Infrared spectroscopy
Infrared spectroscopy involves the interaction of infrared radiation with matter. It covers a range of techniques based on absorption spectroscopy; as with all spectroscopic techniques, it can be used to study chemicals. Samples may be liquid, or gas; the method or technique of infrared spectroscopy is conducted with an instrument called an infrared spectrometer to produce an infrared spectrum. An IR spectrum can be visualized in a graph of infrared light absorbance on the vertical axis vs. frequency or wavelength on the horizontal axis. Typical units of frequency used in IR spectra are reciprocal centimeters, with the symbol cm−1. Units of IR wavelength are given in micrometers, symbol μm, which are related to wave numbers in a reciprocal way. A common laboratory instrument that uses this technique is a Fourier transform infrared spectrometer. Two-dimensional IR is possible as discussed below; the infrared portion of the electromagnetic spectrum is divided into three regions. The higher-energy near-IR 14000–4000 cm−1 can excite overtone or harmonic vibrations.
The mid-infrared 4000–400 cm−1 may be used to study the fundamental vibrations and associated rotational-vibrational structure. The far-infrared 400–10 cm−1, lying adjacent to the microwave region, has low energy and may be used for rotational spectroscopy; the names and classifications of these subregions are conventions, are only loosely based on the relative molecular or electromagnetic properties. Infrared spectroscopy exploits the fact that molecules absorb frequencies that are characteristic of their structure; these absorptions occur at resonant frequencies, i.e. the frequency of the absorbed radiation matches the vibrational frequency. The energies are affected by the shape of the molecular potential energy surfaces, the masses of the atoms, the associated vibronic coupling. In particular, in the Born–Oppenheimer and harmonic approximations, i.e. when the molecular Hamiltonian corresponding to the electronic ground state can be approximated by a harmonic oscillator in the neighborhood of the equilibrium molecular geometry, the resonant frequencies are associated with the normal modes corresponding to the molecular electronic ground state potential energy surface.
The resonant frequencies are related to the strength of the bond and the mass of the atoms at either end of it. Thus, the frequency of the vibrations are associated with a particular normal mode of motion and a particular bond type. In order for a vibrational mode in a sample to be "IR active", it must be associated with changes in the dipole moment. A permanent dipole is not necessary. A molecule can vibrate in many ways, each way is called a vibrational mode. For molecules with N number of atoms, linear molecules have 3N – 5 degrees of vibrational modes, whereas nonlinear molecules have 3N – 6 degrees of vibrational modes; as an example H2O, a non-linear molecule, will have 3 × 3 – 6 = 3 degrees of vibrational freedom, or modes. Simple diatomic molecules have only one vibrational band. If the molecule is symmetrical, e.g. N2, the band is not observed in the IR spectrum, but only in the Raman spectrum. Asymmetrical diatomic molecules, e.g. CO, absorb in the IR spectrum. More complex molecules have many bonds, their vibrational spectra are correspondingly more complex, i.e. big molecules have many peaks in their IR spectra.
The atoms in a CH2X2 group found in organic compounds and where X can represent any other atom, can vibrate in nine different ways. Six of these vibrations involve only the CH2 portion: symmetric and antisymmetric stretching, rocking and twisting, as shown below. Structures that do not have the two additional X groups attached have fewer modes because some modes are defined by specific relationships to those other attached groups. For example, in water, the rocking and twisting modes do not exist because these types of motions of the H represent simple rotation of the whole molecule rather than vibrations within it; these figures do not represent the "recoil" of the C atoms, though present to balance the overall movements of the molecule, are much smaller than the movements of the lighter H atoms. The simplest and most important or fundamental IR bands arise from the excitations of normal modes, the simplest distortions of the molecule, from the ground state with vibrational quantum number v = 0 to the first excited state with vibrational quantum number v = 1.
In some cases, overtone bands are observed. An overtone band arises from the absorption of a photon leading to a direct transition from the ground state to the second excited vibrational state; such a band appears at twice the energy of the fundamental band for the same normal mode. Some excitations, so-called combination modes, involve simultaneous excitation of more than one normal mode; the phenomenon of Fermi resonance can arise. The infrared spectrum of a sample is recorded by passing a beam of infrared light through the sample; when the frequency of the IR is the same as the vibrational frequency of a bond or collection of bonds, absorption occurs. Examination of the transmitted light reveals; this mea
Hydrate
In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies between different classes of hydrates, some of which were so labeled before their chemical structure was understood. In organic chemistry, a hydrate is a compound formed by the addition of water or its elements to another molecule. For example: ethanol, CH3–CH2–OH, is the product of the hydration reaction of ethene, CH2=CH2, formed by the addition of H to one C and OH to the other C, so can be considered as the hydrate of ethene. A molecule of water may be eliminated, for example by the action of sulfuric acid. Another example is chloral hydrate, CCl3–CH2, which can be formed by reaction of water with chloral, CCl3–CH=O. Many organic molecules, as well as inorganic molecules, form crystals that incorporate water into the crystalline structure without chemical alteration of the organic molecule; the sugar trehalose, for example, exists as a dihydrate. Protein crystals have as much as 50% water content.
Molecules are labeled as hydrates for historical reasons not covered above. Glucose, C6H12O6, was thought of as C66 and described as a carbohydrate. Methanol is sold as "methyl hydrate", implying the incorrect formula CH3OH2, while the correct formula is CH3–OH. Hydrates are inorganic salts "containing water molecules combined in a definite ratio as an integral part of the crystal" that are either bound to a metal center or that have crystallized with the metal complex; such hydrates are said to contain water of crystallization or water of hydration. If the water is heavy water, where the hydrogen involved is the isotope deuterium the term deuterate may be used in place of hydrate. A colorful example is cobalt chloride, which turns from blue to red upon hydration, can therefore be used as a water indicator; the notation "hydrated compound⋅nH2O", where n is the number of water molecules per formula unit of the salt, is used to show that a salt is hydrated. The n is a low integer, though it is possible for fractional values to occur.
For example, in a monohydrate n is one, in a hexahydrate n is 6. Numerical prefixes of Greek origin are: A hydrate which has lost water is referred to as an anhydride. A substance that does not contain any water is referred to as anhydrous; some anhydrous compounds are hydrated so that they are said to be hygroscopic and are used as drying agents or desiccants. Clathrate hydrates are water ice with gas molecules trapped within. An important example is methane hydrate. Nonpolar molecules such as methane can form clathrate hydrates with water under high pressure. Although there is no hydrogen bonding between water and guest molecules when methane is the guest molecule of the clathrate, guest-host hydrogen bonding forms when the guest is a larger organic molecule such as tetrahydrofuran. In such cases the guest-host hydrogen bonds result in the formation of L-type Bjerrum defects in the clathrate lattice; the stability of hydrates is determined by the nature of the compounds, their temperature, the relative humidity
Acid dissociation constant
An acid dissociation constant, Ka, is a quantitative measure of the strength of an acid in solution. It is the equilibrium constant for a chemical reaction known as dissociation in the context of acid–base reactions. K a =; the chemical species HA, A−, H+ are said to be in equilibrium when their concentrations do not change with the passing of time, because both forward and backward reactions are occurring at the same fast rate. The chemical equation for acid dissociation can be written symbolically as: HA ↽ − − ⇀ A − + H + where HA is a generic acid that dissociates into A−, the conjugate base of the acid and a hydrogen ion, H+, it is implicit in this definition that the quotient of activity coefficients, Γ, Γ = γ A − γ H + γ A H is a constant that can be ignored in a given set of experimental conditions. For many practical purposes it is more convenient to discuss the logarithmic constant, pKa p K a = − log 10 The more positive the value of pKa, the smaller the extent of dissociation at any given pH —that is, the weaker the acid.
A weak acid has a pKa value in the approximate range −2 to 12 in water. For a buffer solution consisting of a weak acid and its conjugate base, pKa can be expressed as: p K a = pH − log 10 The pKa for a weak monoprotic acid is conveniently determined by potentiometric titration with a strong base to the equivalence point and taking the pH value measured at one-half this volume as being equal to pKa; that is because at this half equivalence point, the number of moles of strong base added is one-half the number of moles of weak acid present, while the concentrations of the conjugate base and the remaining weak acid are the same. Acids with a pKa value of less than about −2 are said to be strong acids. In water, the dissociation of a strong acid in dilute solutions is complete such that the final concentration of the undissociated acid final is low. Consider a strong monoprotic acid, such as HCl; because of their 1:1 ratio, the final concentration of the conjugate base, final, is taken to be equal to the concentration of the hydronium ion, which can be directly measured by a pH meter.
For strong monoprotic acids like HCl, final and are both nearly equal to the initial concentration of initial placed into solution. With conventional acid-base titration methods it is difficult to measure the pH of a strong acid solution and, hence, to determine the or final, with a sufficient number of significant figures to and compute the low values encountered for final, which can be as low as 10-9 mol per liter for some strong acids. Furthermore, if 100% dissociation is assumed, final is zero and the fraction within parenthesis in the equation above becomes undefined; because the second expression on the right-hand side of the above equation is therefore indeterminable by conventional titration methods, the entire equation is not as useful a means of experimentally measuring pKa for strong acids as it is for weak acids. However, pKa and/or Ka values for strong acids can be estimated by theoretical means, such as computing gas phase dissociation constants and using Gibbs free energies of solvation for the molecular anions.
It is possible to use spectroscopy in some cases to determine the ratio of the concentrations of the conjugate base produced and the undissociated acid. For example, the Raman spectra of dilute nitric acid solutions contain signals of the nitrate ion and as the solutions become more concentrated signals of undissociated nitric acid molecules emerge; the acid dissociation constant for an acid is a direct consequence of the underlying thermodynamics of the dissociation reaction. The value of the pKa changes with temperature and can be understood qualitatively based on Le Châtelier's principle: when the reaction is endothermic, Ka increases and pKa decreases with
Safety data sheet
A safety data sheet, material safety data sheet, or product safety data sheet is a document that lists information relating to occupational safety and health for the use of various substances and products. SDSs are a used system for cataloging information on chemicals, chemical compounds, chemical mixtures. SDS information may include instructions for the safe use and potential hazards associated with a particular material or product, along with spill-handling procedures. SDS formats can vary from source to source within a country depending on national requirements. A SDS for a substance is not intended for use by the general consumer, focusing instead on the hazards of working with the material in an occupational setting. There is a duty to properly label substances on the basis of physico-chemical, health or environmental risk. Labels can include hazard symbols such as the European Union standard symbols; the same product can have different formulations in different countries. The formulation and hazard of a product using a generic name may vary between manufacturers in the same country.
The Globally Harmonized System of Classification and Labelling of Chemicals contains a standard specification for safety data sheets. The SDS follows a 16 section format, internationally agreed and for substances the SDS should be followed with an Annex which contains the exposure scenarios of this particular substance; the 16 sections are: SECTION 1: Identification of the substance/mixture and of the company/undertaking 1.1. Product identifier 1.2. Relevant identified uses of the substance or mixture and uses advised against 1.3. Details of the supplier of the safety data sheet 1.4. Emergency telephone number SECTION 2: Hazards identification 2.1. Classification of the substance or mixture 2.2. Label elements 2.3. Other hazards SECTION 3: Composition/information on ingredients 3.1. Substances 3.2. Mixtures SECTION 4: First aid measures 4.1. Description of first aid measures 4.2. Most important symptoms and effects, both acute and delayed 4.3. Indication of any immediate medical attention and special treatment needed SECTION 5: Firefighting measures 5.1.
Extinguishing media 5.2. Special hazards arising from the substance or mixture 5.3. Advice for firefighters SECTION 6: Accidental release measure 6.1. Personal precautions, protective equipment and emergency procedures 6.2. Environmental precautions 6.3. Methods and material for containment and cleaning up 6.4. Reference to other sections SECTION 7: Handling and storage 7.1. Precautions for safe handling 7.2. Conditions for safe storage, including any incompatibilities 7.3. Specific end use SECTION 8: Exposure controls/personal protection 8.1. Control parameters 8.2. Exposure controls SECTION 9: Physical and chemical properties 9.1. Information on basic physical and chemical properties 9.2. Other information SECTION 10: Stability and reactivity 10.1. Reactivity 10.2. Chemical stability 10.3. Possibility of hazardous reactions 10.4. Conditions to avoid 10.5. Incompatible materials 10.6. Hazardous decomposition products SECTION 11: Toxicological information 11.1. Information on toxicological effects SECTION 12: Ecological information 12.1.
Toxicity 12.2. Persistence and degradability 12.3. Bioaccumulative potential 12.4. Mobility in soil 12.5. Results of PBT and vPvB assessment 12.6. Other adverse effects SECTION 13: Disposal considerations 13.1. Waste treatment methods SECTION 14: Transport information 14.1. UN number 14.2. UN proper shipping name 14.3. Transport hazard class 14.4. Packing group 14.5. Environmental hazards 14.6. Special precautions for user 14.7. Transport in bulk according to Annex II of MARPOL73/78 and the IBC Code SECTION 15: Regulatory information 15.1. Safety and environmental regulations/legislation specific for the substance or mixture 15.2. Chemical safety assessment SECTION 16: Other information 16.2. Date of the latest revision of the SDS In Canada, the program known as the Workplace Hazardous Materials Information System establishes the requirements for SDSs in workplaces and is administered federally by Health Canada under the Hazardous Products Act, Part II, the Controlled Products Regulations. Safety data sheets have been made an integral part of the system of Regulation No 1907/2006.
The original requirements of REACH for SDSs have been further adapted to take into account the rules for safety data sheets of the Global Harmonised System and the implementation of other elements of the GHS into EU legislation that were introduced by Regulation No 1272/2008 via an update to Annex II of REACH. The SDS must be supplied in an official language of the Member State where the substance or mixture is placed on the market, unless the Member State concerned provide otherwise; the European Chemicals Agency has published a guidance document on the compilation of safety data sheets. The German Federal Water Management Act requires that substances be evaluated for negative influence on the physical, chemical or biological characteristics of water; these are classified into numeric water hazard classes. WGK nwg: Non-water polluting substance WGK 1: Slightly water polluting substance WGK 2: Water polluting substance WGK 3: Highly water polluting substance This section contributes to a better understanding of the regulations governing SDS within the South African framework.
As regulations may change, it is the responsibility of the reader to verify the validity of the regulations mentioned in text. As globalisation increased and countries engaged in cross-border trade, the quantity of hazardous material crossing international borders a
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 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
Melting point
The melting point of a substance is the temperature at which it changes state from solid to liquid. At the melting point the solid and liquid phase exist in equilibrium; the melting point of a substance depends on pressure and is specified at a standard pressure such as 1 atmosphere or 100 kPa. When considered as the temperature of the reverse change from liquid to solid, it is referred to as the freezing point or crystallization point; because of the ability of some substances to supercool, the freezing point is not considered as a characteristic property of a substance. When the "characteristic freezing point" of a substance is determined, in fact the actual methodology is always "the principle of observing the disappearance rather than the formation of ice", that is, the melting point. For most substances and freezing points are equal. For example, the melting point and freezing point of mercury is 234.32 kelvins. However, certain substances possess differing solid-liquid transition temperatures.
For example, agar melts at 85 °C and solidifies from 31 °C. The melting point of ice at 1 atmosphere of pressure is close to 0 °C. In the presence of nucleating substances, the freezing point of water is not always the same as the melting point. In the absence of nucleators water can exist as a supercooled liquid down to −48.3 °C before freezing. The chemical element with the highest melting point is tungsten, at 3,414 °C; the often-cited carbon does not melt at ambient pressure but sublimes at about 3,726.85 °C. Tantalum hafnium carbide is a refractory compound with a high melting point of 4215 K. At the other end of the scale, helium does not freeze at all at normal pressure at temperatures arbitrarily close to absolute zero. Many laboratory techniques exist for the determination of melting points. A Kofler bench is a metal strip with a temperature gradient. Any substance can be placed on a section of the strip, revealing its thermal behaviour at the temperature at that point. Differential scanning calorimetry gives information on melting point together with its enthalpy of fusion.
A basic melting point apparatus for the analysis of crystalline solids consists of an oil bath with a transparent window and a simple magnifier. The several grains of a solid are placed in a thin glass tube and immersed in the oil bath; the oil bath is heated and with the aid of the magnifier melting of the individual crystals at a certain temperature can be observed. In large/small devices, the sample is placed in a heating block, optical detection is automated; the measurement can be made continuously with an operating process. For instance, oil refineries measure the freeze point of diesel fuel online, meaning that the sample is taken from the process and measured automatically; this allows for more frequent measurements as the sample does not have to be manually collected and taken to a remote laboratory. For refractory materials the high melting point may be determined by heating the material in a black body furnace and measuring the black-body temperature with an optical pyrometer. For the highest melting materials, this may require extrapolation by several hundred degrees.
The spectral radiance from an incandescent body is known to be a function of its temperature. An optical pyrometer matches the radiance of a body under study to the radiance of a source, calibrated as a function of temperature. In this way, the measurement of the absolute magnitude of the intensity of radiation is unnecessary. However, known temperatures must be used to determine the calibration of the pyrometer. For temperatures above the calibration range of the source, an extrapolation technique must be employed; this extrapolation is accomplished by using Planck's law of radiation. The constants in this equation are not known with sufficient accuracy, causing errors in the extrapolation to become larger at higher temperatures. However, standard techniques have been developed to perform this extrapolation. Consider the case of using gold as the source. In this technique, the current through the filament of the pyrometer is adjusted until the light intensity of the filament matches that of a black-body at the melting point of gold.
This establishes the primary calibration temperature and can be expressed in terms of current through the pyrometer lamp. With the same current setting, the pyrometer is sighted on another black-body at a higher temperature. An absorbing medium of known transmission is inserted between this black-body; the temperature of the black-body is adjusted until a match exists between its intensity and that of the pyrometer filament. The true higher temperature of the black-body is determined from Planck's Law; the absorbing medium is removed and the current through the filament is adjusted to match the filament intensity to that of the black-body. This establishes a second calibration point for the pyrometer; this step is repeated to carry the calibration to hi
Barium oxide
Barium oxide, BaO, is a white hygroscopic non-flammable compound. It has a cubic structure and is used in cathode ray tubes, crown glass, catalysts, it is harmful to human skin and if swallowed in large quantity causes irritation. Excessive quantities of barium oxide may lead to death, it is prepared by heating barium carbonate with coke, carbon black or tar or by thermal decomposition of barium nitrate. Barium oxide is used for example, those in cathode ray tubes, it replaced lead oxide in the production of certain kinds of glass such as optical crown glass. While lead oxide raised the refractive index, it raised the dispersive power, which barium oxide does not alter. Barium oxide has use as an ethoxylation catalyst in the reaction of ethylene oxide and alcohols, which takes place between 150 and 200 °C, it is a source of pure oxygen through heat fluctuation. It oxidises to BaO2 by formation of a peroxide ion; the complete peroxidation of BaO to BaO2 occurs at moderate temperatures but the increased entropy of the O2 molecule at high temperatures means that BaO2 decomposes to O2 and BaO at 1175K.
The reaction was used as a large scale method to produce oxygen before the air separation became the dominant method in the beginning of the 20th century. The method was named after its inventors the Brin process. Barium oxide is made by heating barium carbonate, it may be prepared by thermal decomposition of barium nitrate. It is formed through the decomposition of other barium salts. 2Ba + O2 → 2BaO BaCO3 → BaO + CO2 Barium oxide is an irritant. If it contacts the skin or the eyes or is inhaled it causes redness. However, it is more dangerous, it can cause nausea and diarrhea, muscle paralysis, cardiac arrhythmia, can cause death. If ingested, medical attention should be sought immediately. Barium oxide should not be released environmentally. Barium International Chemical Safety Card 0778
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