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Crystalline Amorphous
Crystalline has long range order
Particles
Atoms
Interparticle Forces
Dispersion
Physical Behaviour
Soft Very low mp Poor thermal and electrical conductors Fairly soft Low to moderate mp Poor thermal and electrical conductors Soft to hard Low to very high mp Mellable and ductile Excellent thermal and electrical conductors Hard and brittle High mp Good thermal and electrical conductors in molten condition Very hard Very high mp Poor thermal and electrical conductors
Examples
Group 8A Ne to Rn
Molecular
Molecules
Metallic
Atoms
Na, Cu, Fe
Ionic
Ion-ion attraction
Network
Covalent Atoms
SiO2(Quartz) C (Diamond)
Na+ Cl-
Molecular Solids
Covalent Solids
Ionic solids
Metallic solids
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DIAMOND
QUARTZ
GRAPHITE
Unit Cell
The unit cell and, consequently, the entire lattice, is uniquely determined by the six lattice constants: a, b, c, , and . Only 1/8 of each lattice point in a unit cell can actually be assigned to that cell. Each unit cell in the figure can be associated with 8 x 1/8 = 1 lattice point.
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Lattice the underlying periodicity of the crystal Basis Entity associated with each lattice points
Lattice how to repeat Motif what to repeat
Lattice
Translationally periodic arrangement of points
Crystal
Translationally periodic arrangement of motifs
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a = b, U = 90 a a a
a = b, U =120 a
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Na+ Cl-
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Five 2D lattices
a{b K=90r
a=b K=120r
unit cell
Primitive Centered
There are literally thousands of crystalline materials, there are only 5 distinct planar lattices
LATTICE TYPES
Primitive ( P )
Body Centered ( I )
Face Centered ( F )
C-Centered (C )
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Crystalline Solids
There are several types of basic arrangements in crystals, such as the ones shown above.
# of Atoms/Unit Cell
simple cubic unit cell = 1 atom body centered cubic = 2 atoms face-centered cubic = 4 atoms
Crystalline Solids
We can determine the empirical formula of an ionic solid by determining how many ions of each element fall within the unit cell.
BRAVAIS LATTICES
Isometric or Cubic
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Tetragonal
20
Hexagonal
21
Rhombohedral
22
Orthorhombic
23
Monoclinic
24
Triclinic
25
The Choice of a Unit Cell: Have the highest symmetry and minimal size
F K a
E b
c a b
Figure 3.15 Illustration of coordinations in (a) SC and (b) BCC unit cells. Six atoms touch each atom in SC, while the eight atoms touch each atom in the BCC unit cell.
= 2r
or
r = aeasy to see!
Face Centered:
= r (8)
Example 3.2 Determining the Relationship between Atomic Radius and Lattice Parameters
Determine the relationship between the atomic radius and the lattice parameter in SC, BCC, and FCC structures when one atom is located at each lattice point.
Figure 3.14 The relationships between the atomic radius and the Lattice parameter in cubic systems (for Example 3.2).
Example 3.2 SOLUTION Referring to Figure 3.14, we find that atoms touch along the edge of the cube in SC structures.
a0
! 2r
In BCC structures, atoms touch along the body diagonal. There are two atomic radii from the center atom and one atomic radius from each of the corner atoms on the body diagonal, so
a0
4r ! 3
In FCC structures, atoms touch along the face diagonal of the cube. There are four atomic radii along this lengthtwo radii from the facecentered atom and one radius from each corner, so:
a0
4r ! 2
APF =
Coordination # = 8
volume = LxWxH = (length of one side)3 we will use a as the length of one side, so V= a3 Putting them togetherDensity= (# of atoms in the unit cell) 3
(a ) _(formula mass)_ (6.02 x 1023 atoms)
T $ 0.74 18
Example: Cubic unit cell of CsCl, a=b=c E=F=K=90r Cs:(0,0,0) Cl: (1/2,1/2,1/2)
Single Crystal: Composed of only one particular type of space lattice. Polycrystalline matter: Clusters of multiple crystals.
= 2r
or
r = aeasy to see!
Face Centered:
= r (8)
Solving for the triangle in blue c2 = a2 + b2 (4r)2 = a2 + b2 We dont have a value for b, but we can recognize that it is also a hypotenuse of a right triangle b2 = a2 +a2 Substituting (4r)2 = a2 + a2 + a2 Simplifying16r2 = 3a2
a a
(body-centered lattice)
Solving for a a
= r(5 )
3a0
a
2a
a 2 4 3
Coordination # = 12
a
Adapted from Fig. 3.1(a), Callister 7e.
Unit cell contains: 6 x 1/2 + 8 x 1/8 = 4 atoms/unit cell atoms unit cell APF = 4 4 3 T( 2a/4 ) 3 a3 volume atom volume unit cell
Theoretical Density, V
Ex: Cr (BCC) A = 52.00 g/mol R = 0.125 nm n=2 @ a = 4R/3 = 0.2887 nm a 2 52.00 a 3 6.023 x 1023 g mol Vactual atoms mol Vtheoretical = 7.18 g/cm3 = 7.19 g/cm3
V=
volume unit cell
THEORETICAL DENSITY, V
Density = mass/volume mass = number of atoms per unit cell * mass of each atom mass of each atom = atomic weight/avogadros number
# atoms/unit cell
THEORETICAL DENSITY, V
# atoms/unit cell Atomic weight (g/mol)
Example: Copper
Data from Table inside front cover of Callister (see previous slide): crystal structure = FCC: 4 atoms/unit cell atomic weight = 63.55 g/mol (1 amu = 1 g/mol) -7 atomic radius R = 0.128 nm (1 nm = 10 cm) Vc = a3 ; For FCC, a = 4R/ 2 ; Vc = 4.75 x 10-23cm3
Result: theoretical VCu = 8.89 g/cm3 Compare to actual: VCu = 8.94 g/cm3
THEORETICAL DENSITY
# atoms/unit cell Atomic weight (g/mol)
Problem: Compute the density of Copper Given: Atomic radius of Cu = 0.128 nm (1.28 x 10-8 cm)
Atomic Weight of Cu = 63.5 g/mol Crystal structure of Cu is FCC
Solution:
V = n A / Vc NA
10-8 cm
Density V !
(number of atoms/cell)(atomic mass of iron) (volume of unit cell)(Avogadro' s number) ( 2)(55.847) V ! ! 7.882 g / cm 3 ( 23.54 v 10 24 )(6.02 v 10 23 )
Calculate Unit-Cell Dimension from Unit-Cell Type and Density: Pt crystallizes in a face-centered cubic (fcc) lattice with all atoms at the lattice points. It has a density of 21.45 g/cm3 and an atomic weight of 195.08 amu. Calculate the length of a unit-cell edge. Compare this with the value of 392.4 pm obtained from X-ray diffraction. STRATEGY: We can calculate the mass of the unit cell from the atomic weight. Knowing the density and the mass of the unit cell, we can calculate the volume of a unit cell and then the edge length of a unit cell. Mass of one Pt atom: 195.08 g Pt x 1 mol Pt = 3.239 x 10-22g Pt 1 mol Pt 6.022 x 1023Pt atoms 1 Pt atom Since there are 4 atoms of Pt per fcc unit cell, the mass per unit cell = 4 x 3.239 x 10-22 = 1.296 x 10-21 g Pt 1 unit cell Since d = m/V; the Volume of the unit cell is: V = m/d V = (1.296 x 10-21 g Pt/cell) /(21.45 g/cm3) V = 6.042 x 10-23 cm3 /cell But the Volume of the cell = a3; therefore, a = V1/3 a = ( 6.042 x 10-23 cm3)1/3 = 3.924 x 10-8 cm a = 3.924 x 10-10 m = 3.924 Angstrom = 392.4 pm This is exactly the number obtained by the x-ray 53 diffraction experiment.
Calculate Atomic Mass from Unit-Cell Dimension and Density: The unit cell length for Ag was determined to be 408.6 pm. Ag crystallizes in a fcc lattice with all atoms at the lattice points. Ag has a density of 10.50 g/cm3. Calculate the mass of a Ag atom, and, using the known atomic weight (107.87 amu), calculate Avogadro's #. STRATEGY: We can calculate the unit cell volume from a. Then, from the density, we can find the mass of the unit cell and then the mass of a single Ag atom. From this, we can find Avogadro's number. The Volume of the cell = a3: V = (408.6 x 10-12 m)3 V = 6.822 x 10-29 m3 The density of silver (in g/m3) is: d =10.50 g/cm3 x (1 cm/10-2m)3 = 1.050 x 107 g/m3 The mass of one unit cell is: m = d*V m = 1.050 x 107 g/m3 x 6.822 x 10-29 m3 m = 7.163 x 10-22 g Ag/cell Because there are 4 atoms in a fcc cell, the mass of a single Ag atom in the cell (7.163 x 10-22 g Ag/cell) / (4 atoms/cell) = 1.791 x 10-22 g Ag/atom The molar mass (Avogadro's number) = N 107.87 g Ag /mol Ag = 6.023 x 1023 atoms/mol 1.791 x 10-22 g Ag/atom OR: rho = Z*M / V*N 54 N = Z*M/rho*V = (4 atoms)(107.87 g/mol) =
Fe
FCC (at Temperature above 912 oC)
to r
Measurement of:
Critical angles, Uc, for X-rays provide atomic spacing, d.
1 g in 2 m co ys in -ra X
g in o tg ou U
d=nP/2sinUc
U Uc
Laue equation
Interference condition: the difference in path lengths of adjacent lattice points must be a multiple integral of the wavelength. AD-CB = hP AD = aS = acosE CB = aS0 = acosE0 a(cosE-cosE0) = hP, h=0, s1, s2 . Where, a lattice parameter E0angle between a and s0 E angle between a and s
For each h value, the diffraction rays from a 1D lattice E make a cone.
E0
This is the Laue Equation! where, a,b,clattice parameter E0,F0,K0angle between a,b,c and s0 E,F,K angle between a,b,c and s h,k,l indices of diffraction, integers
which may not be prime to each other and are different from Miller indices for crystal plane!
In the diffraction direction, the difference between the incident and the diffracted beam through any two lattice points must be an integral number of wavelengths. The vector from (000) to (mnp): Tmnp = ma + nb +pc The differences in wavelengths: ( =Tmnp (S-S0) =(ma + nb +pc) (S-S0) = ma (S-S0)+nb (S-S0)+pc (S-S0) =mhP+ nkP+plP =(mh+nk+pl)P
2. The Braggs Law Bragg discovered that you could consider the diffraction arising from reflection from lattice planes
s0
U O
P
s
U dhkl
Conditions to obtain constructive inferences, a. the scattered x-ray must be coplanar with the incident x-ray and the normal of the lattice plane. b. US=US0
(=AD+DB = 2d(hkl)sinUn Condition for diffraction: 2d(hkl) sinUn = nP (n=1, 2, 3, ) Un: n: the angle of reflection the order of the reflection
(dnhnknl = dhkl/n)
s0
U O U A D
s
dhkl
2dnhnknlsinUnh,nk,nl=P
However, the reflection order n is not measurable! Reformulated Bragg equations: 2dhkl sinU = P reflection indices
2dhkl sinU = P
(dnhnknl = dhkl/n)
The Bragg equation defines the direction of diffraction beams from a given set of lattice planes!
o 1915, the father and son were awarded the Nobel prize for physics "for their
services in the analysis of crystal structure by means of Xrays".
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Bragg Equation
Bragg law identifies the angles of the incident radiation relative to the lattice planes for which diffraction peaks occurs. Bragg derived the condition for constructive interference of the X-rays scattered from a set of parallel lattice planes.
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BRAGG EQUATION
W.L. Bragg considered crystals to be made up of parallel planes of atoms. Incident waves are reflected specularly from parallel planes of atoms in the crystal, with each plane is reflecting only a very small fraction of the radiation, like a lightly silvered mirror. In mirrorlike reflection the angle of incidence is equal to the angle of reflection.
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Diffraction Condition
The diffracted beams are found to occur when the reflections from planes of atoms interfere constructively. We treat elastic scattering, in which the energy of X-ray is not changed on reflection.
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Bragg Equation
When the X-rays strike a layer of a crystal, some of them will be reflected. We are interested in X-rays that are in-phase with one another. X-rays that add together constructively in x-ray diffraction analysis in-phase before they are reflected and after they reflected.
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Bragg Equation
These two x-ray beams travel slightly different distances. The difference in the distances traveled is related to the distance between the adjacent layers. Connecting the two beams with perpendicular lines shows the difference between the top and the bottom beams.
The line CE is equivalent to the distance between the two layers (d)
DE ! d sin U
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Bragg Law
The length DE is the same as EF, so the total distance traveled by the bottom wave is expressed by: EF ! d sin U DE ! d sin U DE EF ! 2d sin U nP ! 2d sin U Constructive interference of the radiation from successive planes occurs when the path difference is an integral number of wavelenghts. This is the Bragg Law.
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Bragg Equation
2d sin U ! nP
where, d is the spacing of the planes and n is the order of diffraction. Bragg reflection can only occur for wavelength
nP e 2d
This is why we cannot use visible light. No diffraction occurs when the above condition is not satisfied. The diffracted beams (reflections) from any set of lattice planes can only occur at particular angles pradicted by the Bragg law.
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There will be constructive interference of the waves scattered from the two successive lattice points A and B in the plane if the distances AC and DB are equal.
D U U A
C 2U B
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75
Coherent scattering from a single plane is not sufficient to obtain a diffraction maximum. It is also necessary that successive planes should scatter in phase This will be the case if the path difference for scattering off two adjacent planes is an integral number of wavelengths
Diffraction maximum
2d sin U ! nP
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which makes n-th order diffraction off (hkl) planes of spacing d look like first-order diffraction off planes of spacing d/n. Planes of this reduced spacing would have Miller indices (nh nk nl).
78
found six values ofU for which a sharp peak in intensity occurred, corresponding to three characteristics wavelengths (K,L and M x-rays) in first and second order (n=1 and n=2 in Bragg law) By repeating the experiment with a different crystal face he could use his eqn. to find for example the ratio of (100) and (111) plane spacings, information that confirmed the cubic symmetry of the atomic arrangement.
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Details of structure
Details of structure were than deduced from the differences between the diffraction patterns for NaCl and KCl. Major difference; absence of (111) reflection in KCl compared to a weak but detectable (111) reflection in NaCl. This arises because the K and Cl ions both have the argon electron shell structure and hence scatter x-rays almost equally whereas Na and Cl ions have different scattering strengths. (111) reflection in NaCl corresponds to one wavelength of path difference between neighbouring (111) planes.
80
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Bragg Equation
Since Bragg's Law applies to all sets of crystal planes, the lattice can be deduced from the diffraction pattern, making use of general expressions for the spacing of the planes in terms of their Miller indices. For cubic structures d! a h2 k 2 l 2
Note that the smaller the spacing the higher the angle of diffraction, i.e. the spacing of peaks in the diffraction pattern is inversely proportional to the spacing of the planes in the lattice. The diffraction pattern will reflect the symmetry properties of the lattice.
2d sin U ! nP
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Bragg Equation
A simple example is the difference between the series of (n00) reflections for a simple cubic and a body centred cubic lattice. For the simple cubic lattice, all values of n will give Bragg peaks. However, for the body centred cubic lattice the (100) planes are interleaved by an equivalent set at the halfway position. At the angle where Bragg's Law would give the (100) reflection the interleaved planes will give a reflection exactly out of phase with that from the primary planes, which will exactly cancel the signal. There is no signal from (n00) planes with odd values of n. This kind of argument leads to rules for identifying the lattice symmetry from "missing" reflections, which are often quite simple.
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Laue
Orientation Single Crystal Polychromatic Beam Fixed Angle
Rotating Crystal
Lattice constant Single Crystal Monochromatic Beam Variable Angle
Powder
Lattice Parameters Polycrystal (powdered) Monochromatic Beam Variable Angle
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CLOSE-PACKING OF SPHERES
86
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Example Problem: What is the packing efficiency in the simple cubic cell of CsCl? What is the percentage of empty space in the unit cell? The chloride ions are at the corners with the cesium in the middle of the unit cell. rCl- = 181 pm; rCs+ = 169 pm
Example Problem
What is the packing efficiency of NaCl? What is the percentage of empty space in the NaCl unit cell? ) rCl- = 181 pm; rNa+ = 98 pm; edge dist.NaCl = 562.8 pm
Hard spheres touch along cube diagonal cube edge length, a= 4R/3 The coordination number, CN = 8 Number of atoms per unit cell, n = 2 Center atom not shared: 1 x 1 = 1 8 corner atoms shared by eight cells: 8 x 1/8 = 1 Atomic packing factor, APF = 0.68
90
SQUARE PACKING
CLOSE PACKING
92
93
94
95
4 atoms in the unit cell (0, 2 atoms in the unit cell (0, 0, 0) 0, 0) (0, 1 /2, 1 /2) (1 /2, 0, 1 /2) (2/3, 1 /3, 1 /2) (1 /2, 1 /2, 0)
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NON-CLOSE-PACKED STRUCTURES
a) Body centered cubic ( BCC ) b) Primitive cubic ( P)
Structure Primitive Cubic Bodycentered Cubic Hexagonal close packed Cubic close packed
Coordination number 6 8
Nonclose packing
12 12
ABABAB ABCABC
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Close packing
Coordination number
12
99
100
ALLOTROPES
Diamond
Graphite
Buckminsterfullerene
101
TETRAHEDRAL HOLES
OCTAHEDRAL HOLES
102
103
104
Ionic structures may be derived from the occupation of holes by oppositely charged ions (interstitial sites) in the close-packed arrangements of ions.
105
Radius ratio
Coordinate number
4 6 8
AX
6 8 6 8 6
6 8 3 4 2
AX2
AX3
CCP Cl- with Na+ in all Octahedral holes Lattice: FCC Motif: Cl at (0,0,0); Na at (1/2,0,0) 4 NaCl in one unit cell Coordination: 6:6 (octahedral) Cation and anion sites are topologically identical
108
CCP S2- with Zn2+ in half Tetrahedral holes ( T+ {or T-} filled) Lattice: FCC 4 ZnS in one unit cell Motif: S at (0,0,0); Zn at (1/4,1/4,1/4) Coordination: 4:4 (tetrahedral) Cation and anion sites are topologically identical
109
HCP with Ni in all Octahedral holes Lattice: Hexagonal - P Motif: 2Ni at (0,0,0) & (0,0,1/2) 2As at (2/3,1/3,1/4) & (1/3,2/3,3/4) 2 NiAs in unit cell Coordination: Ni 6 (octahedral) : As 6 (trigonal prismatic)
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d) WURTZITE ( ZnS )
HCP S2- with Zn2+ in half Tetrahedral holes ( T+ {or T-} filled ) Lattice: Hexagonal - P Motif: 2 S at (0,0,0) & (2/3,1/3,1/2); 2 Zn at (2/3,1/3,1/8) & (0,0,5/8) 2 ZnS in unit cell Coordination: 4:4 (tetrahedral)
111
112
STRUCTURE TYPE - AX
NON CLOSE PACKED STRUCTURES CUBIC-P (PRIMITIVE) ( eg. Cesium Chloride ( CsCl ) )
Motif: Cl at (0,0,0); Cs at (1/2,1/2,1/2) 1 CsCl in one unit cell Coordination: 8:8 (cubic) Adoption by chlorides, bromides and iodides of larger cations, e.g. Cs+, Tl+, NH4+
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CCP Ca2+ with F- in all Tetrahedral holes Lattice: fcc Motif: Ca2+ at (0,0,0); 2F- at (1/4,1/4,1/4) & (3/4,3/4,3/4) 4 CaF2 in one unit cell Coordination: Ca2+ 8 (cubic) : F- 4 (tetrahedral) In the related Anti-Fluorite structure Cation and Anion positions are reversed
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CCP Ca2+ with F- in all Tetrahedral holes Lattice: fcc Motif: Ca2+ at (0,0,0); 2F- at (1/4,1/4,1/4) & (3/4,3/4,3/4) 4 CaF2 in one unit cell Coordination: Ca2+ 8 (cubic) : F- 4 (tetrahedral) In the related Anti-Fluorite structure Cation and Anion positions are reversed
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AntiFlourite structure (or Na2O structure) positions of cations and anions are reversed related to Fluorite structure
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117
HCP of Iodide with Cd in Octahedral holes of alternate layers CCP analogue of CdI2 is CdCl2
118
119
Fluorite
120
121
CCP
Rock salt (NaCl) Zinc Blend (ZnS)
HCP
Nickel Arsenide (NiAs) Wurtzite (ZnS)
AX
AX2
All Tetrahedral Half octahedral (ordered framework) Half octahedral (Alternate layers full/ empty)
Fluorite (CaF2), Not known Anti-Fluorite (Na2O) Anatase (TiO2) Cadmium Chloride (CdCl2) Rutile (TiO2) Cadmium iodide (CdI2)
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PEROVSKITE STRUCTURE
Formula unit ABO3 CCP of A atoms(bigger) at the corners O atoms at the face centers B atoms(smaller) at the body-center
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PEROVSKITE
Lattice: Primitive Cubic (idealised structure) 1 CaTiO3 per unit cell A-Cell Motif: Ti at (0, 0, 0); Ca at (1/2, 1/2, 1/2); 3O at (1/2, 0, 0), (0, 1/2, 0), (0, 0, 1/2) Examples: NaNbO3 , BaTiO3 , Ca 12-coordinate by O (cuboctahedral) CaZrO , YAlO , KMgF 3 3 3 Ti 6-coordinate by O (octahedral) Many undergo small distortions: O distorted octahedral (4xCa + 2xTi) e.g. BaTiO3 is ferroelectric
126
Problem (text) Cobalt(II) oxide is used as a pigment in pottery. It has the same type of crystal structure as NaCl. When exposed to Xrays (P=153 pm) reflections were observed at 42.38, 65.68, and 92.60. Determine the values of n to which these reflections correspond, and calculate the spacing between the crystal layers.
n = 2dsin
SPINEL STRUCTURE
Formula unit AB2O4 (combination of Rock Salt and Zinc Blend Structure) Oxygen atoms form FCC A2+ occupy tetrahedral holes B3+ occupy octahedral holes