per studying this Unit, You will be ple to fevcrbe general characteristics of state: Paguiah between amorphous Gnd crystalline solids; crystalline solids on the basis of the nature of binding forces: define crystal lattice and unit ‘cell; explain close packing of particles; describe different types of voids ‘and close packed structures; calculate the packing efficiency of different types of cubic unit cells; correlate the density of a substance with its unit cell properties: describe the imperfections in solids ‘and their effect on properties: correlate the electrical and magnetic properties of solids and their structure. The Solid State " ¢ The vast majority of solid substances like high temperature ‘superconductors, biocompatible plastics, silicon chips, etc. are destined to play an ever expanding rple in future development of science." From our earlier studies, we know that ids and gases are, cause of their ability to How. idity in both of these states is due to the fact that the molecules are free to move about. On the contrary, the constituent particles in solids have fixed positions and cat oly osllai-about er mean postions aoe explains the rigidity in solids. These pro} depend upon the nature of constituent particles and the binding forces operating between them. The correlation between structure and properties helps in ‘the discovery of new solid materials with desired properties. For-example, et materials may play an future development of science and society. Some other materials which are expected to play an important role in future are high temperature wuperamauerare, magnetic reat. biodegradable polymers for packaging, biocompliant solids for’ , ett, ‘Thus, the study of this state becomes more important in the present scenario. In this Unit, we shall discuss different possible arrangements of particles resulting in several types of structures and explore why different arrangements of structural units lend different properties to solids. We will also learn how these properties get modified due to the structural imperfections or by the presence of impurities in minute amounts.1.2 Amorphous Solids can be classified as crystalline or amorphous on and Crystalline “ature of order present in the arrangement of thelr Solids Aarystalline solid usually consists of a larg is cach of therm having a definite ch: arrangement of constituent particles im is ordered an Fig. ye dimenstonal structure of ______ Chemistry men in ¢ State; earnt that matter can exist in three states 1, tn Class X1 you have = a given set of conditions of tempera," sola, liquid and | eof these would be the most stable state of ES ressure, Substance depen OE eyiieh tend tO a ST i. oh a ht endato ager by mak sparen move faster. At sufficiently low tempe: the thee em intenmolecular forces bring them so close that cling to one another and oceupy fixed positions. These can stil ose" about their mean positions and the substance exists in solid state. following are the characteristic properties of the solid state: _0,"They have definite mass, volume and shape. —{t) Intermolecular distances are short. - At Intermolecular forces are strong. tt) Their constituent particles (atoms, molecules or ions) have 4 Positions and can only oscillate about their mean positions, _-(J They are incompressible and rigid. amorphos, meaning no form.’ (atoms, moleculés or ions) in are conte ees only. Regular patter are scattered and in between thé arrangement is disordered, The: of quartz (crystall ) are himost identical, yet in the case off amorphous quartz glass there 1s no borg} F range order, The structure of amorphous Solids 18 similar to that of liquids. Due © 7 ¢ differences in the arrangement ort’ onstituent particles, th quartz and (6) quartz glass differ in their propertie = (b) ,Crystalline soli arp ig Ps me Solids have a shi melting point. Ata characteristic ley melt abruptly and become iquid. On the other hand, amonphons sale S soften, melt and start flowing over _a range of = and can be moulded and Sa nto various Shay various shapes. conveniently as liquids. They may become = ¢ e ects from ancient: crystallisation Like liquids, amorphous solids have a tendency tolow, ough very slowly. Therefore, sometimes these are called pseudo solids or super cooled liquids. — _ Amorphous solids are isotropic in nature. Their properties such as mechanical strength, refractive index and electrical conductivity, etc., are son Ta 2° curections. Tris because there is no long range order in em ies is not definite along all the directions. Hence, the overall arrangement becomes equivalent in al diree= 7 ould be same Therefore, value of any physical property w any direction. ‘e Crystalline solids are nee cect that D Crystalline is, Some of their physical pro} jes like electrical cireciive index aie diffe © resistance or r ferent values whenmeasured along different directions in the same crystals. This arises from different it © __ofparticles in different directions. This is illustrated in Fig. 1.2. This figure shows a simple two" O dimensional pattern of arrangement of two kinds of atoms. Mechanical property such as resistance to shearing stress might be quite different In two CO directions indicated in the figure. Deformation in CD direction displaces row which has two different types of atoms while in AB direction rows made of one type Sfatoms are displaced. The differences between the crystalline solids and amorphous solids are ong different summarised in Table 1.1. directions. Table 1.1: Distinction between Crystalline and Amorphous Solids Cotati Pry Pty CCC Definite characteristic geometrical shape Melt at a sharp and characteristic temperature When cut with a sharp split into two pieces and the newly Irregular. shape Gradually soften over a range of temperature edged tool, they | When cut with a sharp edged tool, they cut into two pieces with irregular surfaces ~~~ ~~ SS ———— generated smooth ‘They have a definite and characteristic | They do not have definite enthalpy of fusio —— ene enthalpy of TasionAnisotropy Anisotropic in nature Isotropic in nature Nature ‘True slits [Link] oF super cooiey Order in Long range order Only short. range order, —~* eu arrangement of constituent Particles Bésides crystalline and amorphous solids, there which apparently appear amorphous but . These are called poly epee stalling condition, Radar Soon ic sample may appear to be is anisot ” ny is ar Glass, rubber ang Pla find many applications inure esa one - best potveltac material available for conversion of sunlight into e| are s a 1.1 Why are solids rigid? 1.2 Why do solids havea definite volume? _ 1:3 Classify the following as amorphous or crystalline solids: Polyurethane, naphthalene, benzoic acid, teflon, potassium nitrate, cellophane, Polyvinyl chloride, fibre glass, copper. 1.4 Refractive index ofa solid is observed to Comment on the nature of this solid. have the same value along all directions, Would it show cleavage property? 1.3. Classification ia Section 12, we have Jearnt oe amorphous substances and 5 ey have only short range order. However! most of the dl substay af For eer example, all the metallic elements solids -opper and silver like oe on ounds like sodium chloride, zinc sulphide for mm crystalline solide. Crystalline solids can be classified in various ways, The meth depends on the Purpose in hand. Here, we will classify crystalline sol on the basis of he onic bonds; (iii) Covalent bonds; and (iv) Metallic bonds. On this’ yer crystalline solids are classified into four categories viz., molecular. 0 metallic and covalent solids. Let us now learn about these categories 1.3.1 Molecular —Molecules are th € constituent particles of molecular solids. Tes? # Solids further sub divided into the following categories: Non polar Molecular Solids: Th for exam . roa jolar coval ____eremtstry amg °°bonds, for example, Hy, Cl, and molecules ne Te Hs: Cl and I, In, these solids, the atoms or about duc have learnt in Class XI. in Jiquid or gaseous state at room temperat Gi) Polar Molecular Solids: The molecules of substances etc. are formed b i eling points are h higher than those of non polar moTe solids ye examples of Such solide, (iti) Hydrogen Bonded Molecular Solids: The molecules of such solids contain polar covalent bonds between H and F, O or N atoms. Strong hydrogen bonding binds molecules of such solids like H,O (ice). They are Generally they are ‘biel orgs year ga 3.2 Ionic Solids Ions are the constituent particles of ionic solids. Such solids are formed ‘ by the three dimensional arrangements of cations and anions bound by strong b s wees. These solids eee However. in the moiten state or When dissolved in water, a SROre Sbont and The See ne ae Pecome tree te Tons become free to move about and they conduct electricity. 3.3 Metallic Solids When an electric field is applied, these electrons Ug THE ork of positive ions. Similarly, when heat is supplied ‘to one portion of a metal, the thermal energy is uniformly spread throughout by free electrons. Another eogaae characteristic 3.4 Covalent or A wide variety of crystalline solids of non-metals result from the Network formation of covalent bonds between adjacent as throughout the Solids stal. They are also calle nds are oa c in jerefore ane are held very strongly at their Boston, oa solids. are ‘They have bide. are re typical examples of eae a though 1.4) alee belongs to this class of crystals, but it is soft rigity, Its exceptional properties areaue to tim The Solid Statesolid and a The different of the four types od : are listed in Table 12 Fig. 1.3: Network structure Fig. 1.4: Structure of graphite . Ff diamond Table 1.2: Different Types of Solids (RSS ose rsrers ee a eT . | Particles cr acne ee | Cod () Molecular solids W Non polar Insulator {) Polar Insulator (i) Hydrogen i bonded Insulator (2) Ionte solids Insulators (3) Metallic solids in solid state as well as in molten state Chemistry | |Conductor (exception) 1,6 Classify the following solids in different categories based on the nature of intermolecular forces operating in them: Potassium sulphate, tin,(benzeneurea,lammoniq, watej, zinc sulphide, graphite, rubidium{ argon] silicon carbide. 1.7 Solid Ais a very hard electrical insulator in solid as well as in molten state and melts at extremely high temperature. What type of solid is it? 1.8 Ionic solids conduct electricity in molten state but not in solid state. Explain. 1,9 What type of solids are electrical conductors, malleable and ductile? You must have noticed that when tiles are placed to cover a floor, a repeated pattern 1s generated, If after:setting tiles on floor we mark a Lattices and point at same location in all the tiles (e.g. Centre of the tile) [Link] the Unit Cells marked positions only ignoring the tiles, we obtain a set of points. This set of points is the scaffolding on which pattern has been developed by acing tes. This saflng a spaceleie on +h two-dimens! ensional wi icing structural units on its set of le in this placed on points in . space lattice, a'pattern e 6 8 6 PPP: 1 Spot ts yt at 2 anes (two-dimensional) A_ space lattice, a oe also Calleda~ crystal PO © alate Jattice, is the patterrof- Point points representing the Tovations of mt . ‘In other words, space (©) Hypothetical two-dimenstonal ice 15 ; crystal scaffolding for crysi 7 structure. When—we place motifs in an identical manner on Mig.1.5: (a) Motif (b) Space lattice (two-dimensional (c) Hypothetical two-dimensional crystal structure points of space lattice, eden, The Solid Statestructure, Fig. 1.5 shows @ motif, a two.g,, we aan “ihypothetlcal two-dimensional crystal structs by placing motifs in the two-dimensional lattice. arrangement of lattice points gives rise to aiff 7 witdene Fie 1.6 shows arrangement of points in two differ: a Be a © 8 8 o Lattice 3 ~ Pig. 1.6: Arrangement of points in two different lattices Inthe case of crystalline solids, space lattice is a three-dim, array of points. The crystal structure is obtained structurral motifs with lattice points. Each repeated Fame structure [Link] orieritation as ofher one In acy = The environment of each motif is same throughout the e tal exe for on surface. = eet oy ~ Following/are the characteristics of a crystal lattice: & tating : ‘minimum vacant space. Let us consider the constituent ——_Strwetures identical hard epheres and bulld up the three-dimensiongy T°! lonal str in three steps. (a) Close Packing in One Dimension Ther is only one way of arranging spheres in a one-dimensiona ane re rae that to arrange them in a row and touching other (Fig. 1.17). here is a e In this arrangement, each sp with two of its neighbours, Fig. 1.17: Close packing of spheres tn ber. Thus, in one one dimension dimensional close “vragen the cordination nunberke (®) Close Packing in Two Dimensions _—> ‘Two dimensional close packed structure can (placing) the rows of close packed spheres, different ways, The second row may be placed in contact with the first that the spheres of the second row are se a frst row. The spheres of the two rows a be generated by stac This can be done int Chemistry 14,In this arrangement, each s of its neighbours. Thus, th¢ “thie centres of these 4 immediate neighbouring spheres are joined, a wee is formed. Hence this packing is called aquare close packing Ti) The second row may be placed above the first one in uC at its spheres fit in the depressions of the’ r If the arrangement of spheres In the first row Ts called "A type, the one in the second row is different and may be called ‘B’ type. When the third row is placed adjacent to the second in staggered manner, its spheres are aligned with those of the first layer. Hence this layer is also of ‘A’ type. The spheres of similarly placed fourth row will be aligned with those of the second row ('B’ ype. Hence pe They can be ‘obtained by stacking two dimensional layers e the other. In the last Section, we discussed close packing in two dimensions which can be of two types; square close-packed and hexagonal close-packed. Let us see what types of three dimensional close packirig can be obtained from these. ( Three-dimensional close packing forms two-dimensional square close-packed layers: While placing the second square close-packed layer above the first we follow the same rule that was followed when one row was placed adjacent to the other. The Second layer is placed over the first layer such that the pues of the upper layer are 45 shown in Fig, 1.19. Similarly, we may place Tore layers one above the other. If the arrangement of spheres in the first layer is called ‘A’ type, all the layers s ‘Thus this lattice ha (i) Three dimensional close packing from two dimensional hexagonal close packed layers: Three '9: Simple cubic lattice formed dimensional close packed structure can be generated by AA by placing layers one over the other. sl5y_The Solld StateChemistry pl6, lacing second layer over the first layer ee take a two dimensional hexagonal close Packed layer, lace a similar layer above it such that the spheres of the secon gre placed in the depressions of the first layer. Since the sphere two layers are aligned diffe tly, let us call the second laye, 0 ‘Wherever a sphere © Second above the void of the first layer (or vice versa) a tetrahedral 2 A stack of two layers of close packed spheres and voids generated in them. T = Tetrahedral void; O = Octahedral void (>) tose ‘Tetrahedral ; hole ‘hole : / “Tetrahedron hol ad Oct ‘hole ae (@) ) Octahedron ©(a) oon cubic se-packing layers of spheres () four layers stacked in each case land (@) geometry of \Fig. 1.23 l@) ABCABC... larrangement of layers when octahedral void is, \of structure formed by this arrangement resulting in cubic Se Packed (cep) jor face centred cubi ec structure, upwards and the other downwards. ‘O’ in Fig. 1.20. Such voids are ne such void has been shown separately in ff these two types of voids depend upon the number of close packed spherés. (®) Placing third layer over the second layer When third layer is placed over the second, there are two possibilities. ( Covering Tetrahedral Voids: Tetrahedral voids of the second layer may be covered by the spheres ofthe third layer. In this case, th (i) Covering Octahedral Voids: The A third layer may be placed above {he second layerin-& mamnecsuch © that its spheres cover the 4 Solabedral wads. When placed in B (b) this manner, the of tt * o type. when fourth la : @) laced, its spheres are wit jg The Solid State RRSae hen particles are : have leamt that wi é 16.1 Formula ofa Earlier in ihe eee wate ener cece oOo a ee ber of octahedral vo otvese oul nt is cami crocs packed partes, the number of, Filled or generated is twice this number. In ionic solids, the Digger id the Smalley close packed structure an feat te ee the wos. If the latter fon is small en, hee Voids are occupied, if bigger, then caicen or tetrahedral voids are not occu the fraction of octahedral or tetrahedral xment Y. Thus, the atom are \ B equal numbers or 1:1 rai, the formula of the compound is Xy. ‘Atoms of element B form hep lattice and those of. the element Ao 2/3rd of tetrah nd pp at the forma of the cere by the elements A and Be The number of atoms of element B of element A, He re “agence the ratio of the numbe; * Q/3K1 oF 4:3 and the formula of the ¢ that close packeq Volds. Let us take cep (or Fed eee be eS Voids in it, (@) Locating Tetrahedrat Voids Let us consider a unit cello into elght ‘Small cubes | f cep or fee latticg ig: ray, The unit cet) {8 divided Chemistryspall cob has atoms at altemate comers (Ff 1]: In all, ah small hs When joined to each other, they make f regular tetrahedron. tetrahedral void in trahedral re 1s one each small cube and eight tet 8 neg Bach of the eight small cubes have one void in one unit cell of ocP Ty, We now that cop structure has 4 atoms’ per unit cell. Thus. the y ol tetrahedral voids Cae the number of atoms. o w ig. 1: (@) Bight tetrahedral votds per unt cell of cep structure (0) one tetrahedral void showing the geometry. (y vocating Octahedral Voids et us again consider a unit cell of cep or fec lattice [Fig. 2(a)]. The body centre aie ce, C18 not occupied but it is surrounded by sbx atoms on face centres. "f these face centres are joined, an octahedron is ted. Thus, this unit cell has Meides the body centre, there 1s ofthe 12 edges TFs. 2(b)). It is surrounded by six atoms, four oe unt cell (2 on'the corners and 2 on face centre) and two belonging to two ‘Sfacent unit cells, Since each edge of the cube 1s shared Between four adjacent unt cells, so is the octahedral vold located on it. —A Mig. 2: Location of octahedral votds per untt cell af cop or foc lattice (a) at the body centre of the cube and (b) at the centre of each edge (only one such void is shown). : lds The Sold StateOctahedral void at 12 octahedral volds . Total number of in’ cubie close packed ‘Thus the’body-cent Jocated at each ed octahedral voids = 4 ‘We know that in cop structure, each unit ce! of octahedral voids is equal to structure: : tre-of the cube = a fe and share between four unit has 4 atoms. Thus, the nung, this number. particles (atoms, molecules op, 1.7 Dacking In whatever way the constituent the form of y, i d, there i Efficiency Peaking efflelency aie percentage of total SP ace filled by ‘as calculate the packing efficiency 2 1.7.1 Packing Efficiency in calculate the efficien cy of pa hep and cep unit cell edge length be ‘a’ and face diagonal AC : In A ABC AC?=b?= BC? + AB? c = eta? = 2a or B b= oa H Ifris the radius of the sphere, we find | b=4r= oa | (we can also write, r= —*_) z , wa Fig. 1.24: Cubic close packing other sides are not provided with spheres for sake of clarity. We know, that each unit cell i in cc} has effectively 4 spheres. Total volume of spheres is equal to 4x(4/3)mr° and volume of! cube is a® or (2var)° : Chemistry 9205” _4x(4/3)m* x100 (2/2) *S _ (16/3)nr* x100 16V2r°ency of From Fig. 1.25, 885) in _atomat the aes clear that the will be in nee,“ RUihe tier tnoateme ea booted amanged. ly na oe Dy mh 2 gpructre® al tate gat b = 2a Now in A AFD C sab tba a? soe = ga? © = Ba Th cis equa toe wae meena pig, 125: Bodycote aie unt . Where F |. 1.25: Body. of the sphere (atom), as ae cell (sphere along the spheres along th body diagonal are shown earthed eee Ratio with solid boundaries). Therefore, 8a = 4r Also We can write, r In this type of structure, total number of atoms is 2 and their volume A) a8 1s 2x($}a0°. Volume of the cube, a® will be equal to ( ‘Therefore, ‘Volume occupied by twospheres in the unit cell x100 g, Packing efficiency = r Total volumeof the unit cell _2%(4/3) mr? x100 4, [ar8)} _(8/3)ar° 100 9, 64/(3V3)r* 3 Packing Ina simple cubic lattice the atoms are located only on the corners of the Efficiency in cube. The particles touch each other along the edge (Fig. 1.26). Simple Cubic Thus, the edge. length or side of the cube'a’, and the radius of each particle, Lattice rare related as ‘The volume of the cubic unit cell = a° = (21)° = 8° Since a simple cubic unit cell contains only 1 atom ‘The volume of the occupied space = 4m1° e2ig_The Solid StateMig. 1.26 cubic unit cell, The spheres are in ; contact with each | Other ‘ the caper the edge of sh _ ible to calculate 1.8 Calculations From the unit cell dmensions se ne neta we the involving the unit cell Knowing ect orl The del tion of Unit Git mass of the atoms in e ua Sista de tion of srt see 30 aoe of a unit cel of a exp! a a. dthe dest ofthe sot molar mass. In case of cuble crystal: Volume of a unit cell = a? unit cell Tee atoms in unit cell x mass of each atom ~ [Here zis the number of atoms present in one unit cell ang a mass of a single atom) Mass of an atom present in the unit cell; mension M m “7y (Mis molar mass) Ns Therefore, density of the unit cell = Massof unit cell volume of unit cell The density of the soli can always, ot lods. Out of the five Parameters ve de four are known, we can determine the fifth, termine 2M, aand N), 4n element has a body-centred cubte ay 288 pm. The density of the element is 737 CUTE With a cel ll edg ° Present in 208 g of the element? S/en. How many atoms Solution Votume of the unit cell ¢ (288 pm) = 28810" ma? = 66419 : = 2.39%10% oms Say} Chemistry p22jpeof 208 gor the element 1 mass___ 2089 = density ” 72 gem =28-88em? per of unit cells in this volume um __ 28.88cm° ——— = 9,39x10™ cm? /unit ceil = 12.08%10* unit cells each boccubic untt cell contains 2 atoms, therefore, the total number ince joms in 208 & = 2 (atoms/untt cell) x 12.08 x 10 unit cells of 94.16*10® atoms tion studies show that co; ian I ray alia per crystallises in an fec unit le 14 a myith cell dBe of 3.608x10* cm. In a separate experiment, copper is je Setermined to have a density of 8.92 g/cm, calculate the atomic mass of coppe™ case of OC aa number of atoms per unit cell, 2= 4 atoms: Solution = Na qperefore, M = 7 : 2g cm x6.022x10"* atoms mol” x (3.608 x10%em)* 3 eee’: 4atoms = 63.1 g/mol ‘Atomic mass of copper = 63.1u. siiver forms cep lattice and X-ray studies of its crystals show that the edge length of its unit cell is 408.6 pm. Calculate the density of (atomic mass = 107.9 u). . ‘since the lattice is cep, the number of silver atoms per unitcell=2=4 — Solution Molar mass of silver = 107.9 g mol! = 107.9x10* kg mot Bdge length of unit cell = a = 408.6 pm = 408.6x10"m 2M Density; d = G3N,. 4x(107.9x10*kgmol”) * (408.6x10-*m)’ (6.02210 mol") = 10.5 gcm* = 10,5%10° kg mr? 14 What is the two dimensional coordination number of a molecule in close-packed layer? A compound forms hexagonal close-packed structure. What is the total |". number of voids in 0,5 mol of it? How many of these are tetrahedral volds? 23m The Solid Stateforms cep and atoms of M occupy 1/3 is the formula of the compound? packing efletency () g lowing lattices has the highes! _ 1.17 Nee) Sy reyocntred cubic and (iii) hexagonal close-packed Tati 1.18 An element with molar mass 2.7x10? kg mol farms a cubie unit ath edge length 405 pm. If its density is 2.710° kg m®, what jg nature of the cubic unit cell? elements M and N. The elem, We, compound is formed by two rd of tetrahedral voige = 4 4 ‘ Cay the 1.0 Imperfections Although crystalline solids have short range as well as Ip ; ns ales, yet o in Solids der of thelr cor ot perfect. Us oP onal : ects, icles. 3 , the de e of t S, namely, a) ; ects. Point defects are the irregularitig 7 ions from ideal arrangement around a point or an atom re] crystalline substance, whereas the line defects are the irregula or deviations from ideal arrangement in entire rows of lattice pei These irregularities are called crystal defects. We shall confine discussion to point defects only. 1.9.1 Types of Point defects can be classified into three types : () stoichiometric def Point Defects (ii) impurity defects and (tii) non-stoichiometric defects, (@) Stoichiometric Defects ‘These are the point defects that do not disturb th the solid. They are also called int Basically these are of two types, vacancy defects a ) Vacancy Defect: When some of the lattice sit crystal is said to bee vacancy defect (Fig of GEE eae A Interstitial Defect: When some constituent partis (atoms or molecules) occupy an interstitial the crystal is said to have interstitial (Fig. 1.28). This defect F ——— defects, th these def 7 Fig. 1.27: Vacancy defects Schott sutuathese defects as 4 Schottky defects. ——__ Chemis(ii) Frenkel Defect: This — defect is shown by ionic solids. The smaller ion usually cation] Ie site to an interstitial | (Fig. 1.29). Tiaerentes rs Frenkel defect is also Fig, 1.28: Interstitial defects called dislocation defect. Frenkel defect is @ large difference in he size of ions xample, small size of Zn and Ag* Tone (iv) Schottky Defect: It is basically a vacancy defect in ionic solids. In order to maintain electrical neutrality, the number of missing cations and anioné are equal (Fig. 1.30). Like simpl ep eeeercc Schottky defect also decreases the density of the PL th td Substance. Number of such CJT Tee I defects in ionic Fig, 1.30: Schottky defects Schottky . ionic substances in which the cation and anion are ilar sizes. - For example, NaCl, KCI, CsCl and A be noted that oth (b) Impurity Defects If molten NaCl containing a little amount of SrCl, is crystallised, some of the sites of Na’ ions are occupied by Sr” (Fig.1.31). Each Sr” rej a .. It occupies the site of one ion and the other site remains vacant. The cationic vacancies thus ced aré equal in number to that of Sr” ions. Another similar example is the Solid solution of CdCl, and AgCl. ‘NaCl by substitution of Na* by Sr* p25m_The Solid State1.40 Electrical Properties ist (@ Nor ‘the defects 4 ine gnystalline substance. However, a large n e stoichiometric Inorg: constituent el their crystal s excess defect Metal Excess Defect * n-stoichiometric Defects iscussed so far do not disturb the Stole Wy On, nic solids are known why Peet ements in non-stolchiometric ratio que (2% tructures,, These defects are of two ty° and (ii) metal deficiency defect. fy 1s defect due to anionic vacanetes: a of Met ae how this type of defect, When! aC) are heated In an atmosphere o} Sodium ya sodium atoms are deposited on the surface of The Ct tons diffuse to the surface of the en combine-with Na atoms to give NaCl. This hay’ A Metal exzeas defect duc to Ti presence of interstitial sites: Now there is excess of zinc in the crystal and its formula ba ZnO, The excess Zn” tons move to interstitial sites and the ele to neighbouring interstitial sites, (i) Metal Deficiency Defect compared to this conductivi Conductors: te in the order of TO" ohn Soli Sol ie exhibit ¢ of electrical conductivities, = Tanging from _1 Is ne classified into three types Composition and contain less amount of the m# the stoichiome : loss “of positive chil d number of Fe* ions. : the basis o Solids with conductivities ranging betw®# called Conductors. Metals have con =-Ate-godd-eonductors. —,(i) Insulators : These are the solids with low ate very low conductivities (it) Semiconductors These are the solids with conduct intermediate range fror ee A conductor may conduet electricity tht nt of electrons or Ton. ic conductors belong to the former category and el Nicials ‘conduct electricity in solid as well as molten state. ne (Fig. 1.33). If the gap between filled valence band and the next higher unoccupied band (conduiction band) is large, electrons cannot Wand such a Substance has very small conductivity and it behaves as aa an insulator (Fig. 1.33b). the gap between the valence band and [0.2 Conduction .In case of semiconductors, 1,33¢). Therefore, some electrons may Sof conduction band i jump to conduétion Conduction band Empty band Partially filled bands band . Metal i . Semiconductor @ o) © iii The Solid State __Chemistry -30e Diamagnetism: Diamagnetic substances are Ona eld HO, Nac] ait Gy are some exam ces. They are weakly magnetised in a m: 0 aeeaae rection. Diamiagnetism Is showrby tt ate bpwhfetrallte clectrons are paired and there are no wr electrons. Pairing of electrons cancels their magnetic mom, and ty ls lose their magnetic character. tances like iron. cobalt, (ait) rand G0, few subst subst € Ca strong attractions, When the substance is placed in a magnetic field all the dom, get oriented in the direction of the magnetic fleld (Fig. 1.4 and a strong magnetic effect is produced. This ordering domains persist even when the magnetic field is removed the ferromagnetic substance becomes a (iv) Antiferromagnetism: Substances like/MnO showing ferromagnetism have domain struc substance, but their out each other's magnetic moment (Fig. 1.36b). (v) Ferrimagnetism: Ferrimagnetism is observed when the m: moments of the domains in the substance are aligned in p AGES HODOD® -O®OODOH Fig 1.36: Schematio alignment of magnetic moments in (a) ferromagnet (®) antiferromagnetic and (9) ferrimagnetia.present ,as Frenke’ © 1 the ys ot presence of an impurity In we “ jound, Fe J Pr aifferent valence than 1D¢ main comyecess tyPe © introd opin’ stoichiometric defects 47° of 7 mpuriies "ies, Such materials ate Sometimes calculated am, ts “yectsical prove pes of magnetic propertien semiconductors that © ds show many 6 . antiferromagnetism used in electronics industy. em. fesromaen” dio, video and other reco, paramagnetism. diamagnetio™” - used jn audio; electronic confi ma ferrimagnetism. These propertic® “ orrelated with thelr © a can devices. All these prope! or structures. ff amorphous solids, ¢ NENCISes 1 Give a few examples © yid such a§ quartz? Under what ifferent from 2 5 makes a glass 4 be voaverted int© glass? tallic, molecular, network 1.3 Classify each of the (covalent) oF amorphous. (i) Tetra phosphorus decoxide (P,O10) (vii) aig (i) Ammonium phosphate (NH,),PO. (viii) a (ii) SiC fv) & c ) P, (xi) Si yi) Plastic ih ‘What is meant by the term ‘coordination number’? f What is the coordination number of atoms: in a cubic close-packed structure? . ina body-centred cubic structure? termine the atomic mass of an unknown metal 4 How can you det its density and the dimension of its unit cell? Explain. if you know ethyl alcohol, diethyl ether el points of solid water, ut the intermolecular and methane from a data book. What can yor s yu say abo forces between these molecules? J ore Comment. Collect mi nistry 32,yr How will ey Oey between the following pairs of terms: (q) Hexagonal close-packing and cubic close-packing? (u) Crystal. lattice and unit cell? (u) Tetrahedral vold and octahedral votd? How many lattice points are there in one tinit cell of each of the following jattice? Face-centred cuble \ Face-centred tetragonal |+ Wy Body-centred 4 1.9 Explain (i) The basis of similarities and differences between metallic and tonic crystals. {u) Tonic solids are hard and brittle, 6 caloulate the efficlency of packing in case of a metal crystal for ple cubic : ‘pody-centred cubic yf face-centred cubic (with the assumptions that atoms are touching each other). : : we silver crystallises in fee lattice. If edge length of the cell is 4.07 x 10* fom and density is 10.5 g cnr, calculate the atomic mass of silver. 1x Acubic solid is made of two elements P and Q. Atoms of Q are at the comers of the cube and P at the body-centre. What is the formula of the compound? What are the coordination numbers of P and Q? crystallises in body-centred cubic structure. If density is 8.55 ‘cm, calculate atomic radius of niobium using its atomic mass 93 u. If the radius of the octahedral void is r and radius of the atoms in close- packing is R, derive relation between r and R come crystallises into a foe lattice with edge length 3.61 x 10* cm. ‘Show that the calculated density is in agreement with its measured value of 8.92 g cnr’. ‘Analysis shows that nickel oxide has the formula Ni,,.0;.- What fractions of nickel exist as Ni* and Ni** ions? 1.17 What is a semiconductor? Describe the two main types of semiconductors and contrast their conduction mechanism. Ferric oxide crystallises with two out of every in a hexagonal close-packed array of oxide ions three octahedral holes occupied by ferric fons. Derive the formula of the ferric oxide. pm Classify each of the following as being either a p-type or a n-type semiconductor: i |e doped with In } cath 8 dope with BbAQ. (0.4 Gold (atomic radius = 0.144 nm) crystallises in a face-centred unit ogy ‘m) What is the length of a side of the cell? 1.22 In terms of band theory, what is the difference W between a ‘conductor and an insulator (W) between a conductor and a semiconductor? 1.23 Explain the following terms with suitable examples: W Schottiy de id (iv) F-ceng , fect (i) Frenkel defect (u) interstitials ee mean Aluminium ‘crystallises in a cubic close-packed structure. 7 Tadius is 125 pm, . ) What ts the length of the side of the unit cell? 2 0 How many unit eels are there in 1.00 en? of auiniu XE NaCl ts doped with 10° mol % of SrCl,, what is the concentration of cation vacancies? 1.26 Explain the following @ Ferromagnetism (i) Paramagnetism (iii) Ferrimagnetism (iv) Antiferromagnetism ) 12-16 and 13-15 group compounds, with suitable examples: Answers to Some Intext Questions 1.14 4 1.15 Total number of voids = 9.033 x 19% Number of tetrahedral voids = 6.022 x 19s 1.16 MN, 1.18 cep