In the physical sciences, a partition coefficient or distribution coefficient is the ratio of concentrations of a compound in a mixture of two immiscible phases at equilibrium. This ratio is therefore a measure of the difference in solubility of the compound in these two phases; the partition coefficient refers to the concentration ratio of un-ionized species of compound, whereas the distribution coefficient refers to the concentration ratio of all species of the compound. In the chemical and pharmaceutical sciences, both phases are solvents. Most one of the solvents is water, while the second is hydrophobic, such as 1-octanol. Hence the partition coefficient measures how hydrophobic a chemical substance is. Partition coefficients are useful in estimating the distribution of drugs within the body. Hydrophobic drugs with high octanol/water partition coefficients are distributed to hydrophobic areas such as lipid bilayers of cells. Conversely, hydrophilic drugs are found in aqueous regions such as blood serum.
If one of the solvents is a gas and the other a liquid, a gas/liquid partition coefficient can be determined. For example, the blood/gas partition coefficient of a general anesthetic measures how the anesthetic passes from gas to blood. Partition coefficients can be defined when one of the phases is solid, for instance, when one phase is a molten metal and the second is a solid metal, or when both phases are solids; the partitioning of a substance into a solid results in a solid solution. Partition coefficients can be measured experimentally in various ways or estimated by calculation based on a variety of methods. Despite formal recommendation to the contrary, the term partition coefficient remains the predominantly used term in the scientific literature. In contrast, the IUPAC recommends that the title term no longer be used, that it be replaced with more specific terms. For example, partition constant, defined as where KD is the process equilibrium constant, represents the concentration of solute A being tested, "org" and "aq" refer to the organic and aqueous phases respectively.
The IUPAC further recommends "partition ratio" for cases where transfer activity coefficients can be determined, "distribution ratio" for the ratio of total analytical concentrations of a solute between phases, regardless of chemical form. The partition coefficient, abbreviated P, is defined as a particular ratio of the concentrations of a solute between the two solvents for un-ionized solutes, the logarithm of the ratio is thus log P; when one of the solvents is water and the other is a non-polar solvent the log P value is a measure of lipophilicity or hydrophobicity. The defined precedent is for the lipophilic and hydrophilic phase types to always be in the numerator and denominator respectively. To a first approximation, the non-polar phase in such experiments is dominated by the un-ionized form of the solute, electrically neutral, though this may not be true for the aqueous phase. To measure the partition coefficient of ionizable solutes, the pH of the aqueous phase is adjusted such that the predominant form of the compound in solution is the un-ionized, or its measurement at another pH of interest requires consideration of all species, un-ionized and ionized.
A corresponding partition coefficient for ionizable compounds, abbreviated log P I, is derived for cases where there are dominant ionized forms of the molecule, such that one must consider partition of all forms, ionized and un-ionized, between the two phases. M is used to indicate the number of ionized forms. For instance, for an octanol–water partition, it is log P oct/wat I = log . To distinguish between this and the standard, un-ionized, partition coefficient, the un-ionized is assigned the symbol log P0, such that the indexed log P oct/wat I expression for ionized solutes becomes an extension of this, into the range of values I > 0. The distribution co
European Chemicals Agency
The European Chemicals Agency is an agency of the European Union which manages the technical and administrative aspects of the implementation of the European Union regulation called Registration, Evaluation and Restriction of Chemicals. ECHA is the driving force among regulatory authorities in implementing the EU's chemicals legislation. ECHA helps companies to comply with the legislation, advances the safe use of chemicals, provides information on chemicals and addresses chemicals of concern, it is located in Finland. The agency headed by Executive Director Bjorn Hansen, started working on 1 June 2007; the REACH Regulation requires companies to provide information on the hazards and safe use of chemical substances that they manufacture or import. Companies register this information with ECHA and it is freely available on their website. So far, thousands of the most hazardous and the most used substances have been registered; the information is technical but gives detail on the impact of each chemical on people and the environment.
This gives European consumers the right to ask retailers whether the goods they buy contain dangerous substances. The Classification and Packaging Regulation introduces a globally harmonised system for classifying and labelling chemicals into the EU; this worldwide system makes it easier for workers and consumers to know the effects of chemicals and how to use products safely because the labels on products are now the same throughout the world. Companies need to notify ECHA of the labelling of their chemicals. So far, ECHA has received over 5 million notifications for more than 100 000 substances; the information is available on their website. Consumers can check chemicals in the products. Biocidal products include, for example, insect disinfectants used in hospitals; the Biocidal Products Regulation ensures that there is enough information about these products so that consumers can use them safely. ECHA is responsible for implementing the regulation; the law on Prior Informed Consent sets guidelines for the import of hazardous chemicals.
Through this mechanism, countries due to receive hazardous chemicals are informed in advance and have the possibility of rejecting their import. Substances that may have serious effects on human health and the environment are identified as Substances of Very High Concern 1; these are substances which cause cancer, mutation or are toxic to reproduction as well as substances which persist in the body or the environment and do not break down. Other substances considered. Companies manufacturing or importing articles containing these substances in a concentration above 0,1% weight of the article, have legal obligations, they are required to inform users about the presence of the substance and therefore how to use it safely. Consumers have the right to ask the retailer whether these substances are present in the products they buy. Once a substance has been identified in the EU as being of high concern, it will be added to a list; this list is available on ECHA's website and shows consumers and industry which chemicals are identified as SVHCs.
Substances placed on the Candidate List can move to another list. This means that, after a given date, companies will not be allowed to place the substance on the market or to use it, unless they have been given prior authorisation to do so by ECHA. One of the main aims of this listing process is to phase out SVHCs where possible. In its 2018 substance evaluation progress report, ECHA said chemical companies failed to provide “important safety information” in nearly three quarters of cases checked that year. "The numbers show a similar picture to previous years" the report said. The agency noted that member states need to develop risk management measures to control unsafe commercial use of chemicals in 71% of the substances checked. Executive Director Bjorn Hansen called non-compliance with REACH a "worry". Industry group CEFIC acknowledged the problem; the European Environmental Bureau called for faster enforcement to minimise chemical exposure. European Chemicals Bureau Official website
Ultraviolet–visible spectroscopy or ultraviolet–visible spectrophotometry refers to absorption spectroscopy or reflectance spectroscopy in part of the ultraviolet and the full, adjacent visible spectral regions. This means it uses light in the adjacent ranges; the absorption or reflectance in the visible range directly affects the perceived color of the chemicals involved. In this region of the electromagnetic spectrum and molecules undergo electronic transitions. Absorption spectroscopy is complementary to fluorescence spectroscopy, in that fluorescence deals with transitions from the excited state to the ground state, while absorption measures transitions from the ground state to the excited state. Molecules containing bonding and non-bonding electrons can absorb energy in the form of ultraviolet or visible light to excite these electrons to higher anti-bonding molecular orbitals; the more excited the electrons, the longer the wavelength of light it can absorb. There are four possible types of transitions, they can be ordered as follows: σ–σ* > n–σ* > π–π* > n–π*.
UV/Vis spectroscopy is used in analytical chemistry for the quantitative determination of different analytes, such as transition metal ions conjugated organic compounds, biological macromolecules. Spectroscopic analysis is carried out in solutions but solids and gases may be studied. Solutions of transition metal ions can be colored because d electrons within the metal atoms can be excited from one electronic state to another; the colour of metal ion solutions is affected by the presence of other species, such as certain anions or ligands. For instance, the colour of a dilute solution of copper sulfate is a light blue. Organic compounds those with a high degree of conjugation absorb light in the UV or visible regions of the electromagnetic spectrum; the solvents for these determinations are water for water-soluble compounds, or ethanol for organic-soluble compounds. Solvent polarity and pH can affect the absorption spectrum of an organic compound. Tyrosine, for example, increases in absorption maxima and molar extinction coefficient when pH increases from 6 to 13 or when solvent polarity decreases.
While charge transfer complexes give rise to colours, the colours are too intense to be used for quantitative measurement. The Beer–Lambert law states that the absorbance of a solution is directly proportional to the concentration of the absorbing species in the solution and the path length. Thus, for a fixed path length, UV/Vis spectroscopy can be used to determine the concentration of the absorber in a solution, it is necessary to know how the absorbance changes with concentration. This can be taken from references, or more determined from a calibration curve. A UV/Vis spectrophotometer may be used as a detector for HPLC; the presence of an analyte gives. For accurate results, the instrument's response to the analyte in the unknown should be compared with the response to a standard; the response for a particular concentration is known as the response factor. The wavelengths of absorption peaks can be correlated with the types of bonds in a given molecule and are valuable in determining the functional groups within a molecule.
The Woodward–Fieser rules, for instance, are a set of empirical observations used to predict λmax, the wavelength of the most intense UV/Vis absorption, for conjugated organic compounds such as dienes and ketones. The spectrum alone is not, however, a specific test for any given sample; the nature of the solvent, the pH of the solution, high electrolyte concentrations, the presence of interfering substances can influence the absorption spectrum. Experimental variations such as the slit width of the spectrophotometer will alter the spectrum. To apply UV/Vis spectroscopy to analysis, these variables must be controlled or accounted for in order to identify the substances present; the method is most used in a quantitative way to determine concentrations of an absorbing species in solution, using the Beer–Lambert law: A = log 10 = ε c L,where A is the measured absorbance, I 0 is the intensity of the incident light at a given wavelength, I is the transmitted intensity, L the path length through the sample, c the concentration of the absorbing species.
For each species and wavelength, ε is a constant known as the molar absorptivity or extinction coefficient. This constant is a fundamental molecular property in a given solvent, at a particular temperature and pressure, has units of 1 / M ∗ c m; the absorbance and extinction ε are sometimes defined in terms of the natural logarithm instead of the base-10 logarithm. The Beer–Lambert Law is useful for characterizing many compounds but does not hold as a universal relationship for the concentration and absorption of all s
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 environmental pressure. A liquid in a partial vacuum has a lower boiling point than when that liquid is at atmospheric pressure. A liquid at high pressure has a higher boiling point than when that liquid is at atmospheric pressure. For example, water at 93.4 °C at 1,905 metres altitude. For a given pressure, different liquids will boil at different temperatures; the normal boiling point of a liquid is the special case in which the vapor pressure of the liquid equals the defined atmospheric pressure at sea level, 1 atmosphere. At that temperature, the vapor pressure of the liquid becomes sufficient to overcome atmospheric pressure and allow bubbles of vapor to form inside the bulk of the liquid; the standard boiling point has been defined by IUPAC since 1982 as the temperature at which boiling occurs under a pressure of 1 bar.
The heat of vaporization is the energy required to transform a given quantity of a substance from a liquid into a gas at a given pressure. Liquids may change to a vapor at temperatures below their boiling points through the process of evaporation. Evaporation is a surface phenomenon in which molecules located near the liquid's edge, not contained by enough liquid pressure on that side, escape into the surroundings as vapor. On the other hand, boiling is a process in which molecules anywhere in the liquid escape, resulting in the formation of vapor bubbles within the liquid. A saturated liquid contains as much thermal energy. Saturation temperature means boiling point; the saturation temperature is the temperature for a corresponding saturation pressure at which a liquid boils into its vapor phase. The liquid can be said to be saturated with thermal energy. Any addition of thermal energy results in a phase transition. If the pressure in a system remains constant, a vapor at saturation temperature will begin to condense into its liquid phase as thermal energy is removed.
A liquid at saturation temperature and pressure will boil into its vapor phase as additional thermal energy is applied. The boiling point corresponds to the temperature at which the vapor pressure of the liquid equals the surrounding environmental pressure. Thus, the boiling point is dependent on the pressure. Boiling points may be published with respect to the NIST, USA standard pressure of 101.325 kPa, or the IUPAC standard pressure of 100.000 kPa. At higher elevations, where the atmospheric pressure is much lower, the boiling point is lower; the boiling point increases with increased pressure up to the critical point, where the gas and liquid properties become identical. The boiling point cannot be increased beyond the critical point; the boiling point decreases with decreasing pressure until the triple point is reached. The boiling point cannot be reduced below the triple point. If the heat of vaporization and the vapor pressure of a liquid at a certain temperature are known, the boiling point can be calculated by using the Clausius–Clapeyron equation, thus: T B = − 1, where: T B is the boiling point at the pressure of interest, R is the ideal gas constant, P is the vapour pressure of the liquid at the pressure of interest, P 0 is some pressure where the corresponding T 0 is known, Δ H vap is the heat of vaporization of the liquid, T 0 is the boiling temperature, ln is the natural logarithm.
Saturation pressure is the pressure for a corresponding saturation temperature at which a liquid boils into its vapor phase. Saturation pressure and saturation temperature have a direct relationship: as saturation pressure is increased, so is saturation temperature. If the temperature in a system remains constant, vapor at saturation pressure and temperature will begin to condense into its liquid phase as the system pressure is increased. A liquid at saturation pressure and temperature will tend to flash into its vapor phase as system pressure is decreased. There are two conventions regarding the standard boiling point of water: The normal boiling point is 99.97 °C at a pressure of 1 atm. The IUPAC recommended standard boiling point of water at a standard pressure of 100 kPa is 99.61 °C. For comparison, on top of Mount Everest, at 8,848 m elevation, the pressure is about 34 kPa and the boiling point of water is 71 °C; the Celsius temperature scale was defined until 1954 by two points: 0 °C being defined by the wate
The flash point of a volatile material is the lowest temperature at which vapours of the material will ignite, when given an ignition source. The flash point is sometimes confused with the autoignition temperature, the temperature that results in spontaneous autoignition; the fire point is the lowest temperature at which vapors of the material will keep burning after the ignition source is removed. The fire point is higher than the flash point, because at the flash point more vapor may not be produced enough to sustain combustion. Neither flash point nor fire point depends directly on the ignition source temperature, but ignition source temperature is far higher than either the flash or fire point; the flash point is a descriptive characteristic, used to distinguish between flammable fuels, such as petrol, combustible fuels, such as diesel. It is used to characterize the fire hazards of fuels. Fuels which have a flash point less than 37.8 °C are called flammable, whereas fuels having a flash point above that temperature are called combustible.
All liquids have a specific vapor pressure, a function of that liquid's temperature and is subject to Boyle's Law. As temperature increases, vapor pressure increases; as vapor pressure increases, the concentration of vapor of a flammable or combustible liquid in the air increases. Hence, temperature determines the concentration of vapor of the flammable liquid in the air. A certain concentration of a flammable or combustible vapor is necessary to sustain combustion in air, the lower flammable limit, that concentration is different and is specific to each flammable or combustible liquid; the flash point is the lowest temperature at which there will be enough flammable vapor to induce ignition when an ignition source is applied There are two basic types of flash point measurement: open cup and closed cup. In open cup devices, the sample is contained in an open cup, heated and, at intervals, a flame brought over the surface; the measured flash point will vary with the height of the flame above the liquid surface and, at sufficient height, the measured flash point temperature will coincide with the fire point.
The best-known example is the Cleveland open cup. There are two types of closed cup testers: non-equilibrial, such as Pensky-Martens, where the vapours above the liquid are not in temperature equilibrium with the liquid, equilibrial, such as Small Scale, where the vapours are deemed to be in temperature equilibrium with the liquid. In both these types, the cups are sealed with a lid through which the ignition source can be introduced. Closed cup testers give lower values for the flash point than open cup and are a better approximation to the temperature at which the vapour pressure reaches the lower flammable limit; the flash point is an empirical measurement rather than a fundamental physical parameter. The measured value will vary with equipment and test protocol variations, including temperature ramp rate, time allowed for the sample to equilibrate, sample volume and whether the sample is stirred. Methods for determining the flash point of a liquid are specified in many standards. For example, testing by the Pensky-Martens closed cup method is detailed in ASTM D93, IP34, ISO 2719, DIN 51758, JIS K2265 and AFNOR M07-019.
Determination of flash point by the Small Scale closed cup method is detailed in ASTM D3828 and D3278, EN ISO 3679 and 3680, IP 523 and 524. CEN/TR 15138 Guide to Flash Point Testing and ISO TR 29662 Guidance for Flash Point Testing cover the key aspects of flash point testing. Gasoline is a fuel used in a spark-ignition engine; the fuel is mixed with air within its flammable limits and heated by compression and subject to Boyle's Law above its flash point ignited by the spark plug. To ignite, the fuel must have a low flash point, but in order to avoid preignition caused by residual heat in a hot combustion chamber, the fuel must have a high autoignition temperature. Diesel fuel flash points vary between 52 and 96 °C. Diesel is suitable for use in a compression-ignition engine. Air is compressed until it has been heated above the autoignition temperature of the fuel, injected as a high-pressure spray, keeping the fuel–air mix within flammable limits. In a diesel-fueled engine, there is no ignition source.
Diesel fuel must have a high flash point and a low autoignition temperature. Jet fuel flash points vary with the composition of the fuel. Both Jet A and Jet A-1 have flash points between 38 and 66 °C, close to that of off-the-shelf kerosene, yet both Jet B and JP-4 have flash points between −23 and −1 °C. Flash points of substances are measured according to standard test methods described and defined in a 1938 publication by T. L. Ainsley of South Shields entitled "Sea Transport of Petroleum"; the test methodology defines the apparatus required to carry out the measurement, key test parameters, the procedure for the operator or automated apparatus to follow, the precision of the test method. Standard test methods are written and controlled by a number of national and international committees and organizations; the three main bodies are the CEN / ISO Joint Working Group on Flash Point, ASTM D02.8B Flammability Section and the Energy Institute's TMS SC-B-4 Flammability Panel. Autoignition temperature Fire point Safety data sheet
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 can be conceptualized as quantifying the frictional force that arises between adjacent layers of fluid that are in relative motion. For instance, when a fluid is forced through a tube, it flows more near the tube's axis than near its walls. In such a case, experiments show; this is because a force is required to overcome the friction between the layers of the fluid which are in relative motion: the strength of this force is proportional to the viscosity. A fluid that has no resistance to shear stress is known as an inviscid fluid. Zero viscosity is observed only at low temperatures in superfluids. Otherwise, the second law of thermodynamics requires all fluids to have positive viscosity. A fluid with a high viscosity, such as pitch, may appear to be a solid; the word "viscosity" is derived from the Latin "viscum", meaning mistletoe and a viscous glue made from mistletoe berries.
In materials science and engineering, one is interested in understanding the forces, or stresses, involved in the deformation of a material. For instance, if the material were a simple spring, the answer would be given by Hooke's law, which says that the force experienced by a spring is proportional to the distance displaced from equilibrium. Stresses which can be attributed to the deformation of a material from some rest state are called elastic stresses. In other materials, stresses are present which can be attributed to the rate of change of the deformation over time; these are called. For instance, in a fluid such as water the stresses which arise from shearing the fluid do not depend on the distance the fluid has been sheared. Viscosity is the material property which relates the viscous stresses in a material to the rate of change of a deformation. Although it applies to general flows, it is easy to visualize and define in a simple shearing flow, such as a planar Couette flow. In the Couette flow, a fluid is trapped between two infinitely large plates, one fixed and one in parallel motion at constant speed u.
If the speed of the top plate is low enough in steady state the fluid particles move parallel to it, their speed varies from 0 at the bottom to u at the top. Each layer of fluid moves faster than the one just below it, friction between them gives rise to a force resisting their relative motion. In particular, the fluid applies on the top plate a force in the direction opposite to its motion, an equal but opposite force on the bottom plate. An external force is therefore required in order to keep the top plate moving at constant speed. In many fluids, the flow velocity is observed to vary linearly from zero at the bottom to u at the top. Moreover, the magnitude F of the force acting on the top plate is found to be proportional to the speed u and the area A of each plate, inversely proportional to their separation y: F = μ A u y; the proportionality factor μ is the viscosity of the fluid, with units of Pa ⋅ s. The ratio u / y is called the rate of shear deformation or shear velocity, is the derivative of the fluid speed in the direction perpendicular to the plates.
If the velocity does not vary linearly with y the appropriate generalization is τ = μ ∂ u ∂ y, where τ = F / A, ∂ u / ∂ y is the local shear velocity. This expression is referred to as Newton's law of viscosity. In shearing flows with planar symmetry, it is what defines μ, it is a special case of the general definition of viscosity, which can be expressed in coordinate-free form. Use of the Greek letter mu for the viscosity is common among mechanical and chemical engineers, as well as physicists. However, the Greek letter eta is used by chemists and the IUPAC; the viscosity μ is sometimes referred to as the shear viscosity. However, at least one author discourages the use of this terminology, noting that μ can appear in nonshearing flows in addition to shearing flows. In general terms, the viscous stresses in a fluid are defined as those resulting from the relative velocity of different fluid particles; as such, the viscous stresses. If the velocity gradients are small to a first approximation the v
Vapor pressure or equilibrium vapor pressure is defined as 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 evaporation rate, it relates to the tendency of particles to escape from the liquid. A substance with a high vapor pressure at normal temperatures is 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 kinetic energy of its molecules increases; as the kinetic energy of the molecules increases, the number of molecules transitioning into a vapor increases, thereby increasing the vapor pressure. The vapor pressure of any substance increases non-linearly with temperature according to the Clausius–Clapeyron relation; the atmospheric pressure boiling point of a liquid is the temperature at which the vapor pressure equals the ambient atmospheric pressure.
With any incremental increase in that temperature, the vapor pressure becomes sufficient to overcome atmospheric pressure and lift the liquid to form vapor bubbles inside the bulk of the substance. Bubble formation deeper in the liquid requires a higher temperature due to the higher fluid pressure, because fluid pressure increases above the atmospheric pressure as the depth increases. More important at shallow depths is the higher temperature required to start bubble formation; the surface tension of the bubble wall leads to an overpressure in the small, initial bubbles. Thus, thermometer calibration should not rely on the temperature in boiling water; the vapor pressure that a single component in a mixture contributes to the total pressure in the system is called partial pressure. For example, air at sea level, saturated with water vapor at 20 °C, has partial pressures of about 2.3 kPa of water, 78 kPa of nitrogen, 21 kPa of oxygen and 0.9 kPa of argon, totaling 102.2 kPa, making the basis for standard atmospheric pressure.
Vapor pressure is measured in the standard units of pressure. The International System of Units recognizes pressure as a derived unit with the dimension of force per area and designates the pascal as its standard unit. One pascal is one newton per square meter. Experimental measurement of vapor pressure is a simple procedure for common pressures between 1 and 200 kPa. Most accurate results are obtained near the boiling point of substances and large errors result for measurements smaller than 1kPa. Procedures consist of purifying the test substance, isolating it in a container, evacuating any foreign gas measuring the equilibrium pressure of the gaseous phase of the substance in the container at different temperatures. Better accuracy is achieved when care is taken to ensure that the entire substance and its vapor are at the prescribed temperature; this is done, as with the use of an isoteniscope, by submerging the containment area in a liquid bath. Low vapor pressures of solids can be measured using the Knudsen effusion cell method.
In a medical context, vapor pressure is sometimes expressed in other units millimeters of mercury. This is important for volatile anesthetics, most of which are liquids at body temperature, but with a high vapor pressure. Anesthetics with a higher vapor pressure at body temperature will be excreted more as they are exhaled from the lungs; the Antoine equation is a mathematical expression of the relation between the vapor pressure and the temperature of pure liquid or solid substances. The basic form of the equation is: log P = A − B C + T and it can be transformed into this temperature-explicit form: T = B A − log P − C where: P is the absolute vapor pressure of a substance T is the temperature of the substance A, B and C are substance-specific coefficients log is either log 10 or log e A simpler form of the equation with only two coefficients is sometimes used: log P = A − B T which can be transformed to: T = B A − log P Sublimations and vaporizations of the same substance have separate sets of Antoine coefficients, as do components in mixtures.
Each parameter set for a specific compound is only applicable over a specified temperature range. Temperature ranges are chosen to maintain the equation's accuracy of a few up to 8–10 percent. For many volatile substances, several different sets of parameters are available and used for different temperature ranges; the Antoine equation has poor accuracy with any single parameter set when used from a compound's melting point to its critical temperature. Accuracy is usually poor when vapor pressure is under 10 Torr because of the limitations of the apparatus used to establish the Antoine parameter values; the Wagner equation gives "o