Sie sind auf Seite 1von 14

With the particles in every next row are placed in the depressious between the particles of first row.

The particles of third row will show vertical alignment with the first row as shown below -

Such a packing gives hexagonal pattern thus called HEXAGONAL CLOSE PACKING The hexagonal close packing is more efficient than square close packing as here more space is occupied by spheres. The above two packings under category (b) are considered as 2 dimensional packing. The packing which we will discuss now onwords are considered as 3 dimensional packings. As among 2 dimensional packings hexagonal close packings are more efficients, the 3 dimensional packings are based upon this hexagonal close packing patterns. In 2 dimensional packings the voids are also 2 dimensional similarly in 3 dimensional packings the voids are 3 dimensional. The three dimensional packing may be of (a) Hexagonal close packing (hcp) (b) Cubic close packing (ccp) (c) Body centred cubic packing (bccp) The 2 dimensional hexagonal close packing observation show types of voids in it as shown below -

keeping both the types of void in mind in 3 dimensional packing when the IInd row of spheres is placed in such a way that its spheres find place in the voids marked X of first row (void marked Y left unoccupied) as shown below-

In the second layer 2 types of voids seen again(i) Those which lie above the spheres of first layer (marked l in above diagram) (ii) Those which lie above the voids Y of first layer (marked m in above diagram). Now when the third layer is placed in such a way that the spheres cover the l voids of second layer, thus a three dimensional cubic packing is obtained where the spheres in every 3rd or alternate layer are vertically aligned i.e.,, 3rd layer is directly above 1st or 4th layer is directly above 2nd. The arrangement is also called as ABAB ....... if we designate first layer as A and second layer as B as seen below-

Such a ABAB ..... packing is called HEXAGONAL CLOSE PACKING (3 dimensional) e.g., Be, Mg crystals etc. Now, consider the same arrangment described above till 2nd layer, and if a 3rd layer is placed in such a way that spheres cover the void m of second layer, a layer different from A and B described above is seen. Let us call it as layer C. Continuing further, if the forth layer is placed over the 3rd layer in such a way that each sphere of it align vertically with the first layer, the packing is called CUBIC CLOSE PACKING with ABC, ABC ......... pattern of layers as shown below -

The packing is also called face centred cubic packing (fccp). The examples of ccp include Iron, Ni,Cu,Ag,Au,and Al etc. Both the above patterns are almost equally efficient and occupy maximum possible space i.e., about 74% of the available volume with variable coordination nos. from 4 to 12 i.e., 4, 6, 8 and 12. The bccp structure has a central atom occuping a lattice site with 8 atoms at the corner of cube. Here the space occupancy is only 68% and coordination no. is almost constant i.e., 8. For example Li, Na, K, Rb and Cs. In closely packed structures the empty space is called interstitial site or void. This void can be a simple triangular space in the case of 2 dimensional packing i.e., when all the spheres lie in same plane such voids present as triangular spaces in 2 dimensional packing patterns are called TRIGONAL VOIDS.

In 3 dimensional close packing patterns the voids can be(a) Tetrahedral (b) Octohedral A tetrahedral void is a simple triangular space surrounded by 4 spheres as shown below -

An octohedral void is a double triangular void surrounded by 6 spheres as shown below -

The sizes of above written voids can be seen in increasing order as Trigonal <> Their sizes can be calculated on the basis of sizes of spheres involved in the formation of solids. (i) The size of triagonal void is 0.115 times of the radius of bigger sphere involved. (ii) The size of tetrahedral void is 0.2247 times of the radius of bigger sphere involved. (iii) The size of octohedral void is 0.414 times of the radius of bigger sphere involved. In a closely packed structure containing x spheres (atoms, or molecules or ions) there are 8 x trigonal voids, 2 x tetrahedral voids and x octohedral voids. The packing fraction i.e., the space occupied in different packings is as follows (a) In a simple cubic unit cell =

(b) In hexagonal close packing and face centre cubic

structure=

The density of a unit cell and hence the density of a crystal is given by the formula.

Here, Z = No.of particles present per unit cell i.e., 1 for simple, 2 for Bcc, 4 for Fcc. M = Atomic mass of element a = Edge of the unit cell NA= Avogadro number. for ionic crystals the formula used is same and the difference lies in (1) Z = No. of formula units in one unit cell. (2) M = formula Mass (Molecular Mass) of the compd. (3) a = Edge which is 2 x distance between Na+ and Cl- in NaCl crystal. The ionic radius ratios (of cation and anion) play a very important role in giving a clue to the nature of crystal structure of the ionic substance. This can be clear from the table given below -

The ionic crystals may be Formation of substitutional solid depends upon the electronic structure of impurity while that of latter on the size of impurity. The number (n) of defects per cm3 is given by n = N x ew/2RT Where N = no. of sites per cm3

W = Work of energy requried to produce a defect. T = Absolute temperature R = Gas constant e = base of natural logarithm Solids are classified into 3 groups namely (i) Conductors with conductivity range of the order of 107 (Wm )-1 e.g Metals (ii) Semiconductors with conductivity range 10-6 - 104(Wm)-1 e.g. Semi metals (iii) Insulators with conductivity range 10-10 -10-20 (Wm)-1 e.g.Non metals In most of the solids conduction is through electron movement under an electric field, however, in some ionic solids the conduction is through ions. In metals conductivity strongly depends upon the no. of valence electrons available per atom. The atomic orbitals form molecular orbitals which are so close to each other as to form a BAND. The conducitivity of solids can be better explained on the basis of energy gap present between the conduction band (HIGHER UNOCCUPIED BAND) and the valence band. (i) In metals the conduction band is almost overlapping with the valence band i.e., there is no energy gap present between these two bands or valence band is not completely filled. Then electrons can flow easily under the influence of electric field in both the cases.

(ii) In the case of semimetals the gap between valence band and conduction band is small and therefore some of the electrons may jump from valence band to conduction band and some conductivity is observed. The conductivity here increases in temperature. The reason for such an increase in lowering of energy gap shown below in the figure.

The heat is actually responsible for ejection of electrons from their place thus leaving a (+)ve change their (positive hole). The crystal can now conduct electricity because on applying the electric field the electrons, and holes migrate in opposite directions. This type of conductance is called INTRINSIC CONDUCTANCE : For Example Si, Ge etc. NOTE : (1) For practical pruposes the conductivity of pure Si and Ge is very low at room temperature. In order to increase their conductance the pure substances are carefully doped (introduced with small amount of impurities in the form of elements of the 13 and 15 group of periodic table) . (2) The group 15 elements have 1 electron excess to Si or Ge after forming 4 covalent bonds with group 14 member (Si or Ge). this excess free electron is responsible for electrical

conductivity in them. Group 14 elements when doped with group 15 elements are called ntype semiconductors. Here n specifies that negative charge flows in them. (3) The group 13 elements have 1 electron short to Group 14 elements, thus giving rise to electron deficient band or a hole. Here such holes are responsible for electrical conductivity. Thus group 14 elements when doped with elements of group 13, these are called p-type semiconductors. Here, p specifies that conduction is through positive holes in them.

(4) Various combiantions of n-type and p-type semiconductors are used to make electronic components. For example, diode is a combination of p and n-type semiconductors and used as rectifier, TRANSISTORS which are pnp or npn sandwich semiconductor are used to detect or amplify radio or audio signals.

(iii) In the case of non metals (insulators) the energy gap between valence band and conduction band is so large that it can not even covered up by supplying energy in the form of heat.

Besides conductivity solids also show magnetic properties and dielectric properties. On the basis of magnetic properties solids can be categorised to (a) Diamagnetic i.e., which are feebly repelled by magnetic field. These have the characteristic absence of unpaired electrons in them i.e., their all electrons are paired. For Example - Non metallic elements (except O2 and S) inert gases and species with paired electrons e.g. T1O2, V2O5, C6H6 NaCl etc. (b) Paramagnetic i.e., which are attracted by magnetic field due to the presence of atoms, ions or molecules with impaired electron in them (e.g., O2, Cu++, Fe3+ etc.). In magnetic field these tend to orient themselves parallel to the direction of magnetic field. These are used in electronic appliances. (c) Ferromagnetic i.e., which show magnetism even in the absence of magnetic field, Fe, Co and Ni are 3 elements which show ferromagnetism at room temperature. A spontaneous alignment of magnetic moments in the same direction gives rise to ferromagnetism. The ferromagnetism is not seen above a temperature called CURIE TEMPERATURE. (d) Antiferromagnetic i.e., those which have net magnetic moment zero due to compensatory alignment of magnetic moments. For example MnO, MnO2, FeO,NiO, Cr2O3 etc. The dielectric properties are seen in insulators, which, when are placed in on electric field, show generation of dipoles in them due to the pulling of electrons & nuclei of atoms or molecules in opposite directions. These dipoles- (a) may align themselves in an ordered manner so that there is a net dipole moment in the crystal. (b) may align themselves in such a manner that dipole moments may cancel each other (c) It is also possible that there are no dipoles in the crystal but only ions are present. The crystals where situation (a) is found exhibit PEIZOELECTRICITY or PRESSURE ELECTRICITY, which is production of electricity by a polar crystal when mechanical stress is applied to it. Peizoelectric crystals also show development of mechanical stress when electric field is applied to them, thus acting as a mechanical electrical transducer. Note : 1. Peizoelectric crystals with permanent dipoles are said to have ferroelectricity e.f. Rochelles salt, BaTiO3, KH2PO4 etc. 2. Peizoelectric crystals with zerodiople are said to have ANTIFERROELECTRICITY 3. Some peizoelectric crystals, when heated produce small electric potential or PYROELECTRICITY The phenomenon where electricity passes through a material without resistance is called SUPERCONDUCTIVITY. The material showing this property is said to be SUPERCONDUCTOR. It was KAMMERLINGH ONNES of Netherlands who first reported the case of Hg as superconductor at a very low temperature of 4.2 K. Afterwords some metals alloys and certain organic solids have been reported to be superconducting bUt at very low

temperatures. Now a days superconductors are also reported at comperatively higher temperatures for example YBa2,Cu3O7 at 90K, Bi2 Ca2Sr2Cu3O10 at 105 K, and Tl2 Ca2 Ba2 Cu3O10 at 125 k etc

Question

1. ABABA......... represents an arrangement of layers called(a) hexagonal closed packing (b) cubic closed packing (c) body centred cubic packing (d) fluorite close packing 2. The number of molecules per unit cell which crystalizes in the form of end face centred (monoclinic) lattice with a molecule at each lattice site (a) 1 (b) 2 (c) 4 (d) 6 3. In diamond the coordination no. of carbon is(a) 4 and its unit cell has 8 carbon atoms. (b) 4 and its unit cell has 6 carbon atoms (c) 6 with 4 carbon atoms in unit cell (d) 4 with 4 carbon atoms in unit cell Hint : The space lattice of Diamond is fcc 4. Which of the following crystals does not have 8 : 8 coordination. (a) NH4Cl (b) AlFe (c) MnO (d) NH4Br 5. The bond length and bond angles in molecules in the solid state are calculated by x-ray differaction technique because x-rays are scattered by (a) Nucleus (b) Protons only (c) Neutrons only (d) Electrons only 6. Mark the incorrect statement (a) In hcp and ccp the sphere is in contact with 6 spheres of its own layer. (b) In both hcp and ccp the sphere has 3 spheres above it and 3 below it. (c) In both hcp and ccp the coordination no. is 12. (d) In inverse spinel (e.g. magnetite, Fe3O4) only dipositive ions occupy octohedral voids while tripositive ions occupy tetrahedral voids. 7. A compound formed by elements A and B crystallises in cubic structure, in which atoms of A are at the corners while that of B are at the face centre. The formula of the compound is -

(a) AB3 (b) AB (c) A3B (d) None of these 8. Na atom crystallises in bcc lattice with cell edge (a) = 4.29A The radius of Na atom is (a) 18.6A (b) 1.86A (c) 1.86 pm (d) 1.860 pm 9. Pick out the incorrect statement (a) NaCl structure transform to CsCl structure on heating (b) In CaF2 structure each F- ion is coordinated by 4 Ca++ ions and each Ca++ ion is coordinated by 8F- ions. (c) NaCl has 6:6 coordination, while CsCl is with 8:8 coordination (d) In Na2O each oxide ion is coordinated by 8 Na+ ions and each Na+ ion by 40 oxide ions 10. NaCl is doped with 2 x 10-3 mole % of SrCl2. The concentration of cation vacancies is (a) 6.02 x 108per mol (b) 12.04 x 1018 per mol (c) 3.01 x 1018 per mol (d) 12.04 x 1020per mol 11. CaO and NaCl have the same crystal structure and nearly the same ionic radii. If x is the lattice energy of NaCl, the lattice energy of CaO is very nearly : (a) 2 x (b) x (c) 4x (d) x / 2 12. Which of the following expression is correct for a CsCl unit cell with lattice parameter a.

13. Which of the following crystals have 6:6 coordination? (a) NH4l (b) MnO (c) ZnS (d) None 14. Match list I with list II and select the correct answer by using the codes given below : List I (Shape) List II (Radius ratio) (A) Planer triangle 1 0.732 (B) Square Planer 2 0.225 (C) Body Centred cubic 3 0.115 (D) Tetrahedral 4 0.414 Codes A B C D (a) 3 4 1 2 (b) 3 2 1 4 (c) 2 1 4 3 (d) 1 3 4 2 15. Calculate the ionic radius of a Cs+ion assuming the cell edge length for CsCl is 0.4123 nm and that the ionic radius of a Cl- ion is 0.181 nm. (a) 0.176 nm (b) 0.231 nm (c) 0.358 nm (d) 0.116 nm 16. Because of anisotropy (a) Mica cleaves into long, rod like peices and asbestos cleaves into thin sheets. (b) Mica as well as asbestos cleaves into thin sheets. (c) Mica cleaves into thin sheets and asbestos cleaves into long rod like peices

(d) Mica as well as asbestos cleaves into long rod like peices. 17. Which of the following crystals has 4:4 coordination ? (a) HgS (b) NH4F (c) NaCl (d) None 18. The hcp and ccp structure for a given element would be expected to have (a) the same alignment of layers. (c) the same density (c) the same packing fraction (d) All the above 19. Which of the following statements is correct (a) The coordination number of each ion in a CsCl crystal is 9. (b) A metal that crystallizes in a bcc structure has a coordination number of 12. (c) A unit cell an ionic crystal shares some of its ions with other unit cells. (d) The length of unit cell in NaCl is 552 pm withrNA= 95 pm and rCL= 181 pm 20. Iron crystalizes in a bcc system with a lattice parameter of 2.861 A. Calculate the density of Iron in it (at wt. of iron = 56, NA = 6.02 x 1023 permole) (a) 7.92 g/ml (b) 8.96 gm/ml (c) 2.78 gm/ml (d) 6.72 gm/ml 21. Which of the following statements is incorrect ? (a) A substitutional solid solution is one in which atoms of the solute metal occupy some locations that solvent metal atoms are expected to occupy (b) An interstitial solid solution is one in which the solute atoms occupy the interstices between the solvent atoms. (c) An intermediate compound is a compound formed between metals and metalloids. (d) Cu3Zn is an intermetallic compound. 22. MZXhave a structure closely related to that of fluorite it is actually reverse of fluorite structure hence called ANTIFLUORITE structure. In such a structure(a) Smaller cations occupy the position of fluoride ion and larger anions that of Ca++ ions. (b) Larger cations occupy the position of F- ions and smaller anions that of ca++ ions. (c) Each F- is surrounded by 4 Ca++ in a tetrahedral arrangement (d) F- ions occupy all the 8 octohedral voids. 23. The incorrect statements for sphalerite, a form of ZnS is(a) It structure is similar to diamond except that alternate atoms are Zn and S. (b) Because the S- is larger than the Zn ion only 6 rather than 4 or 8 sulfide ions can be packed around a Znion. (c) As s- is larger than Zn++ only 4 rather than 6 or 8 s- can be packed around Zn++ (d) ZnS is a polar covalent compound. 24. The fluorite structure shows 8:4 coordination, which of the following lattices have fluorite like structure (a) SrCl2 (b) BaF2 (c) ThO2 (d) All the above 25. In an NaCl structure all the (a) Octohedral voids are unoccupied (b) Tetrahedral voids are unoccupied (c) Octohedral as well as tetrahedral voids occupied

(d) Octohedral as well as tetrahedral voids unoccupied. 26. Which of following structures have layered lattices(a) Diamond (b) Ice (c) Cadmium lodide (d) All 27. T1O2 (rutile) shows 6:3 coordination. The solid having rutile like structure among the following is (a) ZnS (b) KCl (c) SnO2 (d) None of the above 28. The statement correct for rock salt structure is (a) The tetrahedral voids are larger than octohedral voids (b) The tetrahedral voids are unoccupied while octohedral voids are occupied by cations. (c) The radius ratio is 0.732 (d) The radius ratio is 0.999. 29. How many octohedral voids are there per sphere in a ccp structure. (a) 4 (b) 2 (c) 1 (d) 6 30. Which of the following crystals shows 4:2 coordination? (a) CaF2 (b) SiO2 (c) PbO2 (d) None of the above 31. The coordination no. of fcc structure for metals is 12, since(a) each atom touches 4 others in same layer, three in layer above and 3 in layer below. (b) each atom touches 4 others in same layer, 4 in layer above and 4 in layer below(c) Each atom touches 6 others in same layer, 6 in layer above and 6 in layer below. (d) Each atom touches 3 atoms in the same layer, 6 in layer above and 6 in layer below. 32. Amorphous solids may be classified as (a) Isotropic and super cooled liquids (b) Anisotropic and super cooled liquids (c) Isoenthalpic and superheated liquids (d) Isotropic and superheated solids 33. Correct statement for ccp is (a) each octohedral void is surrounded by 6 spheres & each sphere is surrounded by 30 octohedral voids. (b) each octohedral void is surrounded by 6 sphere & each sphere is surrounds by 6 octohedral voids. (c) each octohedral void is surrounded by 6 spheres and each sphere is surrounded by 8 octohedral void (d) each octohedral void is surrounded by 6 sphere and each sphere is surrounded by 12 octohedral voids. 34. If hcp and ccp structures are made up of spheres of equal size, the volume occupied per sphere is (given r=radius of sphere) (a) 1.33 r3 (b) 5.66 r3 (c) 2.66 r3 (d) 7.40 r3 35. F - centres are (a) The electrons trapped in anionic vacancies (b) The electrons trapped in cation vaccancies (c) Non equivalent sites of stoichiometric compounds (d) All of the above. 36. Mark the incorrect relation (a) No. of octohedral voids (In hcp, ccp) = No. of atoms present in closed packed

arrangement (b) No. of tetrahedral voids = 2 x no. of octohedral voids (c) ABAB ..... is cubic close packing and ABC ABC .... hexagonal close packing (d) Radius of octohedral void r = 0.414 R 37. It was found that parazoxyanide melts at 389 K to give a turbid non uniform liquid but at 408 K, it melts to form clear uniform isotropic liquid. What type of crystal is being described. (a) Molecular crystal (b) covalent crystal (c) Liquid crystal (d) H-bonded crystal 38. Li metal has a bccp structure. Its density is 0.53g per cm3 and its atomic mass is 6.94 gm per mol calculate the edge length of a unit cell of Li metal (a) 153.6 pm (b) 351.6 pm (c) 527.4 pm (d) 263.7 pm 39. A metal crystalizes in 2 cubic phases i.e., fcc and bcc whose unit cell lengths are 3.5A and 3.0A respectively. The ratio of their densities is (a) 3.12 (b) 2.04 (c) 1.46 (d) 0.72 40. In the x-ray differaction of a set of crystal planes having d equal to 0.18 nm a first order reflection is found to be at an angle of 22. The wave length of x-ray is - (given sin 22 = 0.208 (a) 0.0749 nm (b) 0.0374 nm (c) 0.749 nm (d) None of these 41. For a given crystal the lattice parameter a is 318 pm. The d-spacing for a (III) plane is (a) 225 pm (b) 184 pm (c) 318 pm (d) 390 pm 42. Which of the following statements are correct in context of point defects in a crystal ? (a) AgCl has anion Frenkel defect and CaF2has Schottky defects. (b) AgCl has cation frenkel defects and CaF2has anion frenkel defect. (c) AgCl as well as Ca2 have anion frenkel defects (d) AgCl as well as CaF2has schottky defects. 43. LiBH4 Crystalizes in orthorhombic system with 4 molecules per unit cell. The unit cell dimensions are a = 6.8 Ab=4.4 A and ?c = 7.2A. If the molar mass is 21.76 the density is (a) 0.6708 gm/cm3. (b) 1.6708 gm/cm3. (c) 2.6708 gm/cm3. (d) All of the above 44. NaCl shows Schottky defects and AgCl Frenkel defects. Their electrical conductivity is due to (a) Motion of ions and not the motion of electrons (b) Motion of electrons and not the motion of ions (c) Lower coordination number of NaCl (d) Higher coordination number of AgCl 45. A piece of copper and another of Ge are cooled from room temp. to 80 K. The resistance of (a) Each of them increases (b) Cu increases and that of Ge decrease (c) Cu decrease and that of Ge increases (d) Each of them decreases 46. If a crystal contains a total of N atoms, and n schottky defects are produced by removing n cations and r anions from the interior of the crystal then -

47. Choose the incorrect statement ? (a) The crystal structure of rock salt in an fcc array of anions in which cations occupy all the octohedral voids (b) The sphalerite crystal structure is an expanded fcc anion lattice with cations occupying one type of tetrahedral hole. (c) In fluorite structure, cations occupy half the cubic holes of a primitive cubic array of anions. (d) None of the above. 48. A solid has 3 types of atoms namely x, y and z, x forms a fcc lattice with y atoms occupying all the tetrahedral voids and z atoms occupying half the octohedral voids. The formula of the solid is (a) X2Y4Z (b) XY2Z2 (c) X4Y2Z (d) X4YZ2 49. KCl crystallises in the same type of lattice as does NaCl calculate the ratio of the side of the unit cell for KCl to that for NaCl (a) 1.222 (b) 1.224 (c) 1.414 (d) 0.732 50. Some polar crystals produce small electric current on heating. This phenomenon is called(a) Piezo electricity (b) Pyroelectricity (c) Ferroelectricity (d) Anti ferroelectricity

Das könnte Ihnen auch gefallen