Skip to main content

Laws of Crystallography: boon in Solid State Chemistry

Laws of crystallography
Crystallography is the branch of science which deals with the geometry, properties and structure   of crystals and crystalline substances. It is based on three fundamental laws.

The law of constancy of interfacial angles: It states that the size of the faces or even shapes of the crystals of a substance may vary widely with conditions of crystallization yet the interfacial angles between any two corresponding be 90˚, irrespective of the size and shapes of faces. The measurement of crystal angles is important in the study of crystals.

*Interfacial Angles- The crystals are bound by plane faces. The angle between any two faces is called an interfacial angle.

It is indicated from the above figure that the shapes of crystals are different but the angle between any two corresponding faces is 90˚.

2. Law of rational indices (Hauy’s law): This law states that “the ratio between the intercepts on the axes for the different faces of a crystal can always be expressed by rational numbers”.
Let OX, OY and OZ be the three crystallographic axes and ABC be the unit plane and LMN the plane of the crystal under study. The unit intercepts are a fro OA, b for OB and c for OC. For the plane (face) LMN, the intercepts will be OL (=2a),OM (=4b) and ON(=3c). Thus the intercepts for the plane are in the ratio of 2a : 4b : 3c where 2,4,and 3 are simple intergral whole number and are known as the are Weiss indies of the plane. It must be noted that it is not necessary that the Weiss indices are always simple integral whole number they may be fractional number or even infinity. Hence these are replaced by Miller indices which are always simple intergral whole numbers. These are represented by h, k and l corresponding to a, b and c,



Miller indices of a plane of a crystal are inversely proportional to the intercepts of that plane on the various axes. Miller indices for a plane may be obtained from Weiss indices (coefficients of the unit lengths a, b, and c of the plane) by talking the reciprocals of the coefficients of Weiss indices and multiplying throughout by the smallest number on order to make all reciprocals as intergers.

For illustration, consider a plane which in Weiss notation is given by ∞a: 2b: c. The Miller indices of this plane may be calculated as below


Multiplying by 2 in order to get whole numbers =0, 1, 2
Thus the miller indices of the plane are 0, 1 and 2. Hence the plane is designated as the (012) plane, i.e. h=0, k=1 and l =2.

Let us now describe the planes in a cube. It should be remembered that if a plane is parallel to an axis, its intercept with that axis would be infinity. Thus, the miller index for that plane will be zero (1/ =0). For example, consider the shaded plane in following figure. It is clear from the figure that the fractional intercepts of the shaded plane are: 1, ∞, ∞






Similarly, the miller indices of some planes in cubic crystals, shown shaded in following figure are as given below:


Fractional intercepts                1                 1                1                        
Reciprocal of intercepts            1                 1                1

Miller indices                            1                 1               1

Ex : A crystal plane intercepts the three crystallographic axes at a, 1/2b and 3/2c where a, b and c are the unit lengths along X, Y and Z axes respectively. What are the miller indices of this plane?

  Solution. Form the given data the Weiss indices are 1, ½, 3/2, i.e.

                                      A          b           c
                                     1           ½          3/2
Talking reciproclas     1           2           2/3
Multiplying by 3          3           6           2

Thus the miller indices of the plane are 3, 6, 2 and hence the plane is designated as (362)plane.
Ex: Calculate the miller indices of crystal plane which cut through the crystal axes at 2a, -3b, -3c.
Solution.
Given
                                                              a          b           c
                                                              2         -3          -3
Talking Reciprocals                           1/2       -1/3        -1/3
Multiplying by 6                                  3           -2          -2
Ex : Calculate the miller indicies of crystal plane which cut through the crystal axes at
 (i) (2a, 3b, c)
(ii)(a, b, c)
(iii)(6a, 3b, 3c)
Solution (i):

Following the procedure given above, we prepare the table as follows:
                       a           b         c                     
                       2           3          1                      Fractional intercepts
                      1/2        1/3        1                      Reciprocals
                       3            2         6                      Clear fractions 
Hence, the miller indices are (326).

Solution(ii):
                       a           b         c   
                      1           1         1            Fractional intercepts
                      1           1         1            Reciprocals of intercepts
                      1            1        1            Clear fractions
Hence, the miller indices are (111).
Solution (iii): 

                   a           b         c   
                    6          3         3                     Fractional intercepts
                  1/6       1/3      1/3                     Reciprocals of the intercepts
                          1           2         2                       Clear fractions

Hence, the miller indices are (122).

*Some other planes represented by miller indice (h,k,l) are as follows-

Problems for practice:
1. The Miller Indices of two parallel planes in a crystal are-
(a) Same          (b) Different          (c) May be same or different          (d) None of these
2. Calculate the miller indices of the crystal plane which cut through the crystal axes at (2a, 3b, c)-
(a) 326          (b) 122          (c) 236          (d) 623

3. The miller indices of the shaded plane shown in the figure below are-







(a) (001)          (b) (010)          (c) (011)          (d) (100)    
4. (hkl) represents –
(a) Lattice parameters          (b) Crystal faces          (c) Crystal Systems          (d) Miller Indices
5. If a plane in a cubic crystal intersects the a, b and c axes at 1, 2 and Infinity, respectively. Its Miller Indices will be –                                                       (IISc-Integrated PhD 2010)
(a) (120)          (b) (210)          (c) (12∞)          (d) (21∞)
6. If weiss indices of face of a crystal are 1, ∞, ∞, then its miller indices will be:
(a) 100               (b) 011               (c) 010               (d) 101                     (BHU 2016)
7. In any crystal, ratio of weiss indices of the face is 2:4:3, then the miller indices would be-                                                                                                            
(a) 634               (b) 346              (c) 436               (d) 643                     (BHU 2016)

8. The miller indices of the face having intercept (a/2, 2b, ∞c) where a, b, c are the unit cell axes, is:                                                                                            (University of Hyderabad 2015)
(a) (410)               (b) (220)               (c) (210)               (d) (012)

9. The miller indices of the planes with intercepts 4a, 6b, ∞c where a, b, c are the unit cell edge lengths are-                                                                                  (BHU 2015)
(a) (320)               (b) (230)               (c) (023)               (d) (46∞)

10. A crystal plane is parallel to the x-axis and y-axis and makes an intercept of ½ on the z-axis. The miller indices of the planes are-                                                             (IISc 2012)
(a) 112                    (b) 220                    (c) 001                    (d) 002

Answers:
1 (a)               2. (a)               3. (d)               4. (d)               5. (b)               6. (a)
7. (a)              8. (a)               9. (a)               10. (d)

3. The law of symmetry : it states that all crystals of a substance possess the same elements* of symmetry. The three important elements of symmetry are (i) plane of symmetry, (ii) axis of symmetry, (iii) centre of symmetry.
(i) Plane of symmetry : it is an imaginary plane which can divide the crystal into two halves such that one is the mirror image of the other. A cubic crystal ,e.g., has two types of plane of symmetry-
(a) Rectangular planes of symmetry : These are the planes situated midway and parallel to the two opposite faces. Since a cubic crystal has six faces, i.e. three pairs of opposite faces, it has three rectangular plane of symmetry as shown in following figure-



(b) Diagonal plane of Symmetry: These are the plane touching the opposite edges. Since there are 12 edges or six pairs of edges. So there are 6 diagonal plane of symmetry.As they lie like the diagonal that is why these are called as diagonal plane of symmetry.

(ii) Axis or Line of Symmetry: It is an imaginary axes (line) about which the crystal may be rotated so that it gives the equivalent orientation more than once in a complete rotation through 360˚. It is donated by Cn (n is an integral number)
On the basis of n, these are of following types-
(a) Axes of 2-fold Symmetry (C2): On rotation of 180˚, we can get equivalent orientation. It pass through the diagonally opposite edges. Total edges are 12 so that 6 two fold axes, are present in a cube.









(b) Axes of 3-fold symmetry (C3): On rotation of 120˚ through the diagonally opposite corners of the cube. We can get equivalent orientations. Total corners are eight. So 4 such type of symmetry elements are there i.e. 4 C3 axes.









(c) Axes of 4 fold of symmetry: On rotation of 90˚ through two opposite faces, we will get equivalent orientations. Total faces are 6, so 3 4-fold elements of symmetry are present in a cube.


















Hence Total number of elements of symmetry in a cubic crystal are 6 C2 + 3 C4 + 4 C3 
(iii) Centre of Symmetry: It is a such point in the crystal that any line drawn through it intersects the surface of the crystal at equal distances on either side. A crystalmay have one or more axes of symmetry or plane of symmetry but it never has more than one centre of symmetry.
         So total number of elements of symmetry in a cubic crystal are 23.
         Plane of Symmetry = 3 + 6 = 9
         Axes of Symmetry = 3 + 4 +6 = 13
Centre of symmetry = 1
Problems for practice:

1. The total number of elements of symmetry in a cubic crystal is-
(a) 9        (b) 23        (c) 13        (d) 1
2. A crystal may have one or more planes of symmetry as well as one or more axes of symmetry but it has-
(a) Two centres of symmetry                                    (b) no centre of symmetry  
(c) one centre of symmetry                                       (d) four centres of symmetry
3. Total number of axes of three-fold symmetry in a cubic crystal are-
(a) 3        (b) 4        (c) 6        (d) 13
Answer:
1. (b)          2. (c)          3. (b)  













Comments

Post a Comment

Popular posts from this blog

Aspiring to pursue P.G. or PhD in chemistry: choose CSIR/GATE/ IIT JAM

With the high increasing rate of competition with each passing day, it is difficult for the students to cope up with the fear and pressure. But to make the competition simpler and easier all you need is a good guidance and best institute. One really should know about all the possible prospects in chemistry and chemical sciences. Certain topics that hold a major portion of the paper of IIT-JAM, NET, GATE include topics like solid state, organomettalic chemistry, coordination chemistry, stereochemistry and many more. Catching hold over these topics will lead to definite success path in these competitive exams like CSIR-NET, GATE, IIT-JAM. In case of CSIR-NET (or CSIR-UGC-NET/JRF),  the eligible candidates may apply Online through a link available at CSIR, HRDG website: www.csirhrdg.res.in . In order to apply Online the candidates are required to download Bank challan Performa from the above website and then deposit the requisite examination fee in any of the Indian Bank branch

Surface Tension and capillary action, a characteristic property of Liquids

Surface Chemistry, Surface Tension and Capillary Action Surface Tension: → Surface tension is a characteristic of surface of liquids due to which it try to decrease its area. For this purpose, a force of attraction is applied betweem the molecules of liquids on the surface. For this reason, surface of a liquid behave like a stretched membrane. → Consider a molecule P some where in the body of the liquid. This is attracted equally in all dieactions by auther molecules which surround it as shown in fig and therefore cancel the effect of one another. → Consider, next, a olecule R at the surface of the liquid. THe downward attractive force are greater than the upwardr forces because there are more molecules of liquid below than that in air above the surface. These inbalanced atttractive forces acting downward tend to draw the surface mlecules into the body of the liquild and therefore, tend to reduce the surface to a minimum. → It is well know that force of attr