Analytical chemistry



Analytical chemistry The science of chemical characterization and measure­ment. Qualitative analysis is concerned with the description of chemical composition in terms of elements, compounds, or structural units, whereas quantitative analysis is concerned with the measurement of amount.

Analytical chemistry, once limited to the determination of chemical composition in terms of the relative amounts of elements or compounds in a sample, has been expanded to involve the spatial distribution of elements or compounds in a sample, the distinction between different crystalline forms of a given element or compound, the distinction between different chemical forms (such as the oxidation state of an element), the distinction between a component on the surface or in the interior of a particle, and the detection of single atoms on a surface. To permit these more detailed questions to be answered, as well as to improve the speed, accuracy, sensitivity, and selectivity of traditional analysis, a large variety of physical measurements are used. These methods are based on spectroscopic, electrochemical, chromatographic, chemical, and nuclear principles.

Modern analysis has also placed significant demands on sampling techniques. It has become necessary, for example, to handle very small liquid samples [in the nanoliter (10-9 liter) range or less] as part of the analysis of complex mixtures such as biological fluids and to simultaneously determine many different components. The sample may be a solid that must be converted through vaporization into a form suitable for analysis.

Spectroscopy includes the measurement of emission, absorption, reflection, and scattering phenomena resulting from interaction of a sample with gamma rays and x-rays at the high-energy end of the spectrum and with the less energetic ultraviolet, visible, infrared, and microwave radiation.

Lower-energy forms of excitation such as ultraviolet, visible, or infrared radiation are used in molecular spectroscopy. Ultraviolet radiation and visible radiation, which are reflective of the electronic structure of molecules, are used extensively for quantita­tive analysis. The radiation absorbed by the sample is measured. It is also possible to measure the radiation emitted (fluorescence). The absorption of infrared radiation is controlled by the properties of bonds between atoms, and it is accordingly most widely used for structure identification and determination. It is not widely used for quantita­tive analysis except for gases such as carbon monoxide (CO) and hydrocarbons. X-rays are used through emission of characteristic radiation, absorption, or diffraction. In the last case, characteristic diffraction patterns reveal information about specific structural entities, such as a particular crystalline form. Extended x-ray absorption fine structure (EXAFS) is based on the use of x-rays from a synchrotron source to reveal structural de­tails such as interatomic distances. Though not strictly a spectroscopic technique, mass spectrometry is an important and increasingly applied method of analysis, especially for organic and biological samples. Among the applications are the analysis of more than 70 elements (spark-source mass spectrometry), surface analysis (secondary ion mass spectrometry and ion-probe mass spectrometry), and the determination of the structure of organic molecules and of proteins and peptides (high-resolution mass spectrometry Nuclear magnetic resonance measures the magnetic environment around individual atoms and provides one of the most important means for deducing the structure of a molecule. Atoms possessing nuclear spin are probed by monitoring the interaction between their nuclear spin and an applied external magnetic field. For large molecules these interactions are complex, and a variety of nuclear excitation techniques have been developed that permit establishment of the connectivity between the various atoms in a molecule. Since the technique is nondestructive, it can be used to monitor living systems.

Several forms of spectroscopy are especially useful for surface analysis. The scanning electron microscope (SEM) involves a finely collimated electron beam that sweeps across the surface to produce an image. At the same time the surface atoms are excited to emit characteristic x-rays, thus making it possible to obtain an image of the surface along with its spatially resolved elemental composition. The resolution of this technique (electron microprobe) is in the micrometer (10-4 cm) range. Images with a resolution of angstroms (10-8 cm) have been obtained by using the techniques of atomic force microscopy (AFM) and scanning tunneling microscopy (STM), which correspond to the dimensions of individual atoms. A significant advantage of the latter two techniques is that a high vacuum is not required, so samples can be analyzed at atmospheric pressure.

Potentiometry is the most widely applied electrochemical technique, since it includes a variety of ion-selective electrodes, the most important of which is the glass electrode used to measure pH. Other important ion-selective electrodes measure ions of sodium, potassium, calcium, sulfide, chloride, and fluoride. When the electrodes are used in conjunction with gas-permeable membranes, gases such as ammonia, carbon dioxide, and hydrogen sulfide can be measured. Separation techniques include the various forms of chromatography and elec­trophoresis. They are based on the separation of a mixture of species in a sample due to differential migration. Two forces act in opposition: a stationary phase acts to retard a migrating species, while the mobile phase tends to promote migration. The mobile phase may be liquid (liquid chromatography) or gaseous (gas chromatogra­phy), while the stationary phase may be a solid or a solid covered with a thin film of liquid. The stationary phase is typically packed in a column through which the mo­bile phase is pumped. High-performance liquid chromatography (HPLC) has become especially important for the separation of complex mixtures of nonvolatile materials. Separations may often be accomplished in a matter of several minutes. The stationary phase can preferentially interact with the migrating species according to charge, size, hydrophobicity, or in some cases because of the special affinity which a species has for the stationary phase (affinity chromatography). The stationary phase can also be a thin layer of solid support deposited on a plate (thin-layer chromatography).

Alternatively, the driving force for separation will be the migration of charged species in an electric field (electrophoresis). The stationary phase may be a gel on a plate or in a tube, or a solution maintained in a capillary through which the analytes move. The important techniques in this area are capillary electrophoresis, isotachophoresis, and isoelectric focusingThermal methods are based on the heating of a sample over a range of temperatures.

This approach may result in absorption of heat by the sample or in evolution of heat due to physical or chemical changes. Thermogravimetry involves the measurement of mass; differential thermal analysis involves a detection of chemical or physical processes through a measurement of the difference in temperature between a sample and a stable reference material; differential thermal calorimetry evaluates the heat evolved in such processes. A variety of calorimetric techniques are used to measure the extent of reactions that are otherwise difficult to evaluate.



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