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CH 211 Tutorial New

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CH 211

2019/2020
Crystalline State Chemistry
Tutorial 2

1. a,b,c are the dimensions of a unit cell. Hypothetical planes make the following sets of
intercepts along the a,b,c directions respectively relative to the origin at (0,0,0).
Determine the Miller indices of these planes.

(i) a/2, b/4, c/3 (ii) a, b/4, 2c/3 (iii) a/4, –b/8, -c/6 (iv) a/6, -b/4, -c/2

What are the planes parallel to each other?


What are the planes belonging to the same set ?

2. a,b,c are the dimensions of a unit cell. Hypothetical planes make the following sets of
intercepts along the a,b,c directions respectively relative to the origin at (0,0,0).

(i) 3a/2, b, -c/3 (ii) 3a, 2b, -2c/3 (iii) 2a, 3b, c (iv) 3a/4, b/2, -c/6

(v) -a/2, -b/5, -c/3 (vi) 2a/3, 1b, 2c/5 (vii) a/4, b/10, c/6 (viii) 15a, 6b, 10c

(ix) a/2, b, 2c (x) –a, , 2c/4

Determine the Miller indices of these planes and comment on any relationships among
these planes.

3. Write short notes on,


i) Unit cell ii) Non-primitive lattices iii) Powder diffraction data bases

iv) Radius Ratio rules v) Miller indices

4. Sketch the planes in a tetragonal unit cell having the Miller indices of
(i) (222) (ii) (110) (iii) (-4 2 0) (iv) (-1 0 -1)

5. Write down the Kapustinskii equation.


Using equation estimate the lattice energy of K2SO4. K= 1.21×10−4 J·m·mol−1
d = 3.45×10−11 m. Thermodynamical radii of K+ = 1.38 Å and SO42- = 2.30 Å

6. Describe briefly four applications of X-ray powder diffraction method.

7. Compare and contrast the properties of ionic solids and molecular solids

8. Calculate the atomic packing factors for (i) body centered cubic structure
(ii) face centered cubic structure
9. The unit cell structure of an ionic compound containing anions (X) and cations (M) is
given below.

small –cations (M) large-anions (X)

i) Determine the coordination numbers of the cation and anion


ii) Determine the empirical formula of the ionic compound.
iii) Deduce the number of formula units per unit cell.
iv) If the radii of anion and cation are 1.70 Å and 0.92 Å respectively, calculate the radius
ratio of the ions in the above compound.
v) Describe briefly the packing arrangement of anions and cations in this system.
vi) Name a compound having this structure.

10. Chromium crystallizes in a bcc structure. The chromium atom has a radius of 1.40 Å.
i) Calculate the length of the unit cell edge a
ii) Calculate the volume of the above unit cell
iii) Calculate the packing efficiency (packing factor) of this system.

11. Calculate the incident angles for the maximum reflections occuring at the (200) and ( 4 -
1 0) planes of the cubic AgCl for the filtered Cu radiation ( Cu = 0.15418 nm). Cell
parameter of AgCl is 0.55491 nm.

12. What is lattice energy ?


The lattice energy of an ionic solid could be expressed by considering various fractions of
energies. What are these energy factors ?
Discuss the factors affecting on the magnitude of the lattice energy of a given ionic solid ?

13. Explain, how you would identify an unknown solid crystalline sample using powder
diffraction method.
14. The copper metal has face centered cubic structure with a unit cell edge length of 3.60 A.

(i) Determine the atomic radii of copper.


(ii) What is the closest distance between two copper atoms.
(iii) Calculate packing efficiency of this system.
(iv) Suppose copper combines with a metal M to from an inter-metallic compound MCu
in which both Cu and M have a coordination number of 8. To which crystal class this unit
cell belong ?

15. Sketch and indicate the salient features in the structure of zinc blend, ZnS. The radii of
Zn2+ and S2- are respectively, 0.074 and 0.184 nm.

16. Give the names of seven unit cell types and the general unit cell dimensions of them.

17. Anatase, Rutile and Brucite are three polymorphic forms of TiO2. If you are provided
with three unlabeled samples of TiO2, from which one sample belongs to Rutile form and
other two belong to Anatase form. Explain briefly how you would identify them using X-
ray diffraction technique. ( Experimental details are not required)

18. In the powder X-ray diffraction pattern of compound B, three strong peaks were observed
for the first order diffractions arising from (111), (002), and (500) crystal planes.
Determine the 2 values of those peaks, if the compound belongs to the face centered
cubic type. ( a = 0.460 nm). Wave length of the radiation used is Cu = 0.154 nm.

19. Sketch the crystal structure of CsCl.


ii) Determine the coordination numbers of cation and anion of this system.
iii) Derive an expression to calculate the unit cell dimension a of this system using the
radii of cation and anion
iv) If the radius of Cs+ = 1.74 Å and radius of Cl- = 1.81 Å, calculate the unit cell length (a)
of this system.
v) Calculate the packing factor (packing efficiency) of this system.
vi) Give two compounds having the crystal structure similar to CsCl
vii) Explain briefly, how CsCl structure would be different from CaF2 structure.

20. Calculate the packing factor of KBr if the unit cell length is 6.58 Å and ionic radii of K+ and
Cl- ions are 1.52 Å and 1.67 Å respectively.

21. The diffraction coming from (200) plane of a NaCl crystal occurs at an angle of 5.90o.
Calculate the length of the side of the NaCl unit cell and the d spacing of the (222) plane
(= 0.581 Å).

22. What are characteristic K lines of the X-ray spectrum of an element and how they are
generated?
23. Sketch the unit cells of Body centred cubic(BCC) and Face centred cubic(FCC) and
calculate the number of lattice points per each unit cell.
Explain which polymorphic form can give a higher intense peak in the diffraction pattern
for (200) plane.

24. A crystalline powder sample contains a mixture of NaCl, RbCl and LiCl in 1:1:1 ratio, in which all
three compounds adopt the structure type of NaCl. If you use powder X-ray diffraction(PXRD)
method to identify them, predict giving reasons,
(i) Which compound would give the highest intense peak in the PXRD pattern.
(ii) Which of the following crystal planes would give the strongest peak in the diffraction
pattern? (100) or (200) or (400) plane.

25. The ReO3 structure has a cubic unit cell type with Re at each corner of the unit cell and
one O atom on each unit cell edge at the middle point between Re atoms.
(i) Sketch this unit cell.
(ii) Determine the coordination numbers of cations and anions.
(iii) Calculate the number of formula units per unit cell.
(iv) Calculate the packing factor for this unit cell if both cation and anion have the same
ionic radii, r and unit cell length is a

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