Physical techniques in

inorganic chemistry 8
All the structures of the molecules and materials to be covered in this book have been determined Diffraction methods
by applying one or more kinds of physical technique. The techniques and instruments available 8.1 X-ray diffraction
vary greatly in complexity and cost, as well as in their suitability for meeting particular chal- 8.2 Neutron diffraction
lenges. All the methods produce data that help to determine a compound's structure, its composi-
tion, or its properties. Many of the physical techniques used in contemporary inorganic research Absorption spectroscopy
rely on the interaction of electromagnetic radiation with matter and there is hardly a section of 8.3 Ultraviolet-visible spectroscopy
the electromagnetic spectrum that is not used. In this chapter, we introduce the most important 8.4 Infrared and Raman spectroscopy
physical techniques that are used to investigate the atomic and electronic structures of inorganic
compounds and study their reactions. Resonance techniques
8.5 Nuclear magnetic resonance
8.6 Electron paramagnetic resonance
8.7 Mossbauer spectroscopy
Diffraction methods
Ionization-based techniques
Diffraction techniques, particularly those using X-rays, are the most important methods 8.8 Photoelectron spectroscopy
available to the inorganic chemist for the determination of structures. X-ray diffraction 8.9 X-ray absorption spectroscopy
has been used to determine the structures a quarter of a million different substances, in- 8.1O Mass spectrometry
cluding tens of thousands of purely inorganic compounds and many organometallic com-
pounds. The method is used to determine the positions of the atoms and ions that make up Chemical analysis
a solid compound and hence provides a description of structures in terms of features such 8.11 Atomic absorption spectroscopy
as bond lengths, bond angles, and the relative positions of ions and molecules in a unit cell. 8.12 CHN analysis
This structural information has been interpreted in terms of atomic and ionic radii, which 8.13 X-ray fluorescence elemental
then allow chemists to predict structure and explain trends in many properties. Diffraction analysis
methods are nondestructive in the sense that the sample remains unchanged and may be 8.14 Thermal analysis
analysed further by using a different technique.
Magnetometry
Electrochemical techniques
8.1 X-ray diffraction Computational techniques
Key points: The scattering of radiation with wavelengths of about 100 pm from crystals gives rise to FURTHER READING
diffraction; the interpretation of the diffraction patterns gives quantitative structural information and EXERCISES
in many cases the complete molecular or ionic structure. PROBLEMS

Diffraction is the interference between waves that occurs as a result of an object in their
path. X-rays are scattered elastically (with no change in energy) by the electrons in atoms,
and diffraction can occur for a periodic array of scattering centres separated by distances
similar to the wavelength of the radiation (about 100 pm), such as exist in a crystal. If we
think of scattering as equivalent to reflection from two adjacent parallel planes of atoms
separated by a distance d (Fig. 8.1), then the angle at which constructive interference oc-
curs (to produce a diffraction intensity maximum) between waves of wavelength A is given d
by Bragg's equation:
d sin
2d sin0 n (8.1)
Figure 8.1 Bragg's equation is derived by
where n is an integer. Thus an X-ray beam impinging on a crystalline compound with an treating layers of atoms as reflecting
ordered array of atoms will produce a set of diffraction maxima, termed a diffraction pat- planes. X-rays interfere constructively
tern, with each maximum, or reflection, occurring at an angle O corresponding to a differ- when the additional path length 2d sin O
ent separation of planes of atoms, d, in the crystal. is equal to an integral multiple of the
wavelength A.
224 8 Physical techniques in inorganic chemistry

An atom or ion scatters X-rays in proportion to the number of electrons it

possesses and the intensities of the measured diffraction maxima are proportional to
the square of that number. Thus the diffraction pattern produced is characteristic of
the positions and types (in terms of their number of electrons) of atom present in the
crystalline compound and the measurement of X-ray diffraction angles and intensities
provides structural information. Because of its dependence on the number of electrons,
X-ray diffraction is particularly sensitive to any electron-rich atoms in a compound.
Thus, X-ray diffraction by NaN03 displays all three nearly isoelectronic atoms simi-
larly, but for Pb(0H) the scattering and structural information is dominated by the
2
Pb atom.
Sample
There are two principal X-ray techniques: the powder method, in which the materi-
als being studied are in polycrystalline form, and single-crystal diffraction, in which the
sample is a single crystal of dimensions of several tens of micrometres or larger.
2
(a) Powder X-ray diffraction
X-rays
Key point: Powder X-ray diffraction is used mainly for phase identification and the determination of
Figure 8.2 A cone of diffraction that lattice parameters and lattice type.
results
from X-ray scattering by a powdered A powdered (polycrystalline) sample contains an enormous number of very small crys-
sample. The cone consists of thousands of tallites, typically 0.1 to 10 µm in dimension and orientated at random. An X-ray beam
individual diffraction spots from individual
striking a polycrystalline sample is scattered in all directions; at some angles, those
crystallites that merge together.
given by Bragg's equation, constructive interference occurs. As a result, each set of
planes of atoms with lattice spacing d gives rise to a cone of diffraction intensity. Each
X-ray tube cone consists of a set of closely spaced diffracted rays, each one of which represents
Tube focus diffraction from a single crystallite within the powder sample (Fig. 8.2). With a very
large number of crystallites these rays merge together to form the diffraction cone. A
Detector powder diffractometer (Fig. 8.3a) uses an electronic detector to measure the angles of
the diffracted beams. Scanning the detector around the sample along the circumfer-
Sample ence of a circle cuts through the diffraction cones at the various diffraction maxima
plate 2
and the intensity of the X-rays detected is recorded as a function of the detector angle
(Fig. 8.3b).
Measuring
circle The number and positions of the reflections depend on the cell parameters, crystal
(a) system, lattice type, and wavelength used to collect the data; the peak intensities depend on
the types of atoms present and their positions. Nearly all crystalline solids have a unique
powder X-ray diffraction pattern in terms of the angles of the reflections and their intensi-
ties. In mixtures of compounds, each crystalline phase present contributes to the powder
diffraction pattern its own unique set of reflection angles and intensities. Typically, the
method is sensitive enough to detect a small level (5 to 10 per cent by mass) of a particular
Diffraction intensity

crystalline component in a mixture.

8 16 24 32 40
Diffraction angle, 2 /0
(b)
Figure 8.3 (a) Schematic diagram of
a powder diffractometer operating in reflection
mode in which the X-ray scattering occurs from
a sample mounted as a flat plate. For weakly
absorbing compounds the samples may be
mounted in a capillary and
the diffraction data collected in transmission a calculated diffraction pattern to the experimental trace. The technique is not as powerful
mode. (b) The form of a typical powder
diffraction pattern showing a series of
reflections as a function of angle.
The effectiveness of powder X-ray diffraction has led to it becoming the major technique
for the characterization of polycrystalline inorganic materials (Table 8.1). Many of the
powder diffraction data sets collected from inorganic, organometallic, and organic com-
pounds have been compiled into a database by the Joint Committee on Powder Diffrac-
tion Standards (JCPDS). This database, which contains over 50 000 unique powder X-ray
diffraction patterns, can be used like a fingerprint library to identify an unknown material
from its powder pattern alone. Powder X-ray diffraction is used routinely in the investiga-
tion of phase formation and changes in structures of solids. The synthesis of a metal oxide
can be verified by collecting a powder diffraction pattern and demonstrating that the data
are consistent with a single pure phase of that material. Indeed, the progress of a chemi-
cal reaction is often monitored by observing the formation of the product phase at the
expense of the reactants.
Basic crystallographic information, such as lattice parameters, can normally be extracted
easily from powder X-ray diffraction data, usually with high precision. The presence or
absence of certain reflections in the diffraction pattern permits the determination of the
lattice type. In recent years the technique of fitting the intensities of the peaks in the dif-
fraction pattern has become a popular method of extracting structural information such
as atomic positions. The analysis, which is known as the Rietveld method, involves fitting
as the single-crystal methods, for it gives less accurate atomic positions, but has the advan-
tage of not requiring the growth of a single crystal.
 Diffraction methods 225
Table 8.1 Application of powder X-ray
diffraction
Applicatio Typical use and information
n extracted
Identification of unknown Rapid identification of most crystalline phases
materials
Monitoring the progress of a chemical
Determination of sample purity reaction occurring in the solid state
Determination and refinement Phase identification and monitoring structure
of lattice parameters as a function of composition
Investigation of phase diagrams/ Mapping out composition and structure
new materials
Determination of crystallite Particle size measurement and uses in
size/stress metallurgy

Structure refinement Extraction of crystallographic data from a

Ab initio structure known structure type
determination Structure determination (often at high
precision) is possible in some cases without
Phase changes/expansion initial knowledge
coefficients of the crystal structure
Studies as a function of temperature (cooling
or heating typically in the range 100-1200
K).
E X A M P LE 8 .1 Using powder X-ray diffraction
0bservation of structural transitions Rutile Anatase Brookite

27.50 25.36 19.34

Titanium dioxide exists as several polymorphs, the most common of which are anatase, rutile, and
brookite. The experimental diffraction angles for the six strongest reflections collected from each of 36.15 37.01 25.36
these different polymorphs are summarized in the table in the margin. The powder X-ray 39.28 37.85 25.71
diffraction pattern collected using 154 pm X-radiation from a sample of white paint, known to
41.32 38.64 30.83
contain Ti02 in one or more of these polymorphic forms, showed the diffraction pattern in Fig. 8.4.
Identify the Ti02 polymorphs present. 44.14 48.15 32.85
54.44 53.97 34.90
Answer We need to identify the polymorph that has a diffraction pattern that matches the one
observed. The lines closely match those of rutile (strongest reflections) and anatase (a few weak
reflections), so the paint contains these phases with rutile as the major Ti02 phase.
Self-test 8.7 Chromium(IV) oxide also adopts the rutile structure. By consideration 2 of Bragg's
equation and the ionic radii of Ti4+ and Cr4+ (Resource section 1) predict the main features of the Cr0
powder X-ray diffraction pattern.
(b) Single-crystal X-ray diffraction
Key point: The analysis of the diffraction patterns obtained from single crystals allows the full deter-
mination of the structure.

Analysis of the diffraction data obtained from single crystals is the most important method
of obtaining the structures of inorganic solids. Provided a compound can be grown as a
27.50

54.44
36.15
Counts

41.32
25.36

39.28

44.14
37.85

53.97
37.01

20 30 40 50 60
2 /0
Figure 8.4 A powder diffraction pattern obtained from a mixture
of
Ti02 polymorphs (see Example 8.1).
226 8 Physical techniques in inorganic chemistry
Sampie
2 just a few hours (Fig. 8.6).
Detector
X-ray
beam
Figure 8.5 The layout of a four-circle
diffractometer. A computer controls the
location of the detector as the four
angles are changed systematically.
Figure 8.6 Part of a single-crystal X-
ray
diffraction pattern. Individual spots arise
by diffraction of X-rays scattered from
different planes of atoms within the
crystal.
0 Cs
H C 0
Figure 8.7 An 0RTEP diagram of
caesium
oxalate monohydrate, Cs2C204.H20.
The ellipsoids correspond to a 90 per
cent probability of locating the
atoms.
crystal of sufficient size and quality, the data provide definitive information about molecular
and extended lattice structures.
The collection of diffraction data from a single crystal is normally carried out by using
a four-circle or area-detector diffractometer (Fig. 8.5). A four-circle diffractometer uses a
scintillation detector to measure the diffracted X-ray beam intensity as a function of the
angles shown in the illustration. An area-detector diffractometer uses an image plate that
is sensitive to X-rays and so can measure a large number of diffraction maxima simultane-
ously; many new systems use this technology because the data can typically be collected in
Analysis of the diffraction data from single crystals is formally a complex process in-
volving the locations and intensities of many thousands of reflections, but with increasing
advances in computation power a skilled crystallographer can complete the structure de-
termination of a small inorganic molecule in under an hour. Single-crystal X-ray diffraction
can be used to determine the structures of the vast majority of inorganic compounds when
they can be obtained as crystals with dimensions of about 50 X 50 X 50 µm or larger.
Positions for most atoms, including C, N, O, and metals, in most inorganic compounds
can be determined with sufficient accuracy that bond lengths can be defined to within a
fraction of a picometre. As an example, the S-S bond length in monoclinic sulfur has been
reported as 204.7 ± 0.3 pm.
A note on good (or at least conventional) practice Crystallographers still generally use the
angstrom
(1 A = 10 -10 m = 10 -8 cm = 10 -2 pm) as a unit of measurement. This unit is convenient because
bond lengths typically lie between 1 and 3 A. The s-s bond length in monoclinic sulfur would
be reported as 2.047 ± 0.003 A.
The positions of H atoms can be determined for inorganic compounds that contain only
light atoms (Z less than about 18, Ar), but their locations in many inorganic compounds
that also contain heavy atoms, such as the 4d- and 5d-series elements, can be difficult or
impossible. The problem lies with the small number of electrons on an H atom (just 1),
which is often reduced even further when H forms bonds to other atoms. Other tech-
niques, such as neutron diffraction (Section 8.2), can often be applied to determine the
positions of H in inorganic compounds.
Molecular structures obtained by the analysis of single-crystal X-ray diffraction data
are often represented in ORTEP diagrams (Fig. 8.7; the acronym stands for Oak Ridge
Thermal Ellipsoid Program). In an ORTEP diagram an ellipsoid is used to represent the
volume within which the atomic nucleus most probably lies, taking into account its ther-
mal motion. The size of the ellipsoid increases with temperature and, as a result, so does
the imprecision of the bond lengths extracted from the data.
(c) X-ray diffraction at synchrotron sources
Key point: High-intensity X-ray beams generated by synchrotron sources allow the structures of very
complex molecules to be determined.
Much more intense X-ray beams than are available from laboratory sources can be
obtained by using synchrotron radiation. Synchrotron radiation is produced by electrons
circulating close to the speed of light in a storage ring and is typically several orders
of magnitude more intense than laboratory sources. Because of their size, synchrotron
X-ray sources are normally national or international facilities. Diffraction equipment
located at such an X-ray source permits the study of much smaller samples and crystals
as small as 10 X 10 X 10 µm can be used. Furthermore, data collection can be under-
taken much more rapidly and more complex structures, such as those of enzymes, can
be determined more easily.
8.2 Neutron diffraction
Key point: The scattering of neutrons by crystals yields diffraction data that give additional informa-
tion on structure, particularly the positions of light atoms.
Diffraction occurs from crystals for any particle with a velocity such that its associated
wavelength (through the de Broglie relation, A = hlmv) is comparable to the separations
 Absorption spectroscopy 227
of the atoms or ions in the crystal. Neutrons and electrons travelling at suitable velocities
have wavelengths of the order of 100-200 pm and thus undergo diffraction by crystalline
inorganic compounds.
Neutron beams of the appropriate wavelength are generated by 'moderating'
(slowing down) neutrons generated in nuclear reactors or through a process known
as spallation, in which neutrons are chipped off the nuclei of heavy elements by ac-
celerated beams of protons. The instrumentation used for collecting data and ana-
lysing single-crystal or powder neutron diffraction patterns is often similar to that
used for X-ray diffraction. The scale is much larger, however, because neutron beam
fluxes are much lower than laboratory X-ray sources. Furthermore whereas many
chemistry laboratories have X-ray diffraction equipment for structure characteriza-
tion, neutron diffraction can be undertaken only at a few specialist sources world-
wide. The investigation of an inorganic compound with this technique is therefore
much less routine and its application is essentially limited to systems where X-ray
diffraction fails.
The advantages of neutron diffraction stem from the fact that neutrons are scattered
by nuclei rather than by the surrounding electrons. As a result, neutrons are sensi-
tive to structural parameters that often complement those for X-rays. In particular,
the scattering is not dominated by the heavy elements, which can be a problem with
X-ray diffraction for most inorganic compounds. For example, locating the position
of a light element such as H and Li in a material that also contains Pb can be impos-
sible with X-ray diffraction, as almost all the electron density is associated with the
Pb atoms. With neutrons, in contrast, the scattering from light atoms is often similar
to that of heavy elements, so the light atoms contribute significantly to the intensities
in the diffraction pattern. Thus neutron diffraction is frequently used in conjunction
with X-ray diffraction techniques to define an inorganic structure more accurately in
terms of atoms such as H, Li, and O when they are in the presence of heavier, electron-
rich metal atoms. Typical applications include studies of the complex metal oxides,
such as the high-temperature superconductors (where accurate oxide ion positions are
required in the presence of metals such as Ba and Tl) and systems where H atom posi-
tions are of interest.
Another use for neutron diffraction is to distinguish nearly isoelectronic species. In
X-ray scattering, pairs of neighbouring elements in a period of the periodic table, such as
O and N or Cl and S, are nearly isoelectronic and scatter X-rays to about the same extent,
therefore they are hard to tell apart in a crystal structure that contains them both. How-
ever, the atoms of these pairs do scatter neutrons to very different extents, N 50 per cent
more strongly than O, and Cl about four times better than S, so the identification of the
atoms is much easier than by X-ray diffraction.

Absorption spectroscopy
The majority of physical techniques used to investigate inorganic compounds involve
the absorption and sometimes the re-emission of electromagnetic radiation. The fre-
quency of the radiation absorbed provides useful information on the energy levels
of an inorganic compound and the intensity of the absorption can often be used to
provide quantitative analytical information. Absorption spectroscopy techniques are
normally nondestructive as after the measurement the sample can be recovered for
further analysis.
The spectrum of electromagnetic radiation used in chemistry ranges from the short
wavelengths associated with - and X-rays (about 1 nm), to radiowaves with wave-
lengths of several metres (Fig. 8.8). This spectrum covers the full range of atomic and
molecular energies associated with characteristic phenomena such as ionization, vibra-
tion, rotation, and nuclear reorientation. Thus, X- and ultraviolet (UV) radiation can
be used to determine the electronic structures of atoms and molecules and infrared
(IR) radiation can be used to examine their vibrational behaviour. Radiofrequency
(RF) radiation, in nuclear magnetic resonance (NMR), can be used to explore the ener-
gies associated with reorientations of the nucleus in a magnetic field, and those ener-
gies are sensitive to the chemical environment of the nucleus. In general, absorption