_ GENREAL CHARACTERISTICS ~ Incrystalline solid atoms, ions or molecules at d atoms, re arranged orderly ina three dimensional manner due to strong binding forces. ‘Due to this arrangement, crystalline solids acquire rigidity and definite geometric shapes or line structures, In amorphous solids constituent particles are arranged randomly (irregularly) in three dimensional space. Characteristic properties of the solids {) They have definite mass, volume and shape. ii) Intermolecular distances are short iii) Intermolecular forces are strong, iv) Their constituent particles (atoms, molecules. or ions) have fixed positions and ean only oscillate about their mean positions. v) They are incompressible and rigid * The existance of a substance in more than one solid modification is called polymorphism. =D Distinction between crystalline and a Crystal ‘Definite characteritle £60F id characteristic Property Melting point harp an a with a sharp ediged 100}, they Ht ieces are plain and we definite and cha cept ui crystal true solids ng range Order Ne vars SOLID STATE CLASSIFICATION OF SOLIDS W.R.T Pl EE-ADV CHEM-VOL-II CONSTITUENT PARTICLES ARRANGEMENT Annealing: An amorphous substance, on heating at a certain temperature, may attain ‘crystalline nature while on cooling regains its amorphous nature, This phenomenon is called antiealing. Eg : Glass on keeping in semi-solid state for a long time or on heating, it melts very slowly, it becomes opaque duc to development oferystal i it Isotropy: Amorphous solids on the other hand are isotropic in nature, It is because there is no Jong range order in them and arrangment is irregular along all the directions. Therfore, value ‘of any physical property would same along any direction. Anisotropy: Crystalline solids are anisotropic innature, that is, some oftheir physical properties like electrical resistance or refractive index show different values when measured along different directions in the same crystals. This arises different arrangement of particles in different morphous solids “Atworphows solids shape Gila, Rubber, Plastic, Quarta pias © scanned with OKEN Scanneroe Fig. Two dimensional streuture of (a) quartz (crystalline) and (b) quartz glass (amorphous) | Fig. Anisotropy in cryastals is due to different arrangement of particles along different *:); Tad AMORPHOUS, CRYSTALLINE S EXAMPLES Crystalline solids: NaCl, Diamond, MgO, CaF,, Red phosphorus, White phosph Naphthalene , Benzoic acid, KNO,, metals, All ionic solids, etc., Amorphous solids: Glass, Rubber, Plastic, Quartz g Polymers, Teflon, Cellophane, Fibre glass, ete., TYPES OF SOLIDS: A crystals classified as ionic, covalent, and molecular according to the nature off building units, chemical bonding and th intermolecular forces in the crystal The characteristics of various types of solids: given in the table CRYSTALL Molecular 1 | solids sie ea BTS pat on «Polar procs of airection| IF CH. CO, | very ow me |g © | Ncicutar solids Ra eh aes Pepersin Sxces): FL-CIeHe.the-_”| pues a Cut esusary | « ular solids Dipole, dipole |HC/, SO, Urea is : Molecules capable t form H-bonds H-bonded solids H-bonds NH., ice glucose | Covatent or Diamond quartz |v silica B, black P. AUN, BN etc | Srworksobts |Anme Kee Fett | eapive NaCl, KNO,, . eiewntic CUS, SH, in sed * [forces of attraction} CaF. ZnS, | 50, ce ait Metal atoms Hard bar here outa. As | ain bedded im [Metallic bonds Indy. Fe ductile oa of electrons) high MP © scanned with OKEN Scanner: is highest in Al, due to the presence ee valence electrons. In Mg and Ca, two ence electrons each are present, But due to large size, bond is weaker in Ca than in Mg. Order of metallic bond strength: Ca Applications of amorphous solids: ‘Amorphous solids are used in domestic constructions or appliances like photo voltaic cells (amorphous silicon) where the sun light is transformed into electricity. LAW OF CRYSTALLOGRAPHY Law of crystallography: The branch of science that deals with the study of structure, geometry and properties of crystalline substances is called crystallography Different law of crystallography are 1. Law of constancy of interfacial angle. 2. Law ofconstancy of symmetry. 3. Law of rational indices a,b,c are edge lengths along x, y, 2 axis respectively. a, Bare interfacial angles. Number of planes in a Cubic erystal-6 Number of edges in a Cube=12 Number of comes in a Cube Law of constancy of interfacial angle: Law of constancy of interfacial angle states that similar angles on crystals of the same substance remain constant regard less the size and shape of the crystals when measured at the same temperature Law of symmetry: “The symmetry in all crystals of a particular species isconstant,though they may not be similar in form.” or the crystals of same substance possess same symmetry of elements. Eg: Crystals of mineral galena shows the symmetry elements like 9 plane of symmetry. 13 axes of symmetry and centre of symmetry ‘whether itis octa hedral or cubic. Hany’s law of rational indices: “The intercepts of crystalline solid along X. crystallographic axis can be expressed interms of unit cell edge lens with definite rational numbers) me SYMMETRY ELEMENTS CALCULATIONS FOR CUBIC CRYSTAL ‘Symmetry ofelements are 1. Plane of symmetry 2. Axisof symmetry 3. Centre of symmetry Symmetry elements in cubic Plane of symmetry (P,0.8): Itisan imaginary plane which divides the crystal into exactly two equal halves and one is mirror image to the other. © scanned with OKEN Scanner> ‘Twotypes ofplane of symmetry are (a) Rectangular plane of symmetry: ‘tisan imaganary plane which is situated midway and parallel to the opposite plane faces no of rectangular plane of symmetry ita cubic crystal=3 (3 opposite pair ofplanes) (b) Diagonal plane of symmetry: It is an imaginary plane which touches opposite edges along body diagonal ofthe cube | iF number of'diagonal plane of symmetry ina cubie crystal =6 (6 opposite pair ofedges) Total number of plane of symmetry in a cubic erystal=9 (3 rectangular plane of symmetry+6 diagonal plane of symmetry)measured at the same temperature Axis ofsymmetry (A.0.S): It is an imaginary line which is passing through the crystal, about which when the crystal is rotated by 360%, the number of identical appearances observed is difined as that number of fold axis of symmetry. In a cube 2 fold, 3 fold and 4 fold axis of symmetry are observed. a) 2fold axis syrmmetry: It isan imaginary line passing through the centres of opposite edges Number of fold axis of symmetry ina (6 opposite pairs of edges) 4 3 fold axis symmetry: Itis passing through the opposite comers body diagonal of the cube. Number of 3 fold axis of symmetry ina cubs (4 oposite pairs of corners) ¢)4 fold axis symmetry: Iti passing through the ce ofthe cube. imaginary] it ° i 1 i 1 t ° & ° é ; r Number of fold axis of symmet c G opposite pairs of planes) aco Total number of axis of symmetry in a cube=13 = (6two fold A.O.S+4 three fold A 2 fold AOS) LOSS > Note: Six fold A.O.S is observed ont ed only in hexagonal system. Number of six fold A.0.S in a hexagonal system] gonal system along the body diagonal of the cube. —— A © scanned with OKEN Scanneri é 1 Centre of symmetry is present only in cubic Fal number of symmetry elements in cube=23(9.P.0.S+13 ‘AOStI cos) ACE LATTICE, CRYSTALLATTICE AND UNIT CELLS Space Lattice (or) Crystal Lattice: Aspace lattice is an array of points showing how molecules, atoms or ions are arranged! at ifferent sites in three dimensional space (Regular ‘arragement of lattice points in three dimensional space). > Lattice Point: The point that represents a ‘molecule, an atomor an ion in a space lattice is called Lattice point. Unit Cell: The smallest portion of the crystal which can be used as repetitive unit in three A unit cellis characterised by: ()its dimensionsalong the three edges, a, band ©. These edges may or may not be mutually perpendicular (ii) angles between the edges, a (between b and c) fi (between a anc) and ¥ (between gq and h). Thus, a unit cellis characterised by 2. Apoint alongan edge is shared by __ sixparameters, a,b,c,a, 8 and 7 Pret of bea ‘TYPES OF UNIT CELLS, CONTRIBUTION OF LATTICE POINT TOWARDS ONE UNIT CE > (a) Primitive unit cells : When constituent particles are present only on the comer positions of. unit cel.tis called as primitive unit cell. (b) Centred unit cells : When a unit cell contains one or more constituent particles present at positions other than comers in addition to those at comers, itis called Centred unit cell Centred unit cells re of three types: (i) Body-centred unit cells : Such 4 unit ‘cell contains one constituent particle (atom. molecule o ion) at its body-centre besides the ‘ones that are at its corners. (ii) Face-centred unit cells : Suc cell contains one constituent particle presen the centre of each face, besides the ones that are at its corners. aunit tat (iii) End-centred unit cells: In such a nit cell, one constituent particles is present at besides the the centre of any two opposite fa ‘ones present at its comers. Effective Number of Lattice points in a Unit Cell Ina crystal lattice face center and edge centre shared by other cells and only a portion of such an lattice point actually lies within a given unit cell ‘A point that lies at the corner of unit cell is Shared! among eight unit cells and therefore, only cone eighth ofeach such point lies within the unit cell points Jocated at the corner, ofa unit cell are our unit cells and only one-fourth of it lies within any one cell, 3. A face-centred point is shared by two unit cells ly one half of itis present in a given u cell. 4. Abody-centred point lies entirely within the unit cell and contributes one complete point to the cel. 5. In H.C.P, corner lattice point is shared by 6 neighbour unit cells, Type of Lata polnt Gy cynic Uiteaty cLP Vs V6 Edge centred LP v4 Ww Face-centred L.P 12 v2 Body centred L.P 1 1 © scanned with OKEN Scannerei eae ¢) Lattice points are joinedt PARAMETERS) BRAVAIS LATTICE, bring out the geometry of the POSSIBLE UNIT CELLS & EXAMPLES | * These 14 Bravais latices are Crystal systems: crystal system based on ur > On the basis of inter facial angles, axis (crystallographic parameters) and symmetry Cost |B clements crystalline solids are classified into 7 can crystal systems. Cable: > Match box has orthorhombic geometry > Ice may give hexagonal or trigonal crystals Pe > Quartz may give hexagonal or trigonal crystals 7 Crystal systems and 14 Bravais lattices: ca 4 > From fundamental laws of rystallography there are 14 basic arrangements known as Bravais gon Lattices. > — Bravais showed that the 4 types of unit cells can am | be arranged in 7 crystal systems in 14 different | Primo dean possible ways in three dimerisional space which on cence are 14 Bravais lattices (or) 14 Space lattices (or) ie Trine pave Crystal lattices ee > The geometric shape of the erystal lattice must be same as that of solid crystal itself, Ex ; [funit lattice is having cubical structure the crystal isalso a cube. > The following are characteristics ofa erystal tice 4) Bach point ina lattice is called lattice point or lattice site, ) Each point in a crystal lattice represents one i constituent particle which may be an atom, a molecule or an ion and treated as regid sphears. 7 CRYSTALSYSTEMS WITH CHARACTERISTIC PROPERTIES [system © scanned with OKEN ScannerBody - centred (or simple) ‘The three cubic latices: all sides of same length, angles between faces all 90° Primitive Body - centred “The two tetragonal: one side different in length to the other, two angles between faces all 90° Primitive End - centred Body - centred Face - centred ‘The four orthohombic lattices: unequal sides, angles between faces all 90° 4 More than — # | Less tham | 2 ow E centred ‘The two monoclinic latices: unequal sides, ‘two faces have angles different to 90° Neo eet | ae one ‘i “Tren atice tna sides a, b,c AB, are unequal ‘angles wih none equal to 90 NARAYANA GROUP © scanned with OKEN ScannerNUMBER OF LATTICE POINTS INA UNIT. CELL (RANK OF UNIT. CELL) Rank: Rank ofa unit cell means the number of effective lattice points ina unit cell Simple Cubic Cell : Ina lattice of this type, each comer atom iy shared by eight unit cells, four in one layer and four in the layer above if, as shown in figure. Ty) BB eB (a) (b) (ce) ‘Thus, the contribution of each atom placed at the comer of single cubic unit celtis 1/8, Since, there are eight corners of a cube, the effective number of atoms associated with single primitive unit cells 1/8 * 8 1. Thus, the rank of simple cubic unit cell is | ‘Thus, the rank ofa primitive cubic unit cel is | BCC Unit Cell : Ina BCC lattice, each comer atom is shared by 8 unit cells while the body centered atom is not shared by any other unit cell, So, the number of effective atoms associated (4 with a BCC unit cell is| 8) +1 =2, Thus, the rank of'a BCC unit cell is 2. aes (a) (b) (©) FCCL Cell: In a FCC corner atom is shared by 8 unit cells and each face centered atom is shared by 2 unit cells, so the number of effective atoms in a FCC unit cell unit cell, ©: 4 ( 1 would be 378} 378) °4. Thus the rank ofa FCC unit cell is 4, This is shown in Figure: 3 86 (b) ) Tt AS Hexagonal Close Packing: atom would be common to 6 ot therefore thew contribution to one an be 1/6, Total number of atom in | hep) a (fiom 12 comers) 15, rom? fin 3 + 4 (from body centre) = 6. HCP Unit Cell: (b) ui closest packing of spheres (a) normal and (bjdiagramatic view WE. 2: What is the simplest formuta ofa whose unit cell has the atom A att corner, the am Bat each fai 4 atom C at the body centre, (A) ABC (BA, (©) ABC (D) ABC, Sol: Anatom at the comer ofa , Sunit cells. As there are 8 corners in #6 number of corner atom (A) per unit (2) & A fice-centred siom ina cub De is shared unit cells, As ther are 6 a faces in.a cube, nut of fce-centred atoms(13)per unitecetl» 6x 2 cells Number ‘Mons (C) at the by - unitcell= | Jat the body centre pee Hence (C), the formula of the solid iNABC, ' (ay Pron) eo © scanned with OKEN Scannerae ‘in a body centred the rf itl nd opts = of potassium = 39 (B) 2.09 * 10" (D) 3.09 x 10" 02310" Sain 3-09 10 Hence ‘A’ isthe correet Choice. Calculation of the contribution of lattice points per unit cell of substance. 1 ax =| 2 2 sxr=3] 6 1 il fxbaa)en sl ~ Alattice point at the comer ofa unt cellisshared by8 vicinal unit cells in cubie and six vicinal unit cells in HCP ‘A face centered point is shared by two adjacent unit cell, ‘Acdge centered point s shared by four adjacent ‘unit cells in cubic in three vicinal unit cells in HCP ‘Abody centered lattice point belongs completely toaspecific unit cell c 2D, 3D PACKING OF LATTICE POINTS. JEE-ADV CHEM-VOL-ll CLOSED PACKED STRUCTURE OF SOLIDS lose packed structures Packing of Solids and Voids solids constituent particles are arranged as spheres in close structure. > In > In close packed structure, maxinwum space is ed by constituent particles and leave ‘When the spheres are closely packed the different crystal systems are generated. Coordination Number for elemental crystallization: the number of surrounding @ latt the co-ordination number is ftice points point ina crystal lattice Void or Hole: Itis ant space among lattice points in three dimensional space A) Close packing in one dimension : YOY Y Close paking of spheres in one dimension Co- ordination number is 2 B)Close packing in two dimensions : Square close packing hes hexa Pree (AAA Type) coordination nod (ABA) Type al close packing coordination no.6 © scanned with OKEN ScannerC) Close packing in three dimensions : (i) Three dimensional close packing from two dimensional square close-packed layers: a) Simple cubic packing: 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 spheres of the upper layer are exactly above those of the first layer. In this arrangement spheres of both the layers are perfectly aligned horizontally as well as vertically. Similarly, we may place more layers one above the other. Ifthe arrangement of spheres in the first layer is called ‘A’ type, all the layers have the same arrangement. Thus this lattice has AAA... typepatiern. The lattice thus generated isthe simple cubic lattice, and its unit cell is the primitive cubic unit cell b) BCC Packing: When the second square close packing 2D layer is placed over the first layer such that the spheres of the upper layer are placed inthe depression ofthe first layer. Since the spheres of the two layers are alligned differently. This is AB AB AB .... type packing. ‘The lattice thus generated is the body centred cubic, and its unt cell isthe body centred cubic unit cell. BCC unit cell is (ii) Three dimensional close two dimensional hexa packed layers. Three dimensional close packed i be generated by placing layers One® (a) Placing second layer over s 1wo dimension A and placea pheres of the ed in the depressions of the fit of the two layers: BAB type nd Jaye voids ofthe ‘ent arr -cond layer er (or view T d octahedral voids. Let the number of close packed sphere N, then: The number of octahedral generated ~ N The number of tetrahedral voids generated = (b) Placing third layer over the see layer: When third layer is placed overt ‘bili -cond, are two po: © scanned with OKEN ScannerTetrahedral voids : ral voids of the second layer may be d by the spheres of the third layer, In this _ ease, the spheres of the third layer are exactly aligned with those of the first layer. Thus, the pattern of spheres is repeated in alternate layers. This patternis often written asABAB... pattem. This structure is called hexagonal close packed | (hep) structure. This sort of arrangement of atoms is found in many metals like magnesium ‘and zine. (ii) Covering octahedral voids : The third ayer may be placed above the second layer in a ‘manner such that its spheres coverthe octahedral voids. When placed in this manner, the spheres of the third layer are not aligned with those of| either the first or the second layer. This arrangement is called “c” type. Only when fourth layers placed, its spheres are aligned with those ofthe first layer. This pattern of layers is often written as ABCABC..... This structure is called cubic close packed (cep) or face-centred cubic (ec) structure. Metals such as copper and silver cerysallise inthis structure. "both these types of close packing are highly “efficient and 74% space in th filed, In either of them, each sphere is in contact with twelve spheres. Thus, the coordination ‘number is 12 in either of these two structures. * The HCP and CCP arrangements can also be shown as below : © scanned with OKEN ScannerSIMPLE CUBIC, BODY CENTERED CUBIC | > CCP, HCPLATTICES, UNIT CELLS, EFFECTIVE NO OF ATOMS PER UNIT. CELL, COORDINATION NUMBER, RELATION OF EDGE LENGTH WITH. zi 2 25 Ft ii z & a 7a, «) 4 < FCC layer diagram: ‘A- Layer ‘C-Layer ‘A - Layer B - Layer > © Body diagonal length v3 VOLUME FRACTION IN ELEMENT CRYSTALLIZATION (SC, BCC, Ct HCP) Packing Fraction (volume fraeti¢ Efficiency (or packing fr packing) ofa unit cel is defined in term percentage volume occupied by spheresif unit cell, out of total available vol calculated by the following formula. % efficiency = No of spheresper unit cell x volume occupied by each sphere total volume of unit cell Packing fraction in erystalliza' 1. Efficiency of packing in simple unit cell : A simple cube is having 1 sf perunit cell, Let consider the edge ofa cubic unit as @ , then the volume of unit elemel a’, we known from the earlier discussi insimple cube a= 2r, where 'y," is the of sphere. Percentage eflicienty of simple cubic unit volume of one sphere / volume of unit cell] (or) V3a = distance between A-B-C-A © scanned with OKEN Scanner* (or) 3+ 100=52.3=52 “Tihs, the volume occupied by sphere in simple “eubic unit cell is $2.3% and void volume is in Fe “unit cell : Consider a body-centred unit cell ‘with edge length 'q' and with radius of sphere ~ ‘x, As body centred unit cell is having two spheres per unit cell and 4° is the volume of unit cell by taking edge length 2°. From aac, 4c=/2a snd from ADF, ap ~V3a and we know Body diagonal of cubic unit cell's va 4 Thus, 4F = 47, = V3a or? Fh" percentage efficienty ofbody-centered unit cell =Volume oftwo sphere / Volume ofcube x 100 4 dn Bie 503) 0 @ fot ue Ae axtx(n) —3_ «100 = 68.05 = 68 (or) (5 r) ae “Thus, the volume occupied by spheres in body centred unit cell is 68.05% and void volume is 31,95%=32%. Efficiency of packing in face-centred unit cell : Consider a face-centred unit cell with edge length ‘a’ and volume a° . Radius of sphere i taken as r,. Ibis clear from the figure that touch \with the two other atoms diagonally arr From MBC, 4c=V2a=4r, (or) 4 4x ta(n) (2v2r,) We know that there are four spheres per unit «100 = 74.06 = 74 cell ina fi efficiency o| centred unit cell and thus per cent centred unit cell. © scanned with OKEN ScannerDENSITY ee = Volume of four spheres / Volume of cube x 100 Thus, the volume occupied by spheres in face-centred unit cell (cep arrangement) 1s 74.06% and void volume is 25.94%=26%. Volume fraction in HCP: AGS PP K 4 y i i fa Wau V.F=-—— F v Vuce~ Area of base x Height =3V3a° =24V2R" Volume faction of HCP=0.74 i Note : Height of HCP =4ck Note : Distance between ‘Aand B layer inCCP or HCP =2y3 CRYST ALIZATE HCP) lattice is atencive property’ Kno re density ofa crystalline ed from the formula density owing: equalto the Density of ofunit cell since it ism the unit cell dimens) ns, th substance can be calcula Density of the unit cell, d = cm" Sok ° Z=No. of atoms (or) formula units} M-=Gramatomic weight of Formula weight of ionic co @= unit cell edge length for eubic meter, v= volume Note : Volume of HCP: atomic radius of niobium, atomic mass is 93 W) is q (A) 49.8 pm (B) 150.1 pm (D) 143.1 pm (C) 143.14 Sol: oe Mz s3gmor'=2 my, g58gcm 6.024105 molt = 3.61» 10" = 36.1% 10" a= (96.1)'° « 10°pm = 3.304 «10pm aa [ix (36.1)?.loax = 1g 36.1 4 ‘.4.5575= 3 5! or x=antilog 0.519 = 3.304] For body-centred cubic é Hence *D’ is correct choice. 5: Copper crystallizes into a fee tattle edge length 3.61 x 10° cm. The eal (B) 10.9 gmc (D) 6.02 gmvec (A) 8.97 gmvice (5.45 gmice for fee lattice per, atomic mass of copper, M~ 63.5gmol* 4.63.5qmol pe ; GSte10 cm) i0"mar") =8,97gem ° Hence “A’ is the correct choi (N,-Avogadro’s number) © scanned with OKEN ScannerNEAREST NEIGHBOURS DISTANCE & NUMBERS CALCULATIONS IN ELEMENTAL CRYSTALIZATION SC, BCC, CCP UNIT CELLS on of nearest neighbours and distances for corner lattice point in diffferent cube crystals | f fares LP) NameorLep | Distance | NTS osnace Pw | ast adjacentC.L.P | a 6(CNo) 2nd Opp.C.L.P alone . 5 mi 12 = 2,4 face diagonal Opp.C.LP alone 3rd | pody diagonal Via 8 ol caren anber of seh ° Nearest Name of Lat | Distance fin AD space r, ww |ACLe 8(CNo) 'o- ¢ at rnd | agacmcle | a ‘ ee xt | eet | Bn 2 P| fs Plas fetes | P| x 4 so |omGition) a | 3. FOC an he! ‘Nearest Number of such rT ” istance D> cares! Name of LP Distanee f'pin 3p space © scanned with OKEN ScannerVOIDS IN 3D-CLOSE PAC] DIFFERENT PLANES IN SC, BCC & CCP CCP & HCP) NUMBER OF" LATTICI In ss ter k MERMS OF LATTICE POR Saat Walaa TERMS OF LATT! Sse cohen engines | Interstitial Voids + The a between the three dimensional layer 4 as holes or voids. The holes are interstices. There are three typ possible. 1) Tetrahedral holes : A hole three spheres in contact with each other The hole is capped by a sphere froman yer (Planar triangle with vertex do A hole formed by three spheres of contact with each other and also witha ofanext lower layer (planar triangles W upward) Note : Inthe above types of holes the are arranged at the vertices of a tetrahedron, If*X’ spheres form a solid there are *2X" tetrahedral holes. Radius ratio of tetrahedral _ 0.225 Tetrahedral voids : Tetrahedral a Rectangle plane ofsyinmety a packing 20- layer Fig. (9) Bight tetrahedral vols (b) One etme voids pect ell wing the gy © scanned with OKEN Scanner‘number of tetrahedral holes is double the ber of octahedral holes. The size of these depends on the size of the spheres ing them. Fig. Location of octahedral voids per unit cell of cep or fee lattice. At the body centre of the cube and at the _ gentre of each edge. 3) Cubic voids: the vacant space among cight spheres when arranged in simple cubic manner o o ‘Middle point is cubic void for eight comer lattice points Ifthere are X lattice points in a solid, there are total of X cubic voids Radius ratio of octahedral void Fe wes = 0-732 VOIDS IN FCC UNIT CELI Locating Tetrahedral and Octahedra Voids: Generally close packed structures have both tetrahedral and octahedral voids take cep (or fec) structure and locate these init (a) Locating Tetrahedral Voids: c The unit fh small cube Hi small cube has 4 atoms. When joined to each other, they make a regular tetrahedron. Thus, there is one tetrahedral void in each small jedral voids in total, Each ofthe eight small cubes have one void in one unit cellofcep structure. We know that cep structure has 4 atoms per unit cell. Thus, the number of \ctrahedral voids is twice the number of atoms. stom at alternate corners. © scanned with OKEN Scanner(8) TVS A p OVS. FORMATIG LOCATION OF VOIDS, B NUMBER OF VOIDS PERE (b) Locating Octahedral Voids: Let us again consider a unit cell of cep or fec lattice. “This unit cell has one octahedral void atthe body centre ofthe cube. Besides the body centre, there is one octahedral void at the centre ofeach of the 12 edges. Each edge of the cube is shared etween fouradjacent unit eells. 1/4th ofeach oid belongs to a particular unit cell. Thus in cubic close packed structure Octahedral void at the body-centre of the cube=1- 12 octahedral voids located at each edge and Three dimentional view H.CP unit ceils: PCCP I shared between four unit cells =127 =3 _. Total mumber of octahedral voids = 4 ° We know that in cep structure, each unit cell has ° > 4atoms. Thus, the number of octahedral voids 9 we is equalto this number. ¢ = 3 RO No.of CCP Las . EMUNGLOf octabctrat voids acy wer ces et Se No. oft 4 BCLP + 12 BO vids = § (8 BCLP) © scanned with OKEN ScannerNoid er o V Number oflattic points = 1 (8CLP) Number of cubic voids = 1 (1 BCLP) Ferric oxide crystallizes in a hexagonal ched oxide ions with vo three. Octahedral holes Every The formula of the ecto. ic (B) FeO, (@D) None of these Prana A fons eee a nber of oxide ions (O*) in the ey Sere, core mmbe offers rest Therefore, ratio of Fe: OF AN=2:3 ‘Hence ‘C’, the formula of ferric oxide is FeO, Formula of a Compound aad Number of Voids Filled £7 Acompound is forned by two elements ‘Xand ¥. Atoms of the element Y(as anions) ‘make cep and those of the element X(as cations) oecupy all the octahedral voids. What is the formula of the compound? Sol: The cep lattice is formed by the element Y. The ‘number of octahedral voids generated. would be ‘equal to thenumber ofatoms of Y present i it Since all the octahedral voids are occupied by the atoms of X, their number would also be equal to that of the element Y. Thus, the atoms of ‘elements X and Y are present in equal numbers or 1:1 ratio. Therefore, the formula of the ‘compound is XY. WE fis Atoms of element B from hep lattice and those of the element A occupy 2/3rd of tetrahedral voids. What is the formula of the ‘compound formed by the elements Aand B? Sol: The number of tetrahedral voids formed is equal to twice the number of atoms o felement B and ly 2/3rd of these are occupied by the atoms ofelement A. Hence the ratio of the number of ‘atoms of A and B is 2x(2/3):1 or 4:3 and the formula ofthe compound is 4,2, ic solids: Limiting Radius ratio :~ Itis the ratio of the smaller ion radius to that of p= the larger ion ite. © scanned with OKEN Scannera ane ofanion. The shape ofthe crystals ordination number, . ~The structure of inany ionic solids can be: accounted by considering the relative sizes of the ‘cation and anion, and their relative numbers. By simple calculations, we can work out as how many ions of a given size can be in contact with a smaller ion, Thus, we can predict the co- ordination number from the relative size of the ons. Calculation of some limiting radius ratio values 1. Co-ordination Number 3: “The adjacent figure shows the smaller positive ion of radius r’ incontact with three larger anion: ofradius In this figure, AB = =AC=2r BE=r BD=r tr ZABC = 60° = ZBDC=120" or ZBDE=60° , cos ZABD) = 0.7071 BD_ ‘Br © scanned with OKEN Scanner(b) 0.414 0.732 9 (d) None e complex [Ni(CN),]* is square planar. limiting Beto as octahedral i¢.0.414—0.732. In closest packing of A type of atoms eee pn ram void is (b) 0.1254, (a) 0.732", " Coordination Number of Crystals ‘For elemental crystallization: ‘The coordination number ofelement in solid is “the number ofnearest such neighbours for that element " Insimple cubic, C.No of metal = 6 ic, C.No of metal = 8 In H.C.P, C.No of met Note: 1) Inmetal lattices the coordination “number ofa metal atom is usually 8 or 12 2) Simple cubic elemental crystallization is “observed only in polonium keene For ionic solids: The co-ordination numberof an ion in ionic sold the number of oppositively charged ions surrounding that ion in 3D space. Inbody centered cubic, C.No of ion = 8 (CsCl type) In face centered cubic, C.No of ion (NaCl type)=6 Note ; 1) Coordination number of C in diamond is 4 2)In SiO, coordination of 57 is 4 while that ‘ofoxygenatom is 2 Effect of temperature and pressure on coordination number: a) Effect of temperature on coordination number: As temperature increases, coodination number decreases. Bee b) Effect of pressure on coordinat tion number: As pressure increases, coodi number increases. poses ee CsCl type Be mae SIMPLE IONIC COMPOUNDS BAS ON SC, CCP & HCP UNIT CELLS, RELATIONS, VOLUME FRACTION CALCULATIONS & DENSITY CALCULATIONS Classification of Tonic Struct > Simple ionie compounds are of the type AB.AB.. _B,A,B,...ete., where A and B represent the positively and negatively charged ions respectively. > Inany solid of the type A.B., the ratio of co: ordination number of Ato B would bey: x > Inionic solids bigger size ion makes lattice and smallar size ion enters into the void > For 1:1 ions ratio ionie solids position of cation and anion vice-versa is possible for the unit cell construction, Prod © scanned with OKEN ScannerHold ote Volume action in one solids is usually BERET 9" tht oF clement cystaliall ‘with the same packit © scanned with OKEN Scanner© scanned with OKEN ScannerPe Note : Diamond has same crystalline structure has Zinc blend. All Zn”? and S* are occupied by only carbon atoms, Calculation : V3a = 4d, =8R, ‘Volume fraction =0.34 rovskite Structui Itis ABO, type structure. ‘Where A is dipositive ‘cation which is at all corner lattice points and B js tetra positive cation which is at centre of the bodyandO- is oxide ion which is at all face centre of the cube. Number of ABO, formula units per unit cell=1 Example: CaTiO, formula of AB,O, For example: MgAl,O, In normal spinel structure, LP, divalent metal ions occupy tetrahedral holes and trivalent 1/2 of the octahedral holes. Eg: Ferrites: MALO, (Mot Inverse Spinel Structure: ‘ides with two types of metal nd the other is trivalent am ABO, For example : FeFe.0, . spine! structure, oxide sons a ions occupy 1 sand trivalent met .tahedral holes! sccupies 8th @ In inv LP, divalent m octahedral hol tetrahedral he B~crystoballite structure (SiO.)¢ CRYSTOBALLITE © scanned with OKEN Scannerol Structure of truncated octahedron The truncated octahedron is the |4-faced Archimedean solid, with 14 total faces : 6 squares cell =18 and 8 regular hexagons. ure of Rutile a= fo _ Ww . 7 , ‘The truncated octahedron is formed by removing = the six right square pyramids one from each point Ne RUTILE ofa regular octahedron as ‘of oxygen atoms per unit cell ~ —4 ‘of formula units per unit cell=2 fion number of titanium =6 ion number ofoxygen=3 number ratio = 2:1 toms ratio= 1:2 Truncated octahedron unfolded in two a dimensions. > ZSM-s catalyst has Truncated octahedron shape. NUMBER OF NEAREST IONS CALCULATIONS LN | n, | Forcation, | For cation, | | no.of nearest | no.of nearest | _ cation ‘anion ForCl,6Na | ForC! ,12Cl| ForNa , 12.Na’ | For Na ,6Cl NaCl [CCP CsCl | S.C For) ,8Cs |For! ,6C/ |ForCs',6Cs’ | ForCs 8 C/ ‘ZnS CCP Fors’,42Zn" |ForS’, 12S" |For Zn", 12Zn" | For Zn’, 4S “lies ForF ,6F For Ca”, 12 Ca | For Ca’, 8F mir | CCP ForF ,4 Ca” For O°, 120° | For Na ,6 Na For Na ,4.0° NaO | CCP For 0" ,8Na © scanned with OKEN Scannerdefinite rational :Q.b:R.c where P, Q, Rare weiss indices, may be rational numbers (or) zero (or) interger (or) infinite Miller indices: > Millerindicesare which are multiplied of weiss indices. Miller indices are denoted by (hk/) Fg: Crystal intercepts along xyz axi=2a:3b:206 Weiss indices ratio= 2:32:20 -. Miller indices [si4)-Gsseee Perpendicular distance between two adjacent parallel planes in a cubic crystal: he reciprocals of weiss indices with the LCM ofreciporcals > dy i Different planes in simple cubic crystals is (1.00),(1 10), (11) hs Different planes in body centred cubic erystals > is (2.00), (1 10), (222) BRAGGS EQUATIONS, DETE X-Ray OF CRYSTALINE STRUC] BRAGGS SPECTRO PHOTO! METHOD & POWDERS METH rystal structure=Bi Equation X-raydiflfaction studies of erystale the internal structure Is ie. the pattern of arrangement of crystal compan size and shape of the unit cell Flectromagnetic radiation propagate ia of wa of waves alc displa wave is known as amplitude of the wave. For constructive interference resultant is2B, (F, For destructive inte is Zero= out pl The waves, if pr undergo constructive interf hand ifthe waves a destructive int Max one |: ested that t between the adjacent plane phases j inthe order of wavelength of X-r Giffaction of X-rays by crystalline Bragg’s Equation: w.. p; Bragg worked out and g relation to determin. X-—raydiffraction pattern, theBrage’s equs 3 in all directions ment pe Amplitude) = Jn phase wa nce resultant amp fere © SU ea mathemé ter atornic distance ARO Thisr © scanned with OKEN Scanner‘ofreflection ty ofthe diffracted X —ray fromthe 'is measured on.a photographic plate or nchamber. The ionization chamber tain CH,Br / SO; vapours. ‘extent of ionization in the vapour is shown, ‘the electrometer reading. ‘Asthe intensity of e diffracted X —rays increases, the degree of also increases the angle of incidence the extent of nat different angles is recorded in the ‘The Crests f the graph, taken rom electrometer , Gifiraction. The angl arenotd rom the graphs. anit refisinn acing agi) — From the experimental ) above graph, expermental “d),, and 9 values of the cab be obtained Pons ie be dns Zin > — Experimental ‘d’ (distance) ratio: 1 don deeds “VE = Simple cubic ayo 20 Body centred cubie(CsCl) or Elemental BCC 0.707 1.154 => zg td 4), Face centred cubic( NaCl) The angles are substituted for '@' in E equation and the values of are calculated Eg:-ForNaCl erystal‘d values are inthe ratio l 1: 1:0,707 1.154, Fromthis it of eh Fromthis it jsconfirmed that the crystal has F.C.C, structure. Note : {) Bragg’s method to be used. large s es of the erysta are neccessary. The plan sily identified be filly developed an i) Debye - Scherrer Method is used to determine the crystal structures in the powdered form. CRYSTALL DEFEC ids: At‘0’Kelvin, a perfectly reide: ubstance is said toh crystallin which means that all the lattice occupied by particles of the solid and the crystal ints ar isperfect > _ Asthe temperatures increased, thermal motions fe induced which create solid > Any deviation from the perfectly solid is known as a » 's in the crystals can be divid different kinds > Intrinsic defects : These are seen in pure crystals. > Extrinsic defects : These are due to the impurities in the solids © scanned with OKEN Scanner(defects are the iregulrities or deviations from ideal arrangement around a point oran atom in @ crystalline substance, whereas the line defects are irregularities or deviations from ideal arrangement in some rows of lattice points. Properties like density, entropy and heat capacity are influenced by crystal defects to a lesser extent ‘The defectsin the crystal, influence the properties like mechanical strength, electrical conductivity and chemical activity of the solids to a greater extent. ‘Thermodynamically all solids possess a tendency to acquire defects because defects result in disorder and hence increase the entropy of the system Electron micro scope is used to know the defects in asolid crystal ‘Types of point defects: 1) Stoichiometric defects 2) Non-stoichiometric defects Stoichiometric compounds are called Dalionoides, non-stoichiometric compounds are called Berthollides. Stoichiometric compounds: These are the the same of compounds in which ions ratio that of ions ratio represented by formula Eg: NaCl Non-Stoichiometric compounds: These are the compounds in which ions ratio is not same as that of ions ratio represented by formula Eg: FeO, STOICHIOMETRIC DEFECTS : SCHOTTKY, FRENKEL DEFECTS Stoichiometric defects They are also called intrinsic orthermodynamic defects. These are oftwo types. "Vacancy defect” and ‘interstit defect’. When some of the lattice sites are vacant, the crystal is having vacancy defect. When some constituent particles occupyan interstitial site, the crystal shaving interstitial defect. Theyare shown by non-ionic solids. Jonic solids show two defects 1) Schottky defect a) Schottky defeet (Schottky-Wagner Conditions for this defect Ex oe nces of this defect: This defect arises due to aVae id equal number of vacancies at In ionic crystals electrical maintained r on numbers and ¢ and negative! 2Br t | decreases, nduct electricity tg now move in the defect und in highly cies in the lattice i © scanned with OKEN ScannerCation present in interstitial site Jow since positive ions are smaller thannegative generally the positive ions are found in px + ZnS, AgBr, Agl, AgCl. sme ionie crystals have both the Schottky as vellasFrenkeldefects. Ex: AgBr Consequences of enkel Defe sty of the crystal isnot altered RIC EFFECTS AND METAL ‘Yacaney) ; It is due to absence of anion from lattice site leaving a hole which is occupied by electron to maintain electrical neutrality x B a 8 B a e A F-Centres ; Holes occupied by electrons are called F - Centres (Colour centres). The greater the number of F - centres the greater is the intensity of colour of solid and solids are paramagnetic in nature due to F - centres Eg: NaClis yellow, KClis violet, LiCl is pink Cystals showing schottky defect also show this defect, Metal excess defect due to the presence of extra cations at interstitial sites :200 on heating loses oxygen and turns yellow. Now there is excess of Zinc in the crystal. The S Zn® ions move to interstitial sites and the electrons to neighbouring interstitial sites ZnO det +50, ye Metal deficiency defect due to cation yaeancy; It is due to absence of a metal ion from its lattice site and charge is balanced by ion having higher positive charge. A B oO B B A B A Transition metals exhibits this defect. A typic example of this type is FeO whichis mostly foun witha composition of Fe, ».0. It may actually range from Fe,,,0 to. Fé, In crystals of nd the loss FeO some jre” cations are missing of positive charge is made up by the presence of required number of fe" ions PURITY ¢) Impurity defe containing small quantity of SrCl is crystalised : If molten NaCl some of the Na’ ions are replaced by Sr. Each Sr replaces two Na’ ions. Itoccupies the site of one Na ionand the other site remains vacant Other example is the solid solution of CdCl, and AgCl. Panag © scanned with OKEN Scanner