. Air is the heated drying medium; however, if the liquid is a flammable solvent such as ethanol or the product is oxygen-sensitive then nitrogen is used.

In chemical thermodynamics, activity is a measure of the "effective concentration" of a species in a mixture, in the sense that the species' chemical potential depends on the activity of a real solution in the same way that it would depend on concentration for an ideal solution. The term "activity" in this sense was coined by the American chemist Gilbert N. Lewis in 1907.

In chemistry, colligative properties are those properties of solutions that depend on the ratio of the number of solute particles to the number of solvent particles in a solution, and not on the nature of the chemical species present. The number ratio can be related to the various units for concentration of a solution such as molarity, molality, normality (chemistry), etc. The assumption that solution properties are independent of nature of solute particles is exact only for ideal solutions, which are solutions that exhibit thermodynamic properties analogous to those of an ideal gas, and is approximate for dilute real solutions. In other words, colligative properties are a set of solution properties that can be reasonably approximated by the assumption that the solution is ideal.

Micronization is the process of reducing the average diameter of a solid material's particles. Traditional techniques for micronization focus on mechanical means, such as milling and grinding. Modern techniques make use of the properties of supercritical fluids and manipulate the principles of solubility.

<span class="mw-page-title-main">Crystallization</span> Process by which a solid with a highly organized atomic or molecular structure forms

Crystallization is the process by which solid forms, where the atoms or molecules are highly organized into a structure known as a crystal. Some ways by which crystals form are precipitating from a solution, freezing, or more rarely deposition directly from a gas. Attributes of the resulting crystal depend largely on factors such as temperature, air pressure, and in the case of liquid crystals, time of fluid evaporation.

<span class="mw-page-title-main">Critical point (thermodynamics)</span> Temperature and pressure point where phase boundaries disappear

In thermodynamics, a critical point is the end point of a phase equilibrium curve. One example is the liquid–vapor critical point, the end point of the pressure–temperature curve that designates conditions under which a liquid and its vapor can coexist. At higher temperatures, the gas cannot be liquefied by pressure alone. At the critical point, defined by a critical temperatureTc and a critical pressurepc, phase boundaries vanish. Other examples include the liquid–liquid critical points in mixtures, and the ferromagnet–paramagnet transition in the absence of an external magnetic field.

<span class="mw-page-title-main">Nucleation</span> Initial step in the phase transition or molecular self-assembly of a substance

In thermodynamics, nucleation is the first step in the formation of either a new thermodynamic phase or structure via self-assembly or self-organization within a substance or mixture. Nucleation is typically defined to be the process that determines how long an observer has to wait before the new phase or self-organized structure appears. For example, if a volume of water is cooled below 0 °C, it will tend to freeze into ice, but volumes of water cooled only a few degrees below 0 °C often stay completely free of ice for long periods (supercooling). At these conditions, nucleation of ice is either slow or does not occur at all. However, at lower temperatures nucleation is fast, and ice crystals appear after little or no delay.

This page provides supplementary data to the article properties of water.

Boiling-point elevation describes the phenomenon that the boiling point of a liquid will be higher when another compound is added, meaning that a solution has a higher boiling point than a pure solvent. This happens whenever a non-volatile solute, such as a salt, is added to a pure solvent, such as water. The boiling point can be measured accurately using an ebullioscope.

<span class="mw-page-title-main">Hydrothermal synthesis</span> Techniques for crystallizing substances

Hydrothermal synthesis includes the various techniques of crystallizing substances from high-temperature aqueous solutions at high vapor pressures; also termed "hydrothermal method". The term "hydrothermal" is of geologic origin. Geochemists and mineralogists have studied hydrothermal phase equilibria since the beginning of the twentieth century. George W. Morey at the Carnegie Institution and later, Percy W. Bridgman at Harvard University did much of the work to lay the foundations necessary to containment of reactive media in the temperature and pressure range where most of the hydrothermal work is conducted.

Volatiles are the group of chemical elements and chemical compounds that can be readily vaporized. In contrast with volatiles, elements and compounds that are not readily vaporized are known as refractory substances.

This glossary of chemistry terms is a list of terms and definitions relevant to chemistry, including chemical laws, diagrams and formulae, laboratory tools, glassware, and equipment. Chemistry is a physical science concerned with the composition, structure, and properties of matter, as well as the changes it undergoes during chemical reactions; it features an extensive vocabulary and a significant amount of jargon.

<span class="mw-page-title-main">Protein crystallization</span>

Protein crystallization is the process of formation of a regular array of individual protein molecules stabilized by crystal contacts. If the crystal is sufficiently ordered, it will diffract. Some proteins naturally form crystalline arrays, like aquaporin in the lens of the eye.

Broadband acoustic resonance dissolution spectroscopy (BARDS) is a technique in analytical chemistry. Developed in the late 2000s, it involves the analysis of the changes in sound frequency generated when a solute dissolves in a solvent, by harnessing the hot chocolate effect first described by Frank S. Crawford.

The use of ionic liquids in carbon capture is a potential application of ionic liquids as absorbents for use in carbon capture and sequestration. Ionic liquids, which are salts that exist as liquids near room temperature, are polar, nonvolatile materials that have been considered for many applications. The urgency of climate change has spurred research into their use in energy-related applications such as carbon capture and storage.

References

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