Vous êtes sur la page 1sur 11

SVPrecis_12th_Chemistry_Unit No.

1_The Solid State Unit Wise Weightage : 04 Marks Objectives General Characteristics of solids Amorphous and crystalline solids Classification of crystalline solid based on different type of binding forces (molecular, ionic , covalent and metallic solids). Crystal lattices and unit cells Determination of number of atoms in a unit cell Packing in solids / void in solids. Calculation of density of unit cell. Imperfection in solids Calculation of density of unit cell Imperfection in solids (defects) Electrical & Magnetic properties of solids MEMORY TIPS SOLIDS: The substances which have definite volume, shape and size are called solids. They have regular order of their constituent particles. Held by fairly strong forces. CLASSIFICATION OF SOLIDS: Based on the arrangement of constituent particles:Crystalline solid is the one in which the constituent particles are arranged in a regular manner throughout the entire three dimensional network. A crystal is defined as a solid figure having planar surface, sharp edges and definite geometrical shapes. Amorphous solids are those solids in which the constituent particulars are arranged in haphazard manner and not in a regular fashion. Difference between crystalline solid and an amorphous solid (also called pseudo solids) Crystalline Solid Amorhphous solid (i) The constituent particles are arranged in a regular The constituent particles are not arranged in any fashion having short range as well as long range regular fashion; there may be at the most short order. range order. (ii) They have sharp melting points They melt over a range of temperature (iii) They are anisotropic They are isotropic (iv) They undergo a clean cleavage They undergo an irregular cut (v) Examp. etc Examp. Rubber, glass, polymers etc. Classification of crystalline solids: Depending upon the nature of bonding, the crystalline solids have been classified into four types as given in the table below: Type of Solid Constituent Particles Nature of Forces Example 1. Ionic Positive and negative ions Strong electrostatic forces of attraction 2. Molecular Molecules van der Waals forces (dry ice), solid sulphur, ice 1

3. 4.

Atoms Covalent bonds Diamond, Silicon Positive metal ions (Kernels) and Metallic bonds All metals and some mobile electrons alloys Crystal lattice: A regular arrangement of the constituent particles of a crystal in the three dimensional space is called crystal lattice or space lattice. Unit Cell: The smallest three dimensional portion of the space lattice which when repeated over again and again in different directions produces the complete space lattice is called unit cell. Types of unit cells: i. Simple: Here the particles are present only on the corners. ii. Face centred: here in addition to the particles on the corners, there is one particles present on the centre of every face. iii. End face centred: Here in addition to the particles on the corners, there is one particle in the centre of two opposite faces. iv. Body centred. Here in addition to the particles on the corners, there is one particle present within the body of the unit cell. No. of particles per unit cell: Contribution by an atom, ion, molecule at a) Corner = per unit lattice b) c) Face d) Edge = Body = per unit lattice per unit lattice = 1 per unit lattice

Covalent Metallic

Calculation of number of atoms per unit cell (also known as rank denoted by Z) Type of unit cell At corners = Number of atoms Within body 0 On faces 0 0 = 1 2 4 Total number of atoms per unit cubic cell (Z)

Simple Cube

Body centred cube 1 = (BCC) Face centred cube 0 = (FCC) Type of crystal systems, their axial ratios and angles and unit cells: Crystal System (i) (ii) (iii) (iv) (v) (vi) Cubic Tetragonal Rhombic or Orthorhombic Monoclinic Triclinic Trigonal or Rhombohedral 2 Axial ratios Axial angles

Unit cells / Bravals lattices Simple, face centred, body-centred. Simple, body centred. Simple, face centred, end centred, Body centred Simple, end centred Simple Simple

(vii)

Heaxagonal

simple

Note: In all, there are seven crystal systems and fourteen Bravais lattices (unit cells). Coordination number: The number of nearest neighbors with which a given sphere is in contact Crystal structure and their co-ordination number Crystal structures BCC HCP CCP or FCC Co-ordination number 8 12 12

Types of close packed structure: There are three ways in which atoms in a crystal are packed: i. ii. iii. Hexagonal close packing (hcp) i.e. Cubic closing packing (ccp) i.e. Body centred cubic (bcc)

Percentage of space occupied by spheres :a) b) c) d) e) % of space occupied in (close packing in two dimensions) % of space occupied in square close packing = 52.4% (close packing in two dimensions) % of space occupied in fcc=74% (close packing in three dimensions) % of space occupied in bcc = 68% (close packing in three dimensions) % of space occupied in cubic close packing (CCP) (ABC ABC.)= 74% (close packing in three dimensions).

Calculations of the space occupied i.e. packing fractions

a) In a simple cubic unit cells Suppose the edge length of the unit cell = and radius of the sphere = As spheres are touching each other, evidently, No. of sphere per unit cell = Volume of the sphere = Volume of the cube = ( )

Fraction occupied i.e. packing fraction Or % occupied = 52.4% b) In face centred cubic structure Here

No. of spheres in the unit cell = Or % occupied = 74% 3

c) In body centred cubic structure or

( )

No. of spheres per unit cell = Fraction occupied i.e. packing fraction =

Or % occupied = 68% Relationship between the nearest neighbor distance (d) and the edge (a) of a unit cell of a cubic crystal: Simple Body Centred Face Centred

Nearest neighboring distance is the distance between the centers of two touching spheres Relationship between atomic radius, (which is = for crystals of pure elements) and the edge (a) of the unit cell of a cubic crystal Simple Body centered Face centre

RADIUS RATIO Radius Ratio =


( ( ) )

Relationship between radius ratio, co-ordination no. and structural arrangement Radius Ratio Co-ordination No. 0.155 - 0.225 3 0.225 - 0.414 4 0.414-0.732 6 0.732-1 8 Density of a crystalline solid Structural arrangement Planar Triangular Tetrahedral Octahedral Body-centred cubic Example

Where is Molar mass, edge length in

is Avogadros number, Z is the number of rigid solid particle par unit and

is the

STRUCTURAL FEATURES OF SIMPLE IONIC COMPOUNDS A. AB PATTERN: Sodium Chloride (Rock Salt) has arrangement ions with ions are present at the edge centres and centre of the body. Coordination No.6 A unit cell of this type consists of 4 units.

) is present at the lattice points of a face centred cubic closure structure. a. The anion ( b. ions are occupying all the octahedral voids, so each is surrounded by six ion. c. Since there will be six octahedral voids (holes) around each chloride ion, so each chloride ion is surrounded by six sodium ions d. The co-ordination number of as well as of ion is six. Therefore, it is termed as 6:6 coordinations crystal. ) gives the radius e. The ionic radius of ( ) and the radius of ion ( ratio 0.525. This value of radius ratio suggest an octahedral arrangement of ions. Therefore, the unit cell of has contribution of 4 ions and ions unit per unit cell. The sodium chloride structure is also called rock-salt structure. Example, having rock-salt structure i.e Alkali halides : Oxides of alkaline earth metals : Note : Length of the edge (a) = CASEIUM CHLORIDE ( has ) unit. type of structure are:

arrangement : Coordination no. 8. A unit cell of this type consists of only one

a) Radius Ratio = b) The are present at the corners of the cubic unit cell and the ions are at the body centre of the unit cell. c) Each ion in this mode of packing is touching 8 chloride ions and each are touching eight ion. Therefore, this structure will have coordination. d) Other examples which exhibits strucutre : Factors influencing crystal structure: a) Pressure : Increase in pressure increases the coordination number during epithelization eg. applying high pressure, the crystal structure having 6:6 coordination number changes to having coordination number 8:8 b) Temperature : Increase of temperature however, decrease the coordination number. Zinc Blende ( a) ) form a fee cubic ions are surrounded by four

has arrangment in which tetrahedrally. Coordination no. 4. )

b) Radius ratio (

) occupy face centred cubic lattice points and the zinc ions ( ) occupy half of the c) The sulphide ions ( total number of tetrahedral voids. d) From the crystal structure of it is clear that each sulphide ions is surrounded by ions and each ions is surrounded by Therefore, has coordination. 5

Thus the number of units per unit cell is 4. The following ionic solids are observed to form ZnS type of crystal structure PATTERN Calcium fluoride ( a) In ratio ( ) ) ions form while ions are in all the tetrahedral voids coordination

b) c) The ions are present at the face centred cubic lattice and fluoride ions ( ) occupy all the tetrahedral voids. d) This shows that the coordination number of calcium ion is eight, i..e each calcium cation is surrounded by eight fluoride anions in a body centred cubic arrangement. Each fluoride ion is in contact with four calcium ions. Thus has coordination. e) Therefore, each unit cell has 4 molecules. Solids forming fluorite type of structure are PATTERN SODIUM OXIDE ( ) ANTIFLUORIDE STRUCTURE arrangement lattice whereas and respectively. ) ions occupy all tetrahedral voids.

a) In sodium oxide ions from Coordination number of Rank ( )=4 (

Summarized Characteristics properties of various types of ionic solids Ions forming the close packed structure ions form CCP strucutre type ions form CCP structure BCC structure ions are at the corners of a cube ions form CCP structure Ions present in voids ions in tetrahedral void ion in octahedral holes ion at the centre of the cube F ions in all tetrahedral holes Coordination number Number of Units per unit cell 4

Structure

Example

type

type (Fluorite)

type ions are in ions form (Antifluorite 4 all tetrahedral CCP structure structure) Types of Close-packed structures: There are three ways in which atoms in a crystal are packed. 6

i. ii.

iii.

Hexagonal close packing ( ) Cubic close packing (ccp) i.e. ABCABC.pattern e.g. in Fe, Cu, Ag, Pt, Al and Ni Space occupied = 74%, space unoccupied = 26%. The space occupied by spheres in one layer of the hexagonal close packing is 60.4&. Body-centred cubic (bcc) e.g. in akali metals, space occupied = 68%. Empty space= 32%.

Tetrahedral void: It is a triangular void surrounded by four spheres arranged tetrahedrally around it. Octahedral void. It is a combination of two triangular voids surrounded by six spheres. Radii of the voids in terms of radii of packing spheres (R) Radius (r) of the tetrahedral void = 0.225 R Radii. (r) of the octahedral void = 0.414 R Number of voids in terms of number of atoms No. of octahedral voids = No. of atoms in the close packed arrangement No. of tetrahedral voids = 2 X No. of atoms or octahedral voids Ferrites are the compounds with formula spinelstructure (spinel is the mineral where A is a divalent cation such as . They have

Defects or Imperfection: Any departure from perfect orderly arrangement of atoms in a crystal. When deviation exists around an atom or a group of atoms in a crystalline substance, it is called point defect. Electronic defects: By the rise of temperature from zero Kelvin some of the electrons move to higher energy states. For example, in pure silicon some electrons are released at higher temperature from covalent bonds which are responsible for its electrical conductivity. The bonds from which electrons are lost become electron deficient and are called holes. Free electrons and holes in crystals are considered as electronic imperfection. Electrons and holes are marked as and and their concentration as This gives rise to type and semi conductors. Atomic imperfections or Point defects These defects are caused by the departure of an atom or group from the regular arrangement in a crystal. They may be stoichiometric or non-stoichiometric in nature. Stoichiometric Defects Defects in which the ratio of cations and anions (by number) remains unchanged are called stoichiometric defects. a) Schottky defect Some of the atoms or ions lose their regular lattice sites and are completely expelled out. In case of ionic solid, loss of cations and anions must be in such a way that the electrical neutrality is nearly equal, e.g. At room temperature in solid there are Schottky pairs per consequences of this defect are the decrease of density and increase of conductance. Note : exhibits both Schottky and Frenkel defects. b) Frenkel defect Some of the cations lose their regular lattice sites and occupy interstitial sites between the lattice points. It is possible when the coordination number is low and anions are much bigger in size than the cations e.g. silver halides. The closeness of similar in this defect may increase the dielectric constant of the crystals. In such solids density does not change. Non-Stoichiometric defects In these defects the ratio of cations and anions present in the compound differs from that required by ideal chemical formula 7

a) Metal Excess defect due to anion vacancies some of the anions lose their lattice sites leaving holes occupied by electrons to maintains electrical neutrality. The electrons trapped in anion vacancies are referred to as F-centres (F from the German word Farbe, meaning colour) e.g. the exvess of potassium in makes the crystal violet while excess of makes the pink in appearance. b) Metal excess defect due to extra cations occupying interstitial sites Extra cations may occupy the interstitial sites and the electron in some nearby interstitial sites to maintain electrical neutrality. It is found in c) Metal deficiency defect due to cation vacancies Cati`ons lose some lattice sites while some of the nearby cations are oxidized to maintain charge In case of compounds two out of three ferrous ions in a crystal lattice may be converted into state while the third ion may be lost. Due to the presence of two types of cations there is exchange of electrons between ion may be lost. Due to the presence of two types of cations there is exchange of electron between ions. It causes the metallic luster and electrical conductance in these compounds. Impurity defect (doping) Pure silicon is insulator but on adding in traces of an element belonging to group 13 (Ga or In) or group 15 (As) the electrical conductance is largely increased. Such substances are called extrinsic or impure semiconductors. Doping of group 13 elements in place of some causes semi conductors. Magnetic Properties of Solids a) Diamagnetic They are weakly repelled by the magnetic field e.g. It is due to the presence of paired electrons. b) Paramagnetic they are attracted by the magnetic fields due to presence of permanent magnetic dipoles e.g. etc. It is due to the presence of one or more unpaired electrons. c) Ferromagnetic They are strongly attracted by magnetic field and show the permanent magnetism even when the external field is removed e.g. It is due to the fact that the magnetic moment in all parts of the substance is aligned in one direction. Note Based on alignment of magnetic moments, these substances may be of three types- Ferromagnetic (as discussed above); Antiferromagnetic (alignment is in a compensatory way to give zero magnetic moment and Ferrimagnetic (alignment is in parallel and antiparalled direction in unequal numbers, resulting in less net magnetic moment.) ASSIGNMENTS SECTION A CLASSIFICATION, CRYSTAL SYSTEM RADIUS RATIO CO.NO 1. How will you distinguish between the following pairs of terms: a. Hexagonal close packing and cubic close packing b. Crystal lattice and unit cell c. Tetrahedral void and octahedral void 2. How may lattice points are there in one unit cell of each of the following lattice? a. Face centred cubic b. Face centred tetragonal c. Body centred cubic 3. Calculate the efficiency of packing in case of a metal crystal for a. Simple cubic b. Body centred cubic c. Face centred cubic 8

(with the assumption that atoms are touching each other). 4. Define the term amorphous. Give a few examples of amorphous solids. 5. Calculate the number of atoms in a cube based unit cell having one atom on each corner and two atoms on its each diagonals. [Ans. 9] 6. a. What is meant by the term coordination number? b. What is the coordination number of atoms (i) in a cubic close packed structure , (ii) in a body centred cubic structure. 7. A solid AB has strucutre. If the radius of cation A is 100 pm, what is the radius of anion B? Name the solid substance in which cations occupy all the tetrahedral voids. What positions are occupied by the and ) strucutre? in the fluorite ( 8. What is the coordination number of an octahedral void? 9. When atoms are placed at the corners of all 12 edges of a cube, how many atoms are present per unit cell? [Ans. 1] 10. A unit cell consists of a cube in which there are A atoms at the corners and B atoms at the face centers and A atoms are missing from 2 corners in each unit cell. What is the simplest formula of the compound? 11. A cubic solid is made of two elements P and Q. Atoms Q are at the corners of the cube and P at the body centre. [ ] What is the formula of the compound? What are the coordination number of P & Q? 12. A unit cell consists of a cube in which there are anions (Y) at each corner and cations (X) at the centre of alternate faces of the cube. What is the simplest formula of the compound ? [Ans. ] 13. If three elements crystallize in a cubic solid lattice with P atoms at the corners Q atoms at the cube centre and R atoms at the edges. Write the formula of the compound. [ ] 14. A solid is made of two elements Atoms are in CCP arrangement, while atoms P occupy all the tetrahedral sites what is the formula of the compound? [Ans. ] 15. In a cubic close packed structure of mixed oxides, the lattice is made up of oxide ions, one-eighth of tetrahedral ) while one-half of octahedral voids are occupied by trivalent ions voids are occupied by divalent ions ( ( ) what is the formula of the oxides. [ ] 16. What name is given to 14 possible three dimensional lattices [Ans. Bravis lattices] ) is between 0.225 and 0.414, what will be the coordination number and position of 17. If the radius ratio ( the cation? [Ans 4; tetrahedral void] 18. If the radius of the bromide ion is 0.182nm, how large a cation can fit in each of the tetrahedral hole? [Ans ] 19. If the radius of anion in an ionic solid is 100ppm, what should be the radius on the cation (i) that fits the cubic hole, (ii) that fits the octahedral hole, (iii) that fits the tetrahedral hole. ) crystral structure? 20. What is the arrangement of in Zinc blende ( 21. A silver halide forms crystals similar to those of Under what conditions these change to crystals? 22. What are the coordination numbers of ions in crystal structure? 23. Mention a compound which shows anti-fluorite structure: a. What structural changes will occur if a crystal of is heated to b. What structural changes may occur if crystal is subjected to high pressure? c. What is the effect of high pressure on co-ordination number? d. What is the effect of temperature on co-ordination number? 24. If the radius of the anion in an ionic solid of type is 100pm, find: a. Maximum radius of cation so as to occupy octahedral void. b. Minimum radius of cation so as to occupy tetrahedral void. c. What should be the range of the radius of cation to occupy cubic void. [ ] 25. Classify each of the following solids as ionic, metallic, molecular, network (covalent) or amorphous. 9

a. b. c. d. e.

Tetra phosphorus decoxide ( Graphite Brass ) Ammonium phosphate (

f. g. h. i. j. Plastic

26.

27. 28. 29. 30.

31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43.

44.

SECTION B DETERMINATION OF DENSITY OF UNIT CELL A crystal of lead (II) sulphide has an strucutre. In this crystal the shortest distance between a ion and a is 297 pm. What is the length of the edge of unit cell in lead sulphide? Also calculate the unit cell ) volume. ( [ ( ) Gold crystallizes in a face centred unit cell. What is the length of a side of the cell? What is the distance between in crystal, if the density is crystallizes in ) lattice, ( ] Ans :[ ] A body centred cubic element of density has a cell edge of 314pm. Calculate the atomic mass of the element. [Ans. 96.03g ] Formula mass of is and density of its pure form is The average distance between adjacent sodium and chloride ions in the crystal is Calculate Avogadro constant. [Ans ] has strucutre. What is the distance between if the density is (Atomic masses : ) [Ans. 268 pm] Sodium chloride crystal has fee structure. Its density is Calculate the edge of the unit cell. (mol. Mass: [Ans. ] How can you determine the atomic mass of an unknown metal if you know its density and the dimension of its unit cell? Explain your answer Silver crystallizes in lattice. If edge length of the cell is and density is calculate the atomic mass of silver . [Ans: ] An element of atomic mass of occur in structure. If its unit cell edge length is 500 pm and its density is What is the value of Avogadro constant? [ ] Caesium chloride crystallizes as a lattice and has a density of Calculate length of the edge of the ) unit cell of caesium chloride crystal ( [ ] Chromium has monoatomic body centred cubic structure. If density is Calculate atomic radius of ) niobium? ( [Ans 6.39 gm ] Niobium crystallizes in body centred cubic structure. If density is calculate atomic radius of niobium ) ?( [ ] An element occurs in the BCC structure with a cell edge of The density of the element is . How many atoms of the element does 208 g of the element contains ? [Ans ] ( ) structure. Its density is The compound has the what is the length of the unit cell? (Atomic masses : )( [ ] An element crystallizes in a structure having fcc unit cell of an edge 200pm. Calculate its density, if 200g of this element contains [Ans. ] Show that has a strucutre. ( ) [Ans. 3.893=4] Calculate the density of silver which crystallizes in the fcc structure. The distance between the nearest silver atoms in this structure is ( ) [Ans ] ) having An element ( unit cell, has a density of What is the edge length of the unit cell? [Ans 400 pm] 10

45. Ionic radius of

is 95 pm and of

is 181 pm. What is the length of the edge of the [

unit cell? ]

46.

47. 48. 49. 50. 51. 52. 53. 54. 55. 56. 57. 58. 59. 60. 61.

62. 63. 64. 65. 66. 67. 68.

69. 70. 71. 72.

SECTION-C DEFECTS OF SOLIDS Explain the following terms with suitable examples: a. Schottky deect b. Frenkel defect c. Interstitials d. F-centres What is the difference between Schottky defect and Frenkel defect? Why Frenkel defect is not observed in alkali metal halides? What is the effect of Frenkel structured defect on the electrical conductance of a crystalline solid? Mention one property which is caused due to the presence of F-centre in a solid? Why are solids containing F-centres paramagnetic? What happens when KCl crystal is heated in presence of potassium vapours? Why does white become yellow on heating? What is the effect of the presence of Schottky defect on the density of a crystal? Why is common salt sometime yellow instead of being pure white? Name one solid in which both Frenkel and Schottky defects occur? Why dopes Frenkel defect does not change the density of crystal? Which point defect lowers the density of ionic crystals? Although pure silicon in an insulator, then how does it behave as a semi-conductor on heating? What are the differences between n-type ad p-type semiconductor: Classify each of the following as being either a p-type or an n-type semiconductor: a. Ge doped with In b. B doped with Si What is doping? Why is it done? Pure silicon is an insulator but behave as a semi-conductor on heating. Explain? Pure silicon is an insulator but silicon containing impurity of phosphorous atoms acts as a semit-conductor. Explain? Some of the glass objects recovered from ancient monuments look milky instead of being transparent. Explain? Pure silicon is an insulator. Silicon doped with phosphorous is a semiconductor. Silicon doped with gallium is also a semiconductor. What is the difference between the two doped silicon semiconductors. What other element may be added to silicon to make electrons available for conduction of an electric current? Explain the following with suitable examples: a. Ferromagnetism b. Paramagnetism c. Ferrimagnetism How is ferromagnetism different from paramagnetism? What happens when ferromagnetic is heated at and why? How can a ferromagnetic substance be changed to a paramagnetic one? What is the energy gap in band theory? Compare its size in conductors, semiconductors and insulators.

11

Vous aimerez peut-être aussi