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Superheated water is liquid
water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as ...
under
pressure Pressure (symbol: ''p'' or ''P'') is the force applied perpendicular to the surface of an object per unit area over which that force is distributed. Gauge pressure (also spelled ''gage'' pressure)The preferred spelling varies by country a ...
at temperatures between the usual
boiling point The boiling point of a substance is the temperature at which the vapor pressure of a liquid equals the pressure surrounding the liquid and the liquid changes into a vapor. The boiling point of a liquid varies depending upon the surrounding env ...
, and the
critical temperature Critical or Critically may refer to: *Critical, or critical but stable, medical states **Critical, or intensive care medicine * Critical juncture, a discontinuous change studied in the social sciences. * Critical Software, a company specializing ...
, . It is also known as "subcritical water" or "pressurized hot water". Superheated water is stable because of overpressure that raises the boiling point, or by heating it in a sealed vessel with a headspace, where the liquid water is in equilibrium with vapour at the saturated vapor pressure. This is distinct from the use of the term
superheating In thermodynamics, superheating (sometimes referred to as boiling retardation, or boiling delay) is the phenomenon in which a liquid is heated to a temperature higher than its boiling point, without boiling. This is a so-called '' metastable sta ...
to refer to water at atmospheric pressure above its normal boiling point, which has not boiled due to a lack of nucleation sites (sometimes experienced by heating liquids in a microwave). Many of water's anomalous properties are due to very strong
hydrogen bond In chemistry, a hydrogen bond (or H-bond) is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group (Dn), and another electronegative atom bearing a l ...
ing. Over the superheated
temperature Temperature is a physical quantity that expresses quantitatively the perceptions of hotness and coldness. Temperature is measured with a thermometer. Thermometers are calibrated in various temperature scales that historically have relied o ...
range the hydrogen bonds break, changing the properties more than usually expected by increasing temperature alone. Water becomes less polar and behaves more like an
organic solvent A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for ...
such as
methanol Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical and the simplest aliphatic alcohol, with the formula C H3 O H (a methyl group linked to a hydroxyl group, often abbreviated as MeOH). It is ...
or
ethanol Ethanol (abbr. EtOH; also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound. It is an alcohol with the chemical formula . Its formula can be also written as or (an ethyl group linked to a ...
. Solubility of organic materials and gases increases by several orders of magnitude and the water itself can act as a solvent,
reagent In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...
, and
catalyst Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
in industrial and analytical applications, including extraction, chemical reactions and cleaning.


Change of properties with temperature

All materials change with temperature, but superheated water exhibits greater changes than would be expected from temperature considerations alone.
Viscosity The viscosity of a fluid is a measure of its resistance to deformation at a given rate. For liquids, it corresponds to the informal concept of "thickness": for example, syrup has a higher viscosity than water. Viscosity quantifies the int ...
and
surface tension Surface tension is the tendency of liquid surfaces at rest to shrink into the minimum surface area possible. Surface tension is what allows objects with a higher density than water such as razor blades and insects (e.g. water striders) t ...
of water drop and
diffusivity Diffusivity is a rate of diffusion, a measure of the rate at which particles or heat or fluids can spread. It is measured differently for different mediums. Diffusivity may refer to: * Thermal diffusivity, diffusivity of heat *Diffusivity of mas ...
increases with increasing temperature. Self-ionization of water increases with temperature, and the pKw of water at 250 °C is closer to 11 than the more familiar 14 at 25 °C. This means the concentration of
hydronium In chemistry, hydronium (hydroxonium in traditional British English) is the common name for the aqueous cation , the type of oxonium ion produced by protonation of water. It is often viewed as the positive ion present when an Arrhenius acid ...
ion () and the concentration of hydroxide () are increased while the pH remains neutral.
Specific heat capacity In thermodynamics, the specific heat capacity (symbol ) of a substance is the heat capacity of a sample of the substance divided by the mass of the sample, also sometimes referred to as massic heat capacity. Informally, it is the amount of heat t ...
at constant pressure also increases with temperature, from 4.187 kJ/kg at 25 °C to 8.138 kJ/kg at 350 °C. A significant effect on the behaviour of water at high temperatures is decreased
dielectric constant The relative permittivity (in older texts, dielectric constant) is the permittivity of a material expressed as a ratio with the electric permittivity of a vacuum. A dielectric is an insulating material, and the dielectric constant of an insula ...
(
relative permittivity The relative permittivity (in older texts, dielectric constant) is the permittivity of a material expressed as a ratio with the electric permittivity of a vacuum. A dielectric is an insulating material, and the dielectric constant of an insul ...
).


Explanation of anomalous behaviour

Water is a
polar Polar may refer to: Geography Polar may refer to: * Geographical pole, either of two fixed points on the surface of a rotating body or planet, at 90 degrees from the equator, based on the axis around which a body rotates *Polar climate, the cli ...
molecule, where the centers of positive and negative charge are separated; so molecules will align with an
electric field An electric field (sometimes E-field) is the physical field that surrounds electrically charged particles and exerts force on all other charged particles in the field, either attracting or repelling them. It also refers to the physical field ...
. The extensive hydrogen bonded network in water tends to oppose this alignment, and the degree of alignment is measured by the
relative permittivity The relative permittivity (in older texts, dielectric constant) is the permittivity of a material expressed as a ratio with the electric permittivity of a vacuum. A dielectric is an insulating material, and the dielectric constant of an insul ...
. Water has a high relative permittivity of about 80 at room temperature; because polarity shifts are rapidly transmitted through shifts in orientation of the linked hydrogen bonds. This allows water to dissolve salts, as the attractive electric field between ions is reduced by about 80–fold. Thermal motion of the molecules disrupts the hydrogen bonding network as temperature increases; so relative permittivity decreases with temperature to about 7 at the critical temperature. At 205 °C the relative permittivity falls to 33, the same as methanol at room temperature. Thus water behaves like a water–methanol mixture between 100 °C and 200 °C. Disruption of extended hydrogen bonding allows molecules to move more freely (viscosity, diffusion and surface tension effects), and extra energy must be supplied to break the bonds (increased heat capacity).


Solubility


Organic compounds

Organic molecules In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen or carbon-carbon bonds. Due to carbon's ability to catenate (form chains with other carbon atoms), millions of organic compounds are known. The s ...
often show a dramatic increase in solubility with temperature, partly because of the polarity changes described above, and also because the solubility of sparingly soluble materials tends to increase with temperature as they have a high enthalpy of solution. Thus materials generally considered "insoluble" can become soluble in superheated water. E.g., the solubility of
PAHs A polycyclic aromatic hydrocarbon (PAH) is a class of organic compounds that is composed of multiple aromatic rings. The simplest representative is naphthalene, having two aromatic rings and the three-ring compounds anthracene and phenanthrene. P ...
is increased by 5 orders of magnitude from 25 °C to 225 °C and
naphthalene Naphthalene is an organic compound with formula . It is the simplest polycyclic aromatic hydrocarbon, and is a white crystalline solid with a characteristic odor that is detectable at concentrations as low as 0.08  ppm by mass. As an aromat ...
, for example, forms a 10% wt solution in water at 270 °C, and the solubility of the
pesticide Pesticides are substances that are meant to control pests. This includes herbicide, insecticide, nematicide, molluscicide, piscicide, avicide, rodenticide, bactericide, insect repellent, animal repellent, microbicide, fungicide, and ...
chlorothalonil Chlorothalonil (2,4,5,6-tetrachloroisophthalonitrile) is an organic compound mainly used as a broad spectrum, nonsystemic fungicide, with other uses as a wood protectant, pesticide, acaricide, and to control mold, mildew, bacteria, algae. C ...
with temperature is shown in the table below. Thus superheated water can be used to process many organic compounds with significant environmental benefits compared to the use of conventional organic solvents.


Salts

Despite the reduction in relative permittivity, many
salt Salt is a mineral composed primarily of sodium chloride (NaCl), a chemical compound belonging to the larger class of salts; salt in the form of a natural crystalline mineral is known as rock salt or halite. Salt is present in vast quant ...
s remain soluble in superheated water until the critical point is approached.
Sodium chloride Sodium chloride , commonly known as salt (although sea salt also contains other chemical salts), is an ionic compound with the chemical formula NaCl, representing a 1:1 ratio of sodium and chloride ions. With molar masses of 22.99 and 35. ...
, for example, dissolves at 37 
wt% In chemistry, the mass fraction of a substance within a mixture is the ratio w_i (alternatively denoted Y_i) of the mass m_i of that substance to the total mass m_\text of the mixture. Expressed as a formula, the mass fraction is: : w_i = \frac ...
at 300 °C As the critical point is approached, solubility drops markedly to a few ppm, and salts are hardly soluble in supercritical water. Some salts show a reduction in solubility with temperature, but this behaviour is less common.


Gases

The solubility of gases in water is usually thought to decrease with temperature, but this only occurs to a certain temperature, before increasing again. For nitrogen, this minimum is 74 °C and for oxygen it is 94 °C Gases are soluble in superheated water at elevated pressures. Above the critical temperature, water is completely miscible with all gasses. The increasing solubility of oxygen in particular allows superheated water to be used for wet oxidation processes.


Corrosion

Superheated water can be more corrosive than water at ordinary temperatures, and at temperatures above 300 °C special corrosion resistant
alloy An alloy is a mixture of chemical elements of which at least one is a metal. Unlike chemical compounds with metallic bases, an alloy will retain all the properties of a metal in the resulting material, such as electrical conductivity, ductili ...
s may be required, depending on other dissolved components. Continuous use of
carbon steel Carbon steel is a steel with carbon content from about 0.05 up to 2.1 percent by weight. The definition of carbon steel from the American Iron and Steel Institute (AISI) states: * no minimum content is specified or required for chromium, coba ...
pipes for 20 years at 282 °C has been reported without significant corrosion, and
stainless steel Stainless steel is an alloy of iron that is resistant to rusting and corrosion. It contains at least 11% chromium and may contain elements such as carbon, other nonmetals and metals to obtain other desired properties. Stainless steel's r ...
cells showed only slight deterioration after 40–50 uses at temperatures up to 350 °C. The degree of corrosion that can be tolerated depends on the use, and even corrosion resistant alloys can fail eventually. Corrosion of an
Inconel Inconel is a registered trademark of Special Metals Corporation for a family of austenitic nickel-chromium-based superalloys. Inconel alloys are oxidation-corrosion-resistant materials well suited for service in extreme environments subjected ...
U-tube in a
heat exchanger A heat exchanger is a system used to transfer heat between a source and a working fluid. Heat exchangers are used in both cooling and heating processes. The fluids may be separated by a solid wall to prevent mixing or they may be in direct conta ...
was blamed for an
accident An accident is an unintended, normally unwanted event that was not directly caused by humans. The term ''accident'' implies that nobody should be blamed, but the event may have been caused by unrecognized or unaddressed risks. Most researche ...
at a nuclear power station. Therefore, for occasional or experimental use, ordinary grades of stainless steel are probably adequate with continuous monitoring, but for critical applications and difficult to service parts, extra care needs to be taken in materials selection.


Effect of pressure

At temperatures below 300 °C water is fairly incompressible, which means that pressure has little effect on the physical properties of water, provided it is sufficient to maintain a
liquid A liquid is a nearly incompressible fluid that conforms to the shape of its container but retains a (nearly) constant volume independent of pressure. As such, it is one of the four fundamental states of matter (the others being solid, gas, ...
state. This pressure is given by the saturated vapour pressure, and can be looked up in steam tables, or calculated. As a guide, the saturated vapour pressure at 121 °C is 200  kPa, 150 °C is 470 kPa, and 200 °C is 1,550 kPa. The critical point is 21.7 MPa at a temperature of 374 °C, above which water is supercritical rather than superheated. Above about 300 °C, water starts to behave as a near-critical liquid, and physical properties such as density start to change more significantly with pressure. However, higher pressures increase the rate of extractions using superheated water below 300 °C. This could be due to effects on the substrate, particularly plant materials, rather than changing water properties.


Energy requirements

The energy required to heat water is significantly lower than that needed to vaporize it, for example for steam distillation and the energy is easier to recycle using heat exchangers. The energy requirements can be calculated from steam tables. For example, to heat water from 25 °C to steam at 250 °C at 1 atm requires 2869 kJ/kg. To heat water at 25 °C to liquid water at 250 °C at 5 MPa requires only 976 kJ/kg. It is also possible to recover much of the heat (say 75%) from superheated water, and therefore energy use for superheated water extraction is less than one sixth that needed for steam distillation. This also means that the energy contained in superheated water is insufficient to vaporise the water on decompression. In the above example, only 30% of the water would be converted to vapour on decompression from 5 MPa to atmospheric pressure.


Extraction

Extraction using superheated water tends to be fast because diffusion rates increase with temperature. Organic materials tend to increase in solubility with temperature, but not all at the same rate. For example, in extraction of
essential oil An essential oil is a concentrated hydrophobic liquid containing volatile (easily evaporated at normal temperatures) chemical compounds from plants. Essential oils are also known as volatile oils, ethereal oils, aetheroleum, or simply as the o ...
s from
rosemary ''Salvia rosmarinus'' (), commonly known as rosemary, is a shrub with fragrant, evergreen, needle-like leaves and white, pink, purple, or blue flowers, native plant, native to the Mediterranean Region, Mediterranean region. Until 2017, it was kn ...
and coriander, the more valuable oxygenated
terpene Terpenes () are a class of natural products consisting of compounds with the formula (C5H8)n for n > 1. Comprising more than 30,000 compounds, these unsaturated hydrocarbons are produced predominantly by plants, particularly conifers. Terpenes ...
s were extracted much faster than the hydrocarbons. Therefore, extraction with superheated water can be both selective and rapid, and has been used to fractionate
diesel Diesel may refer to: * Diesel engine, an internal combustion engine where ignition is caused by compression * Diesel fuel, a liquid fuel used in diesel engines * Diesel locomotive, a railway locomotive in which the prime mover is a diesel engi ...
and woodsmoke particulates. Superheated water is being used commercially to extract starch material from marsh mallow root for skincare applications and to remove low levels of metals from a high-temperature resistant
polymer A polymer (; Greek '' poly-'', "many" + '' -mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
. For analytical purposes, superheated water can replace organic solvents in many applications, for example extraction of PAHs from soils and can also be used on a large scale to remediate contaminated soils, by either extraction alone or extraction linked to supercritical or wet oxidation.


Reactions

Superheated water, along with
supercritical water Supercritical water oxidation (SCWO) is a process that occurs in water at temperatures and pressures above a mixture's thermodynamic critical point. Under these conditions water becomes a fluid with unique properties that can be used to advantag ...
, has been used to oxidise hazardous material in the wet oxidation process. Organic compounds are rapidly
oxidised Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...
without the production of toxic materials sometimes produced by combustion. However, when the oxygen levels are lower, organic compounds can be quite stable in superheated water. As the concentration of
hydronium In chemistry, hydronium (hydroxonium in traditional British English) is the common name for the aqueous cation , the type of oxonium ion produced by protonation of water. It is often viewed as the positive ion present when an Arrhenius acid ...
() and
hydroxide Hydroxide is a diatomic anion with chemical formula OH−. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. ...
() ions are 100 times larger than in water at 25 °C, superheated water can act as a stronger
acid In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a se ...
and a stronger base, and many different types of reaction can be carried out. An example of a selective reaction is oxidation of
ethylbenzene Ethylbenzene is an organic compound with the formula . It is a highly flammable, colorless liquid with an odor similar to that of gasoline. This monocyclic aromatic hydrocarbon is important in the petrochemical industry as an reaction interme ...
to
acetophenone Acetophenone is the organic compound with the chemical formula, formula C6H5C(O)CH3. It is the simplest aromatic ketone. This colorless, viscous liquid is a precursor to useful resins and fragrances. Production Acetophenone is formed as a byprodu ...
, with no evidence of formation of phenylethanoic acid, or of
pyrolysis The pyrolysis (or devolatilization) process is the thermal decomposition of materials at elevated temperatures, often in an inert atmosphere. It involves a change of chemical composition. The word is coined from the Greek-derived elements '' ...
products. Several different types of reaction in which water was behaving as reactant, catalyst and solvent were described by Katritzky et al. Triglycerides can be hydrolysed to
free fatty acids In chemistry, particularly in biochemistry, a fatty acid is a carboxylic acid with an aliphatic chain, which is either saturated or unsaturated. Most naturally occurring fatty acids have an unbranched chain of an even number of carbon atoms, f ...
and
glycerol Glycerol (), also called glycerine in British English and glycerin in American English, is a simple triol compound. It is a colorless, odorless, viscous liquid that is sweet-tasting and non-toxic. The glycerol backbone is found in lipids known ...
by superheated water at 275 °C, which can be the first in a two-stage process to make
biodiesel Biodiesel is a form of diesel fuel derived from plants or animals and consisting of long-chain fatty acid esters. It is typically made by chemically reacting lipids such as animal fat ( tallow), soybean oil, or some other vegetable oi ...
. Superheated water can be used to chemically convert organic material into fuel products. This is known by several terms, including direct hydrothermal liquefaction, and hydrous pyrolysis. A few commercial scale applications exist. Thermal depolymerization or thermal conversion (TCC) uses superheated water at about 250 °C to convert turkey waste into a light
fuel oil Fuel oil is any of various fractions obtained from the distillation of petroleum (crude oil). Such oils include distillates (the lighter fractions) and residues (the heavier fractions). Fuel oils include heavy fuel oil, marine fuel oil (MFO), b ...
and is said to process 200 tons of low grade waste into fuel oil a day. The initial product from the hydrolysis reaction is de-watered and further processed by dry cracking at 500 °C. The "SlurryCarb" process operated by EnerTech uses similar technology to decarboxylate wet solid biowaste, which can then be physically dewatered and used as a solid fuel called E-Fuel. The plant at Rialto is said to be able to process 683 tons of waste per day. The HTU or Hydro Thermal Upgrading process appears similar to the first stage of the TCC process. A demonstration plant is due to start up in The Netherlands said to be capable of processing 64 tons of biomass ( dry basis) per day into oil.


Chromatography

Reverse phased
HPLC High-performance liquid chromatography (HPLC), formerly referred to as high-pressure liquid chromatography, is a technique in analytical chemistry used to separate, identify, and quantify each component in a mixture. It relies on pumps to p ...
often uses methanol–water mixtures as the mobile phase. Since the polarity of water spans the same range from 25 to 205 °C, a temperature gradient can be used to effect similar separations, for example of
phenol Phenol (also called carbolic acid) is an aromatic organic compound with the molecular formula . It is a white crystalline solid that is volatile. The molecule consists of a phenyl group () bonded to a hydroxy group (). Mildly acidic, it r ...
s. The use of water allows the use of the flame ionisation detector (FID), which gives mass sensitive output for nearly all organic compounds. The maximum temperature is limited to that at which the stationary phase is stable. C18 bonded phases which are common in HPLC seem to be stable at temperatures up to 200 °C, far above that of pure silica, and polymeric styrene– divinylbenzene phases offer similar temperature stability. Water is also compatible with use of an ultraviolet detector down to a wavelength of 190 nm.


See also

*
Pressurized water reactor A pressurized water reactor (PWR) is a type of light-water nuclear reactor. PWRs constitute the large majority of the world's nuclear power plants (with notable exceptions being the UK, Japan and Canada). In a PWR, the primary coolant (water) i ...
*
Steam cracking Steam cracking is a petrochemical process in which saturated hydrocarbons are broken down into smaller, often unsaturated, hydrocarbons. It is the principal industrial method for producing the lighter alkenes (or commonly olefins), including et ...
*
Supercritical carbon dioxide Supercritical carbon dioxide (s) is a fluid state of carbon dioxide where it is held at or above its critical temperature and critical pressure. Carbon dioxide usually behaves as a gas in air at standard temperature and pressure (STP), or as ...
*
Superheated steam Superheated steam is steam at a temperature higher than its vaporization point at the absolute pressure where the temperature is measured. Superheated steam can therefore cool (lose internal energy) by some amount, resulting in a lowering of ...
*
Water heating Water heating is a heat transfer process that uses an energy source to heat water above its initial temperature. Typical domestic uses of hot water include cooking, cleaning, bathing, and space heating. In industry, hot water and water heated t ...


References

{{Reflist, 30em


External links


The International Association
for the Properties of Water and Steam

for vapour pressure and enthalpy of superheated water. Water physics