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Maria Meisch, Teresa McConville and Rana Salameh

Determination of Crystal Structure by X-ray Diffraction

Introduction:

The crystal structure of a compound was determined from an X-ray powder diffraction pattern. The powder method is limited to the use of cubic systems, but allowed for the determination of the crystal lattice and the dimensions of the unit cell.

Theory:

Perfect crystals are comprised of a repetition of smaller structures called unit cells. The repeating unit cells form lattice structures. It is the planes of these lattice structures that diffract the x-rays. Crystals are most often described in terms of three crystal axes, a, b, and c. These axes which may be any length and do not have to be at right angles, form the basis for the

coordinate system. Within cubic systems a = b = c and all angles of the unit cell are 90 o . crystals can be described using equation one:

All

ha + kb + lc = positive constant

(1)

h, k and l are called Miller indices and are the reciprocals of intersection distances of the lattice planes. Each type of cubic system is defined by a Miller indices series and more specifically by

the gaps that are present. The Miller indices are used to determine the interplanar distance by the following equation:

d = a/(h 2 + k 2 + l 2 ) ½ = a/M

(2)

where a is the unit cell length and M 2 = h 2 + k 2 + l 2 . There are three types of cubic cells, primitive, face-centered and body-centered. In a primitive cubic system the lattice points are located only at the corners. Face-centered cubic cells

contain lattice points at the corners and at the centers of its six faces. Body-centered cubic cells have lattice points at the corners and also the center. These lattice points determine the lattice planes that are produced. Therefore, each cubic system has M 2 values that correspond to each

diffraction powder line. The x-ray powder method consists of a strip of film which was enclosed in a cylinder. The resulting x-ray contains two bulls-eyes and specific diffraction powder lines. The x-ray beam enters at one bulls-eye, reflects off the powder sample, producing the diffraction lines, and exits at the other bulls-eye. The concept of x-ray diffraction by crystal lattice structures is similar to the principle of light diffraction by a ruled grating. The angles of incidence and reflection are equal. Bragg defined the following relationship between this angle and the wavelength of the x-ray beam:

λ = 2 d sin θ

(3)

The interplanar distance from equation two can be substituted in Bragg’s equation to derive the

following linear equation:

(4 sin 2 θ )/ λ 2 = (h 2 + k 2 + l 2 )/a 2

(4)

Using θ from the diffraction pattern and a graph of (4 sin 2 θ )/ λ 2 vs h 2 + k 2 + l 2 , the correct Miller indices series resulting in a straight line verifies the type of cubic system present. The unit cell length can be calculated from the slope, which is 1/a 2 .

Experimental:

X-ray powder diffraction pattern number 24 was obtained. By comparing the film with Atkin’s Figure 21.26 it was determined to be a face-centered cubic system. The film was then held up to a window and each powder line was measured from one end. The top end of the film was the end with the most defined powder lines. The corresponding diffraction rings were measured and averaged to find the precise center of each bulls-eye. The distance between the bulls-eye was known to be 180 o and found to be 18cm therefore each centimeter on the film was equivalent to 10 o in the cylinder. Consequently, ten times the distance from the bulls-eye to the diffraction line corresponded to a diffraction angle of two theta. The distance from the top of the film to the first bulls-eye consistently averaged to 8.6

used were those found between the bulls-eyes. This distance was multiplied by ten to account for the angles of two theta. The angle theta was then used in equation 4 to determine the unit cell length, a.

Table 1: Powder Method Diffraction Data

d from bulls-eye

2 theta

theta

100 sin^2 (theta

4sin^2theta/lamda^2

M^2

2.4

24

12

4.32

0.07

3

2.8

28

14

5.85

0.10

4

3.9

39

19.5

11.14

0.19

8

4.6

46

23

15.27

0.26

11

4.8

48

24

16.54

0.28

12

5.6

56

28

22.04

0.37

16

6.1

61

30.5

25.76

0.43

19

6.3

63

31.5

27.30

0.46

20

7

70

35

32.90

0.55

24

7.5

75

37.5

37.06

0.62

27

8.25

82.5

41.25

43.47

0.73

32

8.7

87

43.5

47.38

0.80

36

8.9

89

44.5

49.13

0.83

36

9.6

96

48

55.23

0.93

40

10.2

102

51

60.40

1.02

44

10.8

108

54

65.45

1.10

48

11.5

115

57.5

71.13

1.20

52

12.2

122

61

76.50

1.29

56

12.7

127

63.5

80.09

1.35

60

13.9

139

69.5

87.74

1.48

64

14.9

149

74.5

92.86

1.56

68

15

150

75

93.30

1.57

68

16.5

165

82.5

98.30

1.65

72

The lambda used in Table 1 (for equation 4) was the mean wavelength of copper (Kα) which is 1.5418A. The Miller indices were obtained from Table 1, SGN pg 478.

Results and Discussion:

Each diffraction line was assigned an M 2 value based on Table 1 in SGN for the face- centered cubic system. Equation four was graphed with h 2 + k 2 + l 2 , or equivalently M 2 as the independent variable. Initially the latter points of the graph did not produce a straight line due to incorrect M 2 assignments. As theta increased some of the M 2 values had to be ignored when the

theta angle of two diffraction lines were very close because the two separate lines were not

indistinguishable. It is also possible that some lines were extra or missing. The M 2 values were

therefore adjusted to produce a straight line.

Unit Cell Length Determination

MM, RS, TM

1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 0 10 20 30 40
1.8
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0
10
20
30
40
50
60
70
80
M^2
(4sin^2(theta))/lamda^2

From the M 2 values, corresponding Miller indices were obtained. The unit cell length, a,

was found from the slope to be 6.60A. Cards corresponding to the appropriate a value were then

compared for similarities in the Miller indices series and unit cell length. The experimental

Miller indices were almost identical with literature values for KBr (a = 6.5966).

Experimental Values (hkl)

Literature Values (hkl)

111

111

200

200

220

220

311

311

222

222

400

400

331

331

420

420

422

422

511

511

440

440

600

600

620

620

622

622

444

640

640

642

642

References:

Shoemaker, D.; Garland, C.; Nibler, J., Experiments in Physical Chemistry, 6 th Edition, New

York: McGraw Hill Co., 1996, p 472-487.

Atkins, P. Physical Chemistry, 6th Edition, New York: W.H. Freeman and Co., 1998.