l

These 2 constructively Interfere good signal!

Braggs Law
l

These 2 destructively Interfere bad signal!

nl=2dsin
Just needs some satisfaction!!

X-Ray Diffraction (XRD) equipment

nl=2dsin nl/2d=sin
XRD machines vary angle as 2 because that angle is always relative to incident X-ray beam trajectory

Solution satisfied at specific angles (n MUST be an integer)

2 X-ray source Typically a Cu or Mo target 1.54 or 0.8 wavelength Sample holder 2

Detector typically moves over range of 2 angles

Orientation of diffracting hkl planes in sample A number of these are possible

XRD Part II
Theoretically, almost an infinite number of planes can exist, but certain ones diffract more strongly Related to the atomic density both of ## of atoms and in those ions atomic density

XRD results
Diffraction pattern Higher symmetry fewer, more intense lines because multiple planes are complimentary (identical d-spacings for different planes yields identical diffraction)

XRD extinctions
Some forms exhibit extinctions when planes should be present (i.e. satisfy Braggs Law) but are not due to destructive interference with another planes diffraction. Useful for determining special conditions of symmetry in a single crystal ID for body, face centered minerals as well as ones with screw axes and glide planes method to see differences between space groups

XRD analyses
Can look at minerals as single crystals or as a powder Single Crystal must be careful about orienting the crystal so Braggs Law is satisfied, use several different techniques, advanced machines manipulate the sample in 3 axes (x,y,z) to catch all the peaks required for structural determination Powder has many particles with planes at many different orientations many orientations satisfy Braggs Law, intensities and locations (2) are characteristic of specific minerals. Technique primarily used for identification

Powder XRD analyses

With a single crystal, alignment of planes which give strong diffraction returns is very exact requires precise alignment With a fine powder, idea is to have crystals at a wide variety of orientations so hitting that exact alignment is possible without manipulating the sample i.e. in a powder we figure a few grains are lined up correctly

Powder X-ray Analyses

XRD analysis of a powder is a common, quick, and relatively easy way to identify minerals. Having a mixture of minerals can be tricky, so grains are first separated if possible (small amounts of other minerals will give other peaks, but intensities are low enough that it is not a big deal) Do lose the ability to see the details of the structure of the mineral however as the precise alignment of the mineral giving the peak is unknown and not changeable

Analytical Techniques for Minerals

XRD (X-ray diffraction) is one of the most powerful tools for mineral identification, structural/chemical refinement, and size determination Microscopy Optical techniques are another very powerful tool for mineral identification, identification of physical/ chemical history of minerals/rocks, and mineral association which we will also study in detail (both lecture and lab)

More analytical techniques

Electron microscopy look at techniques which utilize how electrons (shot through a sample of mineral) interact with minerals imaging possible to very small sizes Scanned-proximity probe microscopy techniques look at forces between probe tip and sample to measure a property (height, optical absorption, magnetism, etc) Spectroscopy different methods of studying how different parts of the electromagnetic spectrum (of which visible light is a small part) are affected by minerals

More analytical techniques

Sychrotron Different techniques (including many spectroscopic techniques) that utilize particles accelerated to very high speeds and high energies Magnetic different techniques that utilize the magnetic properties of minerals Size techniques to determine the sizes of different minerals Chemistry/isotopes techniques to probe chemical and isotopic signatures in minerals

 Spectroscopic techniques investigate the interaction of some part of the electromagnetic spectrum with a material Each technique provides different information about the chemistry, structure, and physics of the material

Spectroscopic Techniques
Utilize the absorption or transmittance of electromagnetic radiation (light is part of this, as is ~UV, IR) for analysis Governed by Beers Law (or BeerLambert-Bouger law, but everyone likes Beer)
A=abc Where: A=Absorbance, a=wavelengthdependent absorbtivity coefficient, b=path length, c=analyte concentration

Spectroscopy
Exactly how light is absorbed and reflected, transmitted, or refracted changes the info and is determined by different techniques
sample

Transmittance spectroscopy Reflected spectroscopy Raman Spectroscopy

Light Source
Light shining on a sample can come from different places (in lab from a light, on a plane from a laser array, or from earth shining on Mars with a big laser) Can tune these to any wavelength or range of wavelengths
IR image of Mars Olivine is purple

Causes of Absorption
Molecular or atomic orbitals absorb light, kicks e- from stable to excited state Charge transfer or radiation (color centers) Vibrational processes a bond vibrates at a specific frequency only specific bonds can absorb IR though (IR active)

Vibrational spectroscopy
Another name applied to absorption spectroscopy in IR range and for Raman spectroscopy Sensitive to the vibrational modes of bonds between atoms rather than of the ions themselves

Optical Spectroscopy
Techniques concerned with how light reflects, absorbs, or transmits through minerals from near UV to mid-infrared (250 3000 nm wavelengths) Dealing with energy which excited electrons from a standard to an excited state

Spectroscopy
Exactly how light is absorbed and reflected, transmitted, or refracted changes the info and is determined by different techniques
sample

Transmittance spectroscopy Reflected spectroscopy Raman Spectroscopy

Reflectance Spectroscopy
Can be optical or vibrational Non-destructive form of analysis, used to see some of the chemistry, bonding Spectroscopy is particularly good at detecting water and OH groups in minerals (especially in IR) Good at differentiating between different clays because it detects OH groups well

Raman Spectroscopy
Another kind of spectroscopy which looks at a scattering effect and what that tells us about the chemistry, oxidation state, and relative proportions of different ions

Mssbauer Spectroscopy
Special effect, restricted to specific isotopes of certain elements which causes a very characteristic emission (after getting hit with a beam of gamma radiation) which is sensitive to the bonding environment of that isotope (only 57Co, 57Fe, 129I, 119Sn, 121Sb) Generally used to study Fe tells us about how Fe is bonded and its oxidation state