Single-crystal X-ray Diffraction

Single-crystal X-ray Diffraction is a non-destructive analytical technique which

provides detailed information about the internal lattice of crystalline substances, including
unit cell dimensions, bond-lengths, bond-angles, and details of site-ordering. Directly related
is single-crystal refinement, where the data generated from the X-ray analysis is interpreted
and refined to obtain the crystal structure.
X-ray diffractometers consist of three basic elements, an X-ray tube, a sample holder,
and an X-ray detector. X-rays are generated in a cathode ray tube by heating a filament to
produce electrons, accelerating the electrons toward a target by applying a voltage, and
impact of the electrons with the target material. When electrons have sufficient energy to
dislodge inner shell electrons of the target material, characteristic X-ray spectra are produced.
These spectra consist of several components, the most common being K and K. K consists,
in part, of K1 and K2. K1 has a slightly shorter wavelength and twice the intensity as K 2.
The specific wavelengths are characteristic of the target material. Filtering, by foils or crystal
monochromators, is required to produce monochromatic X-rays needed for diffraction.
K1and K2 are sufficiently close in wavelength such that a weighted average of the two is
used. Molybdenum is the most common target material for single-crystal diffraction, with
MoK radiation = 0.7107. These X-rays are collimated and directed onto the sample. When
the geometry of the incident X-rays impinging, the sample satisfies the Bragg Equation,
constructive interference occurs. A detector records and processes this X-ray signal and
converts the signal to a count rate which is then output to a device such as a printer or
computer monitor. X-rays may also be produced using a synchrotron, which emits a much
stronger beam.

Chemisorption and physisorption

Chemisorption (or chemical adsorption) is adsorption in which the forces involved
are valence forces of the same kind as those operating in the formation of chemical
compounds. The problem of distinguishing between chemisorption and physisorption (see
below) is basically the same as that of distinguishing between chemical and physical
interaction in general. No absolutely sharp distinction can be made and intermediate cases
exist, for example, adsorption involving strong hydrogen bonds or weak charge transfer.
Some features which are useful in recognizing chemisorption include:
1. the phenomenon is characterized by chemical specificity;
2. changes in the electronic state may be detectable by suitable physical means (e.g. u.v.,
infrared or microwave spectroscopy, electrical conductivity, magnetic susceptibility);
3. the chemical nature of the adsorptive(s) may be altered by surface dissociation or
reaction in such a way that on desorption the original species cannot be recovered; in
this sense chemisorption, may not be reversible;
4. the energy of chemisorption is of the same order of magnitude as the energy change in
a chemical reaction between a solid and a fluid: thus chemisorption, like chemical
reactions in general, may be exothermic or endothermic and the magnitudes of the
energy changes may range from very small to very large;
5. the elementary step in chemisorption often involves an activation energy;
6. since the adsorbed molecules are linked to the surface by valence bonds, they will
usually occupy certain adsorption sites on the surface and only one layer of
chemisorbed molecules is formed (monolayer adsorption).
Physisorption (or physical adsorption) is adsorption in which the forces involved are
intermolecular forces (van der Waals forces) of the same kind as those responsible for the
imperfection of real gases and the condensation of vapors, and which do not involve a

significant change in the electronic orbital patterns of the species involved. The term van der
Waals adsorption is synonymous with physical adsorption, but its use is not recommended.
Some features which are useful in recognizing physisorption include:
1. the phenomenon is a general one and occurs in any solid/fluid system, although
certain specific molecular interactions may occur, arising from geometrical or
electronic properties of the adsorbent and/or adsorptive;
2. evidence for the perturbation of the electronic states of adsorbent and adsorbate is
minimal;
3. the adsorbed species are chemically identical with those in the fluid phase, so that the
chemical nature of the fluid is not altered by adsorption and subsequent desorption;
4. the energy of interaction between the molecules of adsorbate and the adsorbent is of
the same order of magnitude as, but is usually greater than, the energy of
condensation of the adsorptive;