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Term paper CHEMISTRY


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X-rays are electromagnetic radiation of wavelength about 1 (10-10 m), which is about the same size as an atom. They occur in that portion of the electromagnetic spectrum between gamma-rays and the ultraviolet. The discovery of X-rays in 1895 enabled scientists to probe crystalline structure at the atomic level. X-ray diffraction has been in use in two main areas, for the fingerprint characterization of crystalline materials and the determination of their structure. Each crystalline solid has its unique characteristic X-ray powder pattern which may be used as a "fingerprint" for its identification. Once the material has been identified, X-ray crystallography may be used to determine its structure, i.e. how the atoms pack together in the crystalline state and what the inter atomic distance and angle are etc. X-ray diffraction is one of the most important characterization tools used in solid state chemistry and materials science. We can determine the size and the shape of the unit cell for any compound most easily using the diffraction of x-rays. Undoubtedly x- ray diffraction is the most important and useful technique in solid state chemistry.

Diffraction and Bragg's Law

There are measure role of braggle because it proves Braggs lawDiffraction occurs as waves interact with a regular structure whose repeat distance is about the same as the wavelength. The phenomenon is common in the natural world, and occurs across a broad range of scales. For example, light can be diffracted by a grating having scribed lines spaced on the order of a few thousand angstroms, about the wavelength of light. It happens that X-rays have wavelengths on the order of a few angstroms, the same as typical interatomic distances in crystalline solids. That means X-rays can be diffracted from minerals which, by definition, are crystalline and have regularly repeating atomic structures. When certain geometric requirements are met, X-rays scattered from a

crystalline solid can constructively interfere, producing a diffracted beam. In 1912, W. L. Bragg recognized a predicatable relationship among several factors. 1. The distance between similar atomic planes in a mineral (the interatomic spacing) which we call the d-spacing and measure in angstroms. 2. The angle of diffraction which we call the theta angle and measure in degrees. For practical reasons the diffractometer measures an angle twice that of the theta angle. Not surprisingly, we call the measured angle '2-theta'. 3. The wavelength of the incident X-radiation, symbolized by the Greek letter lambda and, in our case, equal to 1.54 angstroms.


The description of the ordering of atoms in a solid comes from simple concepts of how objects stack in an array. If atoms are round and they pack as close as possible, It should look like this:

The close packing of spheres in a plane leads to a repeat unit that has each edge equal in length to the diameter (twice the radius) of the spheres. The angles, edge length, and atomic positions of the repeat unit are sufficient for the visualization of the entire infinite array in the solid. In three dimensions the repeat unit is a 3D shape called the Unit Cell. The unit cell has three uniques crystallographic axies and, in general, three edge lengths. The angles of the edges of the unit cell need not be 90 or 120 degrees. (The figure below shows a possible crystal structure and its unit cell, but it is not a closest-packed structure, like the 2D structure above)

Close packed spheres of the same size in 3D is a little complicated. This packing leads to possibility of two unique structures, depending on how planes of 2D closest packed spheres are layered. If every other layer is exactly the same then we has a so called ABABA... structure. If not, then the structure is ABCABCABC...The figure below shows the difference between these two structures:

The ABABAB structure (panel (b) in the figures above) is called the Hexagonal Closest Packed structure. In this structure, each atom has 12 nearest neighbors and the volume of the spheres fills the maximum posssible space: 74.04%.

The ABCABC structure is called Face Centered Cubic (fcc). It also has each atom with 12 nearest neighbors and the atoms fill 74.04% of the available space. The difference in the structure is in the different long ranged order and the unit cell

The (fcc) structure is just one of the structures that is derived from a cubic unit cell (right angles, equal length edges). (If we allow the edge lengths to be different, but keep the right angles, we create the orthorhombic cells) The Cubic cells are shown below:

The number of atoms in the unit cell is not the same as the coordination number . In the Body Centered Cubic structure above the number of atoms in the unit cell is 2 but the number of nearest neightbors is 8. (The number of gray atoms in the above gives the number of atoms in the unit cell) The (bcc) structure is not as tightly packed as the (hcp) or (fcc) structures, with the atoms occupying only 68.02% of the available space. The NaCl crystal is face centered cubic (fcc) unit cell with the counter ion filling the octahedral holes in the structure. It does not matter which ion is taken to be at the verticies of the cell and which in the holes, the same pattern is obtained, as can be seen in the figure below:

Crystal structures are determined experimentally by X-Ray Diffraction:

The position of the spots observed in X-ray diffraction are determined by Braggs Law:

X-Ray Diffraction Experiment

X-rays are electromagnetic radiation of wavelength about 1 , which is about the same size as an atom. They occur in that portion of the electromagnetic spectrum between gamma-rays and the ultraviolet. The discovery of X-rays in 1895 enabled scientists to probe crystalline structure at the atomic level. X-ray diffraction has been in use in two

main areas, for the fingerprint characterization of crystalline materials and the determination of their structure. Each crystalline solid has its unique characteristic X-ray powder pattern which may be used as a "fingerprint" for its identification. Once the material has been identified, X-ray crystallography may be used to determine its structure, i.e. how the atoms pack together in the crystalline state and what the interatomic distance and angle are etc. X-ray diffraction is one of the most important characterization tools used in solid state chemistry and materials science. We can determine the size and the shape of the unit cell for any compound most easily using the diffraction of x-rays.

Fig. 1 Reflection of x-rays from two planes of atoms in a solid. The path difference between two waves: 2 x wavelength= 2d sin(theta)

For constructive interference between these waves, the path difference must be an integral number of wavelengths: n x wavelength= 2x

This leads to the Bragg equation: n x wavelength = 2d sin (theta) Figure 2 shows the x-ray diffraction pattern from a single crystal of a layered clay. Strong intensities can be seen for a number of values of n; from each of these lines we can calculate the value of d, the interlinear spacing between the atoms in the crystal.

Fig. 2 X-ray diffraction pattern from a layered structure vermiculite clay. EXAMPLE 1 Unit Cell Size from Diffraction Data The diffraction pattern of copper metal was measured with x-ray radiation of wavelength of 1.315. The first order Bragg diffraction peak was found at an angle 2theta of 50.5 degrees. Calculate the spacing between the diffracting planes in the copper metal. The Bragg equation is n x wavelength = 2d sin(theta) We can rearrange this equation for the unknown spacing d: d = n x wavelength/ 2sin(theta). theta is 25.25 degrees, n =1, and wavelength = 1.315, and therefore d= 1 x 1.315/(2 x 0.4266) = 1.541 In this lab you will measure the x-ray powder diffraction pattern from a single crystal. Your TA will give you the sample to be measured and show you how to set up the Minifies xray diffractometer. You should measure all the values of 2theta from the chart, and after converting them into d values calculate the repeat distance in your unit cell. In your lab note book list all the 2theta values with their corresponding values of n and d. Then calculate the mean and median values of the unit cell.

The X-ray diffraction experiment needs an X-ray source, the sample under investigation and a detector to pick up the diffracted X-rays. Fig 3 is a schematic diagram of a powder X-ray diffractometer.

Fig. 3. Schematic of an X-ray powder diffractometer The X-ray radiation most commonly used is that emitted by copper, whose characteristic wavelength for the K radiation is =1.5418. When the incident beam strikes a powder sample, diffraction occurs in every possible orientation of 2theta. The diffracted beam may be detected by using a moveable detector such as a Geiger counter, which is attached to a chart recorder. In normal use, the counter is set to scan over a range of 2theta values at a constant angular velocity. Routinely, a 2theta range of 5 to 70 degrees is sufficient to cover the most useful part of the powder pattern. The scanning speed of the counter is usually 2theta of 2degrees min-1 and therefore, about 30 minutes are needed to obtain a trace.

Schematic illustration of the X-SFA, which was designed for performing x-ray diffraction experiments of samples under confinement and shear while simultaneously measuring normal and lateral forces.

The Diffractometer
A diffractometer can be used to make a diffraction pattern of any crystalline solid. With a diffraction pattern an investigator can identify an unknown mineral, or characterize the atomic-scale structure of an already identified mineral. There exists systematic X-ray diffraction data for thousands of mineral species. Much of these data are gathered together and published by the JCPDS-International Centre for Diffraction Data.

The diffractometer in the IPFW Geosciences Department is a Philips APD3520 built in 1986. It consists of several part.

X-ray diffraction techniques

X ray diffraction finds the geometry of a molecule using X-rays. diffraction techniques are based on the elastic scattering of X-rays from structures that have long range order. The most comprehensive description of scattering from crystals is given by the dynamical theory of diffraction.There are many followings technique of diffraction.

Powder diffraction is a technique used to characterise the crystallographic structure, crystallite size , and preferred orientation in polycrystalline or powdered solid samples. Powder diffraction is commonly used to identify unknown substances, by comparing diffraction data against a database maintained by the Inter national Centre for Diffraction Data. It may also be used to characterize heterogeneous solid mixtures to determine relative abundance of crystalline compounds and, when coupled with lattice refinement techniques, such as Rietveld refinement, can provide structural information on unknown materials.

Powder diffraction is also a common method for determining strains in crystalline materials. An effect of the finite crystallite sizes is seen as a broadening of the peaks in an X-ray diffraction as is explained by the Scherrer Equation. Single-crystal X-ray diffraction is a technique used to solve the complete structure of crystalline materials, ranging from simple inorganic solids to complex macromolecules, such as proteins. High-resolution X-ray diffraction is used to characterize thickness, crystallographic structure, and strain in thin epitaxial films. It employs parallelbeam optics. X-ray pole figure analysis enables one to analyze and deter mine the distribution of crystalline orientations within a crystalline thin-film sample. X-ray rocking curve analysis is used to quantify grain size and mosaic spread in crystalline materials Thin film diffraction and grazing incidence X-ray diffraction may be used to characterize the crystallographic structure and preferred orientation of substrateanchored thin films.

X-ray Powder Diffraction

X-ray powder diffraction is a rapid analytical technique primarily used for phase identification of a crystalline material and can provide information on unit cell dimensions. The analyzed material is finely ground, homogenized, and average bulk composition is determined. Max Von Laue, in 1912, discovered that crystalline substances act as three-dimensional diffraction gratings for X-ray wavelengths similar to the spacing of planes in a crystal lattice. X-ray diffraction is now a common technique for the study of crystal structures and atomic spacing. X-ray diffraction is based on constructive interference of monochromatic X-rays and a crystalline sample. These X-rays are generated by a cathode ray tube, filtered to produce monochromatic radiation, collimated to concentrate, and directed toward the sample. The interaction of the incident rays with the sample produces constructive interference when conditions satisfy Bragg's Law (n=2d sin ). This law relates the wavelength of electromagnetic radiation to the diffraction angle and the lattice spacing in a crystalline sample. These diffracted X-rays are then detected, processed and counted. By scanning the sample through a range of 2angles, all possible diffraction directions of the lattice should be attained due to the random orientation of the powdered material. Conversion of the diffraction peaks to d-spacing allows identification of the mineral because each mineral has a set of unique d-spacing. Typically, this is achieved by comparison of dspacing with standard reference patterns.

All diffraction methods are based on generation of X-rays in an X-ray tube. These X-rays are directed at the sample, and the diffracted rays are collected. A key component of all diffraction is the angle between the incident and diffracted rays. Powder and single crystal diffraction vary in instrumentation beyond this. 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 bombarding the target material with electrons. 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 parts, 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 K2. The specific wavelengths are characteristic of the target material (Cu, Fe, Mo, Cr). Filtering, by foils or crystal monochrometers, 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. Copper is the most common target material for single-crystal diffraction, with Cu K radiation = 1.5418. These X-rays are collimated and directed onto the sample. As the sample and detector are rotated, the intensity of the reflected Xrays is recorded. When the geometry of the incident X-rays impinging the sample satisfies the Bragg Equation, constructive interference occurs and a peak in intensity occurs. 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.

The geometry of an X-ray diffractometer is such that the sample rotates in the path of the collimated X-ray beam at an angle while the X-ray detector is mounted on an arm to collect the diffracted X-rays and rotates at an angle of 2. The instrument used to

maintain the angle and rotate the sample is termed a goniometer. For typical powder patterns, data is collected at 2 from ~5 to 70, angles that are preset in the X-ray scan.

Schematic of an X-ray powder diffractometer USES OF POWDER METHOD

Characterization of materials by x ray fingerprints Qualitative phase analysis Quantitative phase analysis Refinment of unit cell parameter Study of solid solution formation Determination of crystal size Study of crystal distoration by stress Measurment of thermal expansion coefficient Determination of high temperature phase digram Study of phase transformation

Crystal structure determination Study of reaction of solids

At Proto we use the x-ray diffraction method to measure residual stress. X-ray diffraction is presently the only portable nondestructive method that can quantitatively measure residual stress in crystalline and semi-crystalline materials. Our high speed x-ray detector technology enables measurements to be performed easily on metals and ceramics; including traditionally difficult materials such as shot peened titanium. XRD uses the coherent domains of the material like a strain gage which reacts to the stress state existing in the material. Residual stress and applied stress expands or contracts the atomic lattice spacing . Identification: The most common use of powder diffraction is chemical analysis. This can include phase identification (search/match), investigation of high/low temperature phases, solid solutions and determinations of unit cell parameters of new materials. Polymer crystallinity: A polymer can be considered partly crystalline and partly amorphous. The crystalline domains performs as a reinforcing grid, like the iron framework in concrete, and improves the performance over a wide range of temperature. However, too much crystallinity causes brittleness. The crystallinity parts give sharp narrow diffraction peaks and the amorphous component gives a very broad peak (halo). The ratio between these intensities can be used to calculate the amount of crystallinity in the material. Residual stress: Residual stress is the stress that remains in the material after the external force that caused the stress have been removed. Stress is defined as force per unit area. Positive values indicate tensile (expansion) stress, negative values indicate a compressive state. The deformation per unit length is called strain. The residual stress can be introduced by any mechanical, chemical or thermal process. E.g. machining, plating and welding. The principals of stress analysis by the x-ray diffraction is based on measuring angular lattice strain distributions. That is, we select a reflection at high 2-Theta and measure the change in the d-spacing with different orientations of the sample. Using Hookes law the stress can be calculated from the strain distribution. Texture analysis: The determination of the preferred orientation of the crystallites in polycrystalline aggregates is referred to as texture analysis, and the term texture is used as a broad synonym for preferred crystallographic orientation in the polycrystalline material, normally a single phase. The preferred orientation is usually described in terms of polefigures

Crystal structures are determined experimentally by X-Ray Diffraction:

DNA molecule seen through x-ray diffraction

In this process, x-rays are directed toward a macroscopic object and are diffracted by the small spaces between its individual particles. Depending on the size of those spaces, the x-rays will emerge from the macroscopic object in slightly different directions. If the pattern of these directions is recorded (e.g., with a photographic

DNA molecule seen through x-ray diffraction.

plate or specialized digital camera), a computer can then reconstruct what the spacing arrangement was. Once the packing arrangement and the spacing are determined, scientists can reconstruct the size and shape of the individual particles. Since the image we get is not an actual photograph of what the particles look like, but rather a computer-generated model, x-ray diffraction is called an indirect imaging method, as opposed to a direct imaging method.


Solid state chemistry- Anthony R West Fundamental of physics- Halliday, resnick, walker Concept of physical chemistry-H. Mauron