For thermally robust materials, high temperature methods are often employed. For example, bulk solids are prepared using tube furnaces, which allow reactions to be conducted up to ca. 1100 °C. Special equipment e.g. ovens consisting of a tantalum tube through which an electric current is passed can be used for even higher temperatures up to 2000 °C. Such high temperatures are at times required to induce diffusion of the reactants, but this depends strongly on the system studied. Some solid state reactions already proceed at temperatures as low as 100 °C.
One method often employed is to melt the reactants together and then later anneal the solidified melt. If volatile reactants are involved the reactants are often put in an ampoule that is evacuated -often while keeping the reactant mixure cold e.g. by keeping the bottom of the ampoule in liquid nitrogen- and then sealed. The sealed ampoule is then put in an oven and given a certain heat treatment.
It is possible to use solvents to prepare solids by precipitation or by evaporation. At times the solvent is used hydrothermally, i.e. under pressure at temperatures higher than the normal boiling point. A variation on this theme is the use of flux methods, where a salt of relatively low melting point is added to the mixture to act as a high temperature solvent in which the desired reaction can take place.
Many solids react readily with reactive gas species like chlorine, iodine, oxygen etc. Others form adducts with other gases, e.g. CO or ethylene. Such reactions are often carried out in a tube that is open ended on both sides and through which the gas is passed. A variation of this is to let the reaction take place inside a measuring device such as a TGA. In that case stoechimetric information can be obtained during the reaction, which helps identify the products.
A special case of a gas reaction is a chemical transport reaction. These are often carried out in a sealed ampoule to with a small amount of a transport agent, e.g. iodine is added. The ampoule is then placed in a zone oven. This is essentially two tube ovens attached to each other which allows a temperature grandient to be imposed. Such a method can be used to obtain the product in the form of single crystals suitable for structure determination by X-ray diffraction.
Many solids are hygroscopic and/or oxygen sensitive. Many halides e.g. are very 'thirsty' and can only be studied in their anhydrous form if they are handled in a glove box filled with dry (and/or oxygen-free) gas, usually nitrogen.
The synthetic methodology and the characterization of the product often go hand in hand in the sense that not one but a series of reaction mixtures are prepared and subjected to heat treatment. The stoechiometry is typically varied in a systematic way to find which stoechiometries will lead to new solid compounds or to solid solutions between known ones. A prime method to characterize the reaction products is powder diffraction, because many solid state reactions will produce polycristalline ingots or powders. Powder diffraction will facilitate the identification of known phases in the mixture. If a pattern is found that is not known in the diffraction data libraries an attempt can be made to index the pattern, i.e. to identify the symmetry and the size of the unit cell. (If the product is not crystalline the characterization is typically much more difficult.)
Once the unit cell of a new phase is known, the next step is to establish the stoichiometry of the phase. This can be done in a number of ways. Sometimes the composition of the original mixture will give a clue, if one finds only one product -a single powder pattern- or if one was trying to make a phase of a certain composition by analogy to known materials but this is rare. Often considerable effort in refining the synthetic methodology is required to obtain a pure sample of the new material. If it is possible to separate the product from the rest of the reaction mixture elemental analysis can be used. Another ways involves SEM and the generation of characteristic X-rays in the electron beam. The easiest way is to solve the structure is by using single crystal X-ray diffraction.
The latter often requires revisiting and refining the preparative procedures and that is linked to the question which phases are stable at what composition and what stoichiometry. In other words what does the phase diagram looks like . An important tool in establishing this is thermal analysis techniques like DSC or DTA and increasingly also, thanks to the advent of synchrotrons temperature-dependent power diffraction. Increased knowledge of the phase relations often leads to further refinement in synthetic procedures in an iterative way. New phases are thus characterized by their melting points and their stoichiometric domains. The latter is important for the many solids that are non-stoichiometric compounds. The cell parameters obtained from XRD are particularly helpful to characterize the homogeneity ranges of the latter.
In many -but certainly not all- cases new solid compounds are further characterized by a variety of techniques that straddle the fine line that (hardly) separates solid-state chemistry from solid-state physics.
For non-metallic materials it is often possible to obtain UV/VIS spectra. In the case of semiconductors that will give an idea of the band gap.
Four-point (or five-point) probe methods are often applied either to ingots, crystals or pressed pellets to measure resistivity and the size of the Hall-effect. This gives information on whether the compound is an insulator, semiconductor, semimetal or metal and upon the type of doping and the mobility in the delocalized bands (if present). Thus important information is obtained on the chemical bonding in the material.
Magnetic susceptibility can be measured as function of temperature to establish whether the material is a para-, ferro- or antiferro- magnet. Again the information obtained pertains to the bonding in the material. This is particularly important for transition metal compounds. In the case of magnetic order neutron diffraction can be used to determine the magnetic structure.
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