v ' uJ - 2 a oO =SOLID STATE NEET SYLLABUS Solid State : Classification of solids based on different binding forces; molecular, ionic covalent and metalic solids, amorphous and crystalline solids (elementary idea), unit cell in two dimensional and three dimensional lattices, calaulation of density of unit cel, packing in solids, packing efficiency, voids, number of atoms per unit cell in a cubic unit cel, point detects, (electrical and magnetic properties, Band theory of metals, conductors, semiconductors and insulators.) (Explained in Physics)IM crt uacacnsamerenmetende sa sm MONS maar Chas 1.0 INTRODUCTION ‘The solid are characterised by incompressbilty, rigidity and mechanical strength. The molecules, atoms or ions in solids are closely packed means they are held together by strong forces and can not move randomly. ‘Thus solids have definite volume, shape, slow diffusion, low vapour pressure and possesses the unique property of being rigid. Such solids are known as true solids like NaCl, KCI, Sugar, Ag, Cute. On the other hand the solid which loses shapes on long standing, flows under its own weight and easly distorted by even mild distortion forces are called pseudo solids such as glass, pitch etc. ‘Some solids such as NaCl, Sugar, Sulphur etc. have properties not only of rigidity and incompressibilty bt also of having typical geometrical forms. These solids are celled as erystalline solids. In such solids there is definite arrangements of particies (atoms, ions or molecules} throughout the entire three dimensional network of a crystal in long-range order. This three dimensional arrangement is called crystal lattice or space lattice. Other solids such as glass, rubber, plastics etc. have rigidity and ineompressiblty to a certain extent but they do not have definite geometrical forms or do not have long range order are known as amorphous solids. Distinction between Crystalline and Amorphous Solids ‘Shape Definite characteristic geometrical shape | Irregular shape | Melting point __| "Meltata sharp and characteristic Gradually soften over a range of temperature temperature Cleavage When cut with a sharp edged tool, they | When cut with a sharp edged tool, they property split into two pieces and the newly cut into two pieces with irregular rated surfaces are plain and smooth | surfaces Heat of fusion ‘They have a definite and characteristic | They do not have definite heat of fusion heat of fusion [Anisotropic nature | Anisotropic in nature Tsolropic in nature ‘True solids Pseudo solids or super cooled liquids arrangement of | Long range order Only short range order. particles Examples NaCl, Metals, Diamond Rubber, Plastics (a) @) Anisotropy in orystals is due to different ‘Two dimensional structure of arrangement of particles along different (a) quartz and (b) quartz glass directions,Pre-Medical Table (a) : Classification of crystalline solids S. [Type of Solid | Constituent ] Bonding/ | Examples [Physical | Electrical [Melting No. Particles | Attractive Nature | Conductivity |Point Forces 1. [Molecular solids Ji Non polar | Molecules | Dispersion or | Ar, CC, | Soft Insulator Very low London forces| Hl,CO, (ii) Polar Dipole-dipole | HCI, SO, Soft Tnsulator interactions id Fiydrogen Hydrogen [H,Ofice) [Hard | Insulator Low bonded bonding |2.Jlonicsolds [Tons Coulombic or | NaCl, MgO. [Herd but” | Insulators High electrostatic | ZnS, CaF, foritie | in solid state but conductors in molten and in| aqueous state (3. [Metalic solids | Positive metal | Metallic Fe, Gu, Ag, [Hardbut | Conductors [Fairly fons in a sea of | bonding Mg ‘malicable | in solid and in [high delocalised and ductite| molten state fa. [Covalent or | Atoms Covalent | S10, SiC,AIN Vey network solids bonds Cidiemond), |Hard | Insulators [high Cloraphite) [Soft Conductor tT Space Latce/Crstalline atie/3-D Tatice 12 ‘Space lattice is a regular arrangement of lattice points {atoms or ions or molecules) showing how the articles are arranged at different sites in 3D-view, Lattice point Lines are used to represent geometry of crystal * "The three dimensional distribution of component particles in a crystal can be found by X-ray diffraction. of different faces of the crystal. * On the basis of the classification of symmetry, the crystals have been divided into seven systems, These seven systems with the characteristics of their axes (interfacial angies and intercepts) where some examples of each are given in the following table (b) These crystal systems differ in length of unit cell edges (a, b and c) and the angles between the unit cell In cubic and trigonal (rhombohedral) systems, the three unit edges are of equal lengths but for the rest five systems it is not so. ‘The interfacial angles are ali 90" in the cubic, tetragonal and orthorhombic systems but itis not so for the rest four systems, Unit Celt (U.C.) Unit cell of the crystalline substance is defined as the smallest repeating portion which shows the complete geometry of the crystalline substance like brick in wall. A unit cellis the smallest pottion of the whole crystal. A unit cellis characterized by the edge lenaths a, band calong the three axes ofthe unit cell and the angles a, B and y between the pai of ‘edges be, ca and. ab respectively.Chemistry Ss. ‘Name of [Bravais Examples) No. | System | Lengths 1, Cubic a=bec NaCl, Zine blende, Cu 2, | Teragonal [a-bec White tin, Sn0,, THO, CaSO, 3. | Orthorhombicl az b= e Rhombic sulphor. or Rhombie 1, | KNO,, Bas, Body centred, | Match Box, Duster End centred = 4 4. | Rhombohedral a=b=¢ [a=—=7 290 | Primitive= 1 | Calcite (CaCO), HgS (cinnabar) or Trigonal 5. | Hexagonal [a=bee 90°, = 120 Primitive= 1 [Graphite, ZnO, CdS. 6. | Monodinic [asbee la=y=90, p= 90"| Primitive, Monoclinic sulphur, End centred =2_|Na,SO,. 10H,O 7 | Tridlinic aabeo cE #47490" | Primitive = 1 |K,Cr,0,, GxSO,, 5,0, 11,B0, Total = 14 7 eee bi —_ eualtenghy a wee are 90? a primitive primitive body centred face centred ‘Trigonal (Rhombohedral) (One sie lat changes Onesie ‘uo anes hed at 907 a / ‘ne fed at 120° Two side angi mae anal of aneth e tbe same; ene ange tase ‘ad al 12° ‘Alles eo ferent Hes aebee Tovclicarect Sonael ere kgs; ——— ‘Manges a 50) Og primitive body ens cen face centred end centred EDA ARARENOHEN ENCOUN SE HECHES mhve 1.3. Co-ordination Number The number of nearest neighbouring particles around a specific particle in a given crystalline substance is called as co-ordination number of that crystalline substance. 1.4 Packing Efficiency or Packing fraction (P.E.) “Packing efficiencyis defined as the ratio of volume occupied by the atoms to the total volume of the erystalline substance” pE.- Wolume occupied by atoms present ina crystal — Volume of crystal Volume occupied by atoms present in unit cell pp _2x(4/3)m? Volume of unitcell or PES Where z = number of atoms present in unit cell / Number of formula units for ionic crystals. GOLDEN KEY POINTS @ = =Inacube PE= 1, Number of comers = 8 2, Number of faces = 6 3. Number of edges = 12 4, Number of body centre = 1 5, Number of body diagonals = 4 6. Number of face diagonals = 12 ¥ Face centre (6) Comer (8) edge (12)- \ bocy et son Face(6) a cova] ase agen (1) a Contribution of an atom at different lattice points of cube : © — Acorner of a cube is common in 8 cubes. So th part of an atom is present at this comer of cube. © A face of a cube is common in 2 cubes. So ¥f th part of an atom is present at the face of a cube. ‘An edge of a cube is common in four cubes, so }/ th part of the ator is present at the edge of a cube ©} Acube centre is not common in any another cube, so one complete atom is present at the cube centre. eR ORO TAROT NACUBO EOSChemistry Face diagonal W2a} ea Distance between 2 adjacent face centres = ¥ Distance between 2 adjacent edge centre = B 08 Consider the triangle AFD (with the help of pyathogorous theorem) FD = VAF™TAD® =a? va? =a lenath of face diagonal.) Consider the triangle ABFD (with the help of pyathogorous theorem) BD =VBF?+FD! = ya®+ (2a)? = Ja (length of cube diagonal) Illustrations Mlustration 1“ Which of the following is a non-crystalline solid ? ()csct (2) NaCl (3) CaF, (4) Glass, Solution. Ans. (4) Mlustration 2,“Which of the following statements is incorrect ‘about amorophous solids? (1) They are anisotropic (2) They are rigid and incompressible (3) They melt over a wide range of temperature (4) There is no orderly arrangement of particles Solution ‘Ans. (1) Must (Assertion : Crystalline solids ate anisotropic. Reason : The constituent particles are very closely packed. aya 2B @c @D Solution. Ans. (2) 1.6 (I) CLASSIFICATION OF UNIT CELL (As per Bravais) Unit Ceit Primitive unit cell Centered unit cell Same type of particles are ‘Same type of particles are present at comers only present besides corners Face centered Body centered End centered FC (BO) (EC) ‘+ In end centered same type of particles are present at corners and any two opposite face centres. ‘* End centered type of Bravais lattice Is present only in orthorhombic and monoclinic type unit cell. IM Pe coenmextrnemaennowenss ss 10sHm0 EONSPre-Medical (TYPES OF CUBIC UNIT CELL ‘The distance between successive lattice planes of the same type is called the spacing of planes or interplanar distance between the planes. On the basis of this aspect, the lattices may be divided in following classes : (A) SIMPLE/PRIMITIVE/BASIC CUBIC UNIT CELL ‘A.unit cell having lattice point only at corners is calied primitive or simple unit cell. i.e. in this case there is one atom at each of the eight corners of the unit cell considering an atom at one corner as the centre, it will be found that this atom is surrounded by six equidistant neighbours (atoms) and thus the co-ordination number will be six. if’ is the side of the unit cell, then the distance between the nearest neighbours shall be equal to ‘a. Ith @ Relationship between edge length ‘a’ and atomic radius 'r' : a= 2r ie. (One face of SCO) (bo) Number of atoms present in unit celll (2) : In this case one.atom or ion lies af the each Conner, Hence simple cubic unit cll contains ato of £8 «= 1 atom or fon/unit cel © Packing efficiency (P. E.) : PE, = Volume occupied by ators present Volume of unit cel a 4 a dee( 3) ForSC: PE.=—=—\") = Gro 524 oF 52.4% a Jn SC, 52.4% of total volume is occupied by atoms or ions %6 void space = 47.6 IM rrccecneoso htoaceiceasewers. ct0 SHO EDRs IM) esis wtrerenosenreeoNe DTA HOREBama Chemistry (B) BODY CENTRED CUBIC UNIT CELL (bec) A unit cell having lattice point at the body centre in addition to the lattice point at every comer is called as body centered unit cell : where body diagonal particles are touching particle. Here the central atom is surrounded by eight equidistant atoms and hence the co-ordination number is eight. The nearest distance between two atoms till b (a) Relationship between edge length ‘a’ and atomic radius 'r’ In BCC, along cube diagonal all atoms touches each other and the length of cube diagonal is (3a. So, Ba =4r ie so (b) Number of atom present in unit cell (z) x8 }e(Daa)=1122 atoms/unit cell (Comer) (Body centre} In this case one atom or ion lies atthe each corner of the cube. 1 ‘Thus contribution of the 8 corners is Gee, while that of the body centred is 1 in the unit cell. Hence total number of atoms per unit cell is 1 + 1 = 2 atoms (or ions) Packing efficiency : f= InB.C.C., 68% of total volume is occupied by atoms or ions, 46 void space = 32Pre-Medical (C) FACE CENTRED CUBIC UNIT CELL (fcc) A unit cell having lattice point at every face centre in addition to the lattice point at every corner called as face centred unit cel. i. in this case there are eight ators at the eight corners of the unit cell and six atoms at the centre of six faces. The co-ordination number will be twelve and the distance between the two nearest atoms wall be 2 @) o) © Relationship between edge length 'a' and atomic radius 'r' : ace diagonal W—a Jn fec, along the face diagonal all atoms touches each other and the length of face diagonals (Ba a 22 Number of atoms per unit cell (2) : Sodr= 2, ie. iB = 1 1 z= | g*8)*|6%5) =143-=4 atoms/unit cell Comer faces In this case one atom or ion lies at the each comer of the cube and one atom or ion lies at the centre of each face of the cube. It may noted that only ; of each face sphere lie with in the unit ‘cell and there are six such faces, 1 The total contribution of 8 comers is (8) = 1, while that of 6 face centred atoms is, 1 (5) = 3in the unit cell. Hence total number of atoms per unit cellis L + 3 = 4 atoms (or ions) Packing efficiency : @ 4 4 a ) axon 4xq mx a -_3 2) on op ped, =e Ve PEM gyg7 O74 or 74% Wy aed eos at 2 i.e. In fcc, 74% of total volume is occupied by atoms. ‘% void space = 26 Fc eecrune areamoenineincnie seinen ect FM CLERC WITT OENE WOOLEN SAD SAB MEORNSAD sncceonsancsen tance creas WOOK 41 SOM SURO THER Chemistry ‘SUMMARY TABLE Relation jaation ‘occupied between &a | Number by particles (%) Simple cube 6 | F100 =52.4 Body centred 8 «100-68 cube (bce) Face centred a 2 +100=74 aide (fee) Illustrations Mlustration 4. If the radius of an atom of an element is 75 pm and the lattice is body-centred cubic, the edge of the unit cell will be (1)32.475 pm (2) 173.2 pm (3) 37.5 pm @) 212.1 pm Solution. Ans. (2) lustration 5. Assertion : A particle present at the comer of the face centred unt cell has 1/8th ofits contribution of the unit cell, Reason : In any space lattice, the corner of the unit call is always shared by the eight unit calls : Qa QB Bc @D Solution. ‘Ans (3) Im een xomanoesmeucmr sain Sonor Mons Tlustration 6. In.a face centred cubic arrangement of A and B aloms where A are present at the comer and B at the face centres, A atoms are missing from 4 comers in each unit cel? What is the simplest formula of the compound? 1 No. of Batoms = 6x 5 =3 Formule = A,,B,= AB, Solution. No. of A atoms = 1.7 DENSITY OF THE CRYSTAL (d or p) If the length of edge of the unit cell is known we can calculate the density of the crystal as follow Let length of edge of the unit cell be a’ cm. Volume of the unit cell = V em®= 2? em? Mass of unit ce Volume of unit coll Let mass of N particles present in a lattice = m g Density of the unit cell =. sass of 1 particles present ina latice = Fa mass of z particles present in lattice = ys Tem oo Nal umber of particles or number of formula unt (for ionie rstals)Pre-Medical Peed + Ifnumber of particles in alattice=N 0 « For calculation use N, = 6 «102 number of SC unit cell = N number of bee unit cell = . Lpm = 107? m= 10° em numberof fc unit call = . 1A= 10° m=108an BEGINNER'S BOX-1 A Aluminium (Molecular weight = 27) crystalises ino cubic unit cell wth edge length a = 100 bm, with density, d= 180 g/cm, then type of unit cell is (1) sc (2) bee (3) fee (4) hep 4 An element has bec unit cell with edge length 10A, if density is 0.2 ¢/am, then molar mass of ‘the compound is (1) 240 (2) 60 (3) 35 (4) 280 3 Miateragonal ens (a= becae f= 90% ay (ha-B=7-90aeb ec (a=B=y=W ax dye (a= B= 90%, ¥=120%a=b ac <4 Edge length of a cube is 400 Pm, its body diagonal would be~ (1) 500 pm (2) 600 pm (3) 566 pm 4) 693 pm 5. A metal crystallses into two cubie phases fee and bee whose unit lengths are 3.5 and 3.0 A respectively, the ratio of densities of fee and bec is (1.26 (21.75 (3)2.10 (4 1.90 1.8 CLOSE PACKING OF IDENTICAL SOLID SPHERES 10 _ TT. PA scrum canes sao@ f@) ) ®) maaan Chenin ‘Single Layer arrangement The centres of the spheres lie one below another. This type of arrangement is called square packing, In such packing one sphere touches four other spheres, In this case 52.4% of the volume is occupied. The remaining 47.6% of the volume is empty anc is called void volume, In square packing co-ordination number is 4 ‘Another type of arrangement of atoms is shown below. This type of packing is called hexagonal packing In such packing one sphere touches six other spheres. In this case 60.4% of the volume is occupied. The remaining 39.6% of the volume is empty and is called void volume. Therefore this type of packing is ‘more compact than the square packing Multi Layer arrangement When first square arrangement of layer A is exactly placed above occupies 2” square arrangement of layer A and so on. So this type of arrangement is known as AAA. ;,..,, arrangement and its unit cells simple cubic unit cell. Simple cubic lattice formed by A AA .... arrangementPre-Medical 12 (by co There is another possible arrangement of packing of spheres known as body centred cubic (bec) arrangement. This arrangement is observed in square packing In bce arrangement the spheres of the second layer lie at the space in the first layer Body centred cubic lattice formed by ABAB ..... aver B layer A Thus each sphere of the second layer touches four spheres of the first layer. Now spheres of the third layer are placed exactly above the spheres of first layer. In this way each sphere of the second layer touches eight spheres where four of 1st layer and four of Id layer. Therefore coordination number of each sphere is 8 in bec sturcture. The spheres occupy 68% of the total volume and 32% of the volume * is emply space. Close Packing in Multi Layer Inhexagonal close packing, there are iwo types of the voids which are divided into two sels band’ for convenience. The spaces marked ‘¢ are curved triangular spaces with tips pointing upwards witereas spaces marked 'b' are curved triangular spaces with tips pointing downwards. Layer A Ib, cf type voids Layer B —[c, al type voids Now we extend the arrangement of spheres in three dimensions by placing second close packed layer {hexagonal close packing) B) on the first layer (A). The spheres of second layer may placed either on space denoted by orc, It may be noted that itis not possible to place spheres on both types of voids (band c). Thus hal ofthe voids remain unoccupied by the second layer. The second layer also have voids of the types’b’ and in order to build up the third layer, there are following two ways:I resccmas wntamorennescOAE 6 ScLD SiO SOR Chemistry {@) When’ type of voids are covered in 3 layer the spheres of the third layer (C) ie on the second layer (Bhin such a way thet they le over the unoccupied spaces’ of the first layer). f this arrangement is continuous inthe same order this represented as ABC ABC ABC... This type of arrangement represent cubic close packed {ecp) structure A 5 c A ° — i" A B © Cubical closest-oacked structure . A A Exploded view ...+. or cubic closes packing (ccp) of spheres In this system, there is a sphere at the centre of each face of the unit cell and hence this structure is also known as face-centred cubic (fee) structure because unit cell of cep is fee. Ik may be noted that in ocp (or fcc) structures each sphere is surrouneled by 12 spheres hence the coordination number of each sphere is 12. The spheres occupy 74% of the total volume and 26% of is. the empty space in cep structures. (b) When type of voids are covered in 3¥layer; the spheres ofthe thitd layer ie on the spaces of second layer (B) in such a way that they lies directly above those in the first layer, In other words we can say that the third layer becomes identical to the first layer. I this close arrangement is continued infinitely in the same order this represented as ABABAB ....close arrangement. 3Pre-Medicai 6 fold axis ABABAB..._ or hexagonal close packing thep) of spheres, Ceordnation umber of hep al cep strate 4 Number of particles in hexagonal unit ceil Some examples of metals with their lat LD Body-centre Cubic bed Frce cental cable Bh Sinpke Cutie Lio t Ion Erba pe {types and coordination number are given in the following table. (Cros ct nt a e ‘MULTILAYER CLOSE PACKING Contents sc bee cep/fcc_ ‘hep ‘Type of packing | AAAA.. ABAB ‘ABCABC.... ‘ABAB ..... packing butnot| packing but not | close packing close packing close packing _| close packing No. of atoms: T 2 _[ 4 6 Co-ordinationno.| 6 8 12 42 Packing efficiency | 62.496 68% 7496 74% Examples Mn TA, Ba Ca, Sr Al Remaining V& Cr group Co group, Nigroup, | d-block elements Fe Copper group, allinert | Be & Mg | gases except He ‘© Only Mn crystallizes in simple cubic arrangement (sc) © In close packing, number of particles = N, number of OHV = N, Number of THV = 2N TM asncomsansaacn rancor Neo NCOUE 4 SUD SUNG THERES,maaan Chit Illustrations Illustration 7. The arrangement of the first two layers, one above the other, in hep and cep arrangements is (1) Exactly same in both cases (2) Partly same and partly different (3) Different from eath other (4) Nothing definite Solution. Ans. (1) Mlustration 8. Assertion : ABAB.... pattern of close packing gives ccp arrangement. Reason : In fcc arrangement each sphere associated with two tetrahedral voids, aa AaB (3) C yD Solution. Ans. (4) IMustration 9. “Theres no difference in the arrangement of atoms in ccp and hep structure” Do you agree with this statement ? Explain why, Solution. Statement is incorrect cp ABC ABC ABC hep AB AB AB 1.9 INTERSTICES OR VOIDS OR HOLES IN CRYSTALS. thas been shown that the particles are closely packed in the crystals even than there is some empty space left in between the spheres. This is known as interstices (or interstitial site or hole or empty space or voids). In three dimentional close packing (cep & hep) the interstices are of tw types (tetrahedral interstices and (i octahedral interstices, (A) Tetrahedral Interstices We have seen that in hexagonal close packing (hep} and cubic close packing (cep) each sphere of second layer touches with three spheres of first layer. Thus they, leave a small space in between which is known as tetrahedral site or interstices. or The vacant space between 4 touching spheres is called as tetrahedral void. Since a sphere touches three spheres in the below layer and three spheres in the above layer hence there are two tetrahedral sites associated with one sphere. & oo A tetrahedral interstices ‘Tetrahedron geometry It may by noted that a tetrahedral site does not mean that the site is tetrahedral in geometry but it means that this site is surrounded by four ‘spheres and by joining the centres of these four spheres forms a requler tetrahedron. In fcc, one corner and its three face centres form a tetrahedral void In fec, two tetrahedral voids are obtained along one cube diagonal. So in fee, 8 tetrahedral voids are present. In fee, total number of atoms = 4 In fec, total number of tetrahedral voids = 8 So, we can say that, in 3D close packing 2 tetrahedral voids are Telrahedeal void attached with one atom. Cube diagonal 5Pete mma 6) ‘Octahedral Interstices Hexagonal close packing thep) and cubic close packing (cep) also form another type of interstices which is called octahedral site. The vacant space between 6 touching spheres is called as octahedral void. In the figure, two layers of close packed spheres are shown. The spheres of first layer are shown by full circles while that of second layer by dotted circles, Two triangles are drawn by joining the centres of three touching spheres of both the layers In feo, 6 face centres form a octahedral void. On super imposing these triangles on one another one octahedral site is created. ié may be noied iitat ait octahedral site does nick me eda in shape but it means that this site is surrounded by six nearest neighbour fat octahedraliy (Octahedral void (at the edge) 41 {0/4 th part of octahedral ; ‘void is obtained at Octahedral void ach edge) fat the body centre} In fce, total number of octahedral voids = {1x 1) + aaxhin1+3-4 {Cube centre} (edge centre) In fcc, number of atoms = 4 and number of octahedral voids ~ 4 : number of tetrahedral wolds = 8 ‘So we can say that, in 3D close packing one octahedral void is attached with one atom, Illustrations Illustration 10. The number of octahedral sites in a cubical close packed array of N spheres is ne (2)2N (3)N (4)4N Ans. (3) Solution. Mlustration 11. Atom A is every element of FCC, atom B is present at every Octahedral void, atom C is present at Solution. 16 2596 of Tetrahedral void. Find out the possible molecular formula of the compound ? Atomn A is every element of FCC = 4 atoms of A Atom B is present at every octahedral void = 4 atoms of B 25 ‘Atom C is present at 25% of tetrahedral void = 8x". = 2 atoms of C 100 So, the possible molecular formula is A, B,C, = A, B, C.1.10 STUDY OF IONIC CRYSTALS Limiting Radius Ratio An ionic erystal contains a large number of cations and anions. Generally cations are smaller in size than that of anions. The cations are surrounded by anions and they touch each other. These ions are arranged in space fn such a way to produce maximum stability, So the limiting radius ratio tells about + Stability of ionic crystal (i) Coordination number ii) Geometry of voids (a) Triangular : All anions touches each other and co-ordination number is 3 R o- 50 Rae R £0880" = Tp VSR + V8r = 2R vir (2-3)R 027 7370-158 LRR, = 0.195 = F<1 {b) Tetrahedral void : All anions touches each other and co-ordination number of cation is 4. Face diagonal AC = J9a=2R Ro or a= oR Triangle ACD - ADP= AC?+ CD? AD (2a) +(a)’ = 2at+ at= dat AD= Ga ‘According to cube diagonal AD Ga = 2+2R = AD Put the value ofa = v2R V3 xV2R = 2r42R ¥3x VOR _ 2r+2R Bot yy 2R RR or YER B 7Pre-Medical (©) Octahedral void : All the anions ate touch each other and co-ordination number is 6, In SABC AC? = ABP+ BC? (2R + 21F = (2RP + (2rP QR + 21) = JBR® 2R + r= 2OR 2R (v2 -1) = 2r r LaV8-1-0.414 Re (@) Cubic void : All the anions are touch each other and co-ordination number is 8 According to cube diagonal AD = J3a=2r+2R (a= 2R= BC) A MB x2R= 21+ 2R Dividing by 2r on both sides. yD VB apt 1 > pav8-1 = 1.732-1= 0.732 ras PR © The preferrad direction ofthe structure with irzrease in the radius ratio sas folows: Plane triangular 022, Tetrahedral —41_, octahedral 0732, Cubic © LIMITING RADIUS RATIO FOR VARIOUS TYPES OF VOIDS ; Limiting radius Coordination ‘Structural Example i ratio = 1/R Number Arrangement i (Type of voids) i 0.155 < 1/R < 0.225 3 Plane Trigonal Boron Oxide(B,0, ; 0.225 <1/R< 0.414 4 Tetrahedral 208, SiO, : 0.414 s1/R < 0.732 6 Octahedral Nac, MgO i 0,732 s r/R < 1.000 8 Cubical csc | 18 EFM Sencar conewiveous. sew suRoFMORS masses Canin Illustrations ——_—_. Itustration 12. Assertion : In crystal lattice, the size of the cation is iarger in a tetrahedral hole than in an ‘octahedral hole. Reason : The cations occupy more space than atoms in crystal packing, a) A (AB @c @D Solution. Ans. (4) Mlustration13. Each unit cell of NaCl consists of 14 CF ions and (1) 13 Nat (214 Nat (3)6 Nar (4) Alt are wrong Solution. Ans. (1) Iustration14. A solid A*Bs has NaCl type close packed structure. If the anion has a radius of 250 pm, what should be the ideal radius for the cation ? Can a cation C* having a radius of 180 pm be slipped into the tetrahedral ste of the crystal AB" ? Give reason for your answer. Solution In Na’Ct crystal each Na" ion is surrounded by 6 CI fons and vice versa. Thus Nar ion is placed in octahedral hole The limiting radius ratio for octahedral site = 0.414 or ‘Given that radius of anion (B}) R = 250 pm ie, radius of cation (Ar) 1= 0.414 R = 0.414 x250 pm = 108.5 pm. ‘Thus ideal radius for cation (AV) is r # 108.5 pm, ‘We know that (r/R) for tetrahedral hole is 0.225. rors :Sor= 56.25 pm “Thus ideal radius for cation is 56.25 pm for tetrahedral hole. But the radius of C* is 180 pm. Reis much larger than ideal radius ie. 56.25 pm. Therefore we can not slipped cation C* into the tetrahedral site. Mlustration15. Assertion :- In rock salt structure, the sodium ions occupy octahedral voids. Reason :~ The radius ratio r'/r* in case of NaCl lies betwen 0.225 to 0.414, aa QB ac @D Solution. Ans. (3) . 1 TYPE CsCLTYPE For NaCl: For CsCl: Distance between two nearest ions (1 +1") = Distance between fwo nearest ions (r" +.) = — In both structures cation and anion can exchange their position. Or + 2r= Ja ie fF 19-ranoaHL Oams.cnor \yeMnaoM ONE NON BEIVINT NR OR? NT SOX OAWNDE WT IMNONONNNRENIDWIC ERASE OH Jo mowe® Mion knowns 22” © 9m | tour sao eUsoH awareyds suzo ais # “L. ° or UZ" (even) se ures 29> 2.029 ’ {LT ada, suz [+ sy ‘OU ) “d''D Jo OWA Ha9N —_O, S?eN (ORN Orne WHEL ALN Wy ems 99 (eunoynuy) stom 2Ob + Ng (1 = 2) adh OFN | "yP=0 “Ip%0 ) : HEL Bios 1 Lg 2 aao A 4s “os ‘sop 079] wows Kiang & 8D (e46, stony) Pye “ged AB + POP (21) ads "eo 1 TMD 4aND ‘TORO ids pesporpesias rettoy 32 Yeoo (emayeucg) “BY “ORD ‘078 50 WH (0 KOS IV UZ odhy, apuaig 2417) (1: 1) easy suz [i pron ogre Yo on jo anuao fpog ay & $9 OL + 801 STUN aby DBy Gea Key symaur yes “aupesye 0) 4 sapnydins pue sapnig PNP (eck wes »peR) (a r-eN TD 30 sepmeH |" Ob + .eNP (re Den f >in wed Tavs |. soduexg amor yo ody | * A9'D Jo nia Hod 19, Sao AHO Aiea ay & (EN. 3 3 éEM Chemistry 1.12 DEFECTS OR IMPERFECTIONS IN SOLIDS Ideal crystal : The crystal in which al the lattice points are occupi by the component particles or groups of particles is called an ideal crystal. Ideal erystals are grown up at absolute kelvin temperature (zero Ki) Solid state is characterised by vitratory motion about the mean position of constituent particles. At absolute zero allthe types of motions cease, and therefore crstals tend to have a perfeciy ordered arrangement. Aste temperature increases, salecular motions fbratory armpltudes increase and therefore the ions maylose their usual stesand ether get missed or ‘occupy interstitial postions in the esta... deviations irom ordered arrangement tekie place. Any deviation from the perfectly ordered arrangement gives rise fo 2 defector imperfection fn the caytal. Defect in erstals are procucad ether due to thermal effeds or by dking certain impurities in he pure erstab (doping). Defects in crystals maybe discussed as Crystal defects Stoichiometric Impurity defects Non stoichiometric defects (some external impurity is mixed} defects Schottky Frenkel Metal Metal defects defects excess defects deficiency defects (A) Stoichiometric Defects f@ Stoichiometric compounds are these in which the number of positive and negative ions are exactly in the ratio as shown by their chemical formulae. Two types of defects are observed in these compounds. {@) Schottky defect, (b) Frenkel defect Schottky defect : This type of defect is produced when equal number of cations and anions are missing from their respective positions leaving behind a pair of holes. The crystal as a whole remains neutral because the number of missing positive ions (cations) and negative tons (anions) is the samme Scherty defect e It is kind of vacancy defect. © Schottky defect appears generally in tonic compounds in which radius ratio Ir /r isnot far below unity. For this defect, the cations and anion should not differ much in size. © For schottky defect. co-ordination numbers of the ions should be high, Examples of ionic solids showing this defect are NaCl; CsCl, KCL. AgBr etc Consequences of schotthy defect : © Density of the crystal decreases © The crystal begins to conduct electricity to small extent by ionic mechanism, © The presence of too many ‘voids! lowers lattice energy or the stability of the crystal. 24Pre-Medical Any (0) Frenkel defect : This type of defect js created when an ion leaves its appropriate site in the lattice and ‘occupies an interstitial site. A hole or vacancy is thus produced in the lattice. Frenkel detect The electroneutrality of the crystal is maintained since the number of positive and negative ions is the same, Since positive ions are small, in size, they usually leave their positions in the lattice and occupy interstitial positions. itis also calted dislocation defect. Frenkel defect is exhibited in ionic compounds in which the radius ratio [t°/r]is low. The cations and anions differ much in their sizes and the ions have low co-ordination numbers. Examplesare ZnS, AgB, Agl, AgCl Consequences of Frenkel defect : © itis akind of dislocation defect. © The closeness of lke charges tends to increase the dielectric constant ofthe crystal © The crystal showing a frenkel defect conducts electricity to a small extent by ionic mechanism, © The density of the crystal remains the same. (B) Impurity Defects If molten NaC! containing alittle amount of SrC\, is crystallised, some of the sites of Na* ions are occupied by Sr®*, Each Sr replaces two Na* Tons. It occupies the site of one ion and the other site remains vacant. The cationic vacancies thus produced are equal in number to that of Sr* ions, Another similar example is the solid solution of CdCI, and AgCl. Induction of cation vacancy in (C)_ Non-stoichiometric Defects ‘NaC! by substitution of Na” by Sr" These types of defects are observed in the compounds of transitional elements. These defects arise either due to the presence of excess metal ions or excess non-metal ions. {a) Metal excess defect due to anion vacancies : A compound may have excess metal ion if an anion {negative ion) is absent from its appropriate lattice site creating a ‘void which is occupied by an electron. Tonic crystal which are lkely 1o posses schotthy defect, may also develop this type of metal excess defect. ‘When alkali metal halides are heated in a atmosphere of vapours of the alkali metal, anion vacancies are ‘created. The anions thalde ions) diffuse to the surface ofthe erysta from theit appropriate lattice sites to combine with the newly generated metal cations. The e lost by the metal atom diffuse through the crystal are known as Fecentres. The main consequence of metal excess defect is the development of colour in the crystal. For example, when NaC! caystal is heated in an atmosphere of Na vapours, it becomes yellow. Similarly, KCI crystal when heated i an atmosphere of potassium vapours, it appear violet. ID ncrearnais anecer cine NcRE SOD STOLE SS BEd (b) Metal excess defect due to interstitial cations : This type of defect is shown by crystals which are likely to exhibit Frenkel defect. An excess positive ton is located in the interstitial site. To maintain electrical neutrality, an electron is present inthe intrestitial site. An example showing this type of defect is ZnO. When ZnO is heated, it loses oxygen reversibly, The excess Zn“* ions are accommodated in the interstitial sites, the, electrons are enclosed in the neighbouring interstitials. The yellow colour of ZnO when hot is due to these trapped electrons. These electrons also explain electrical conductivity of the Zn0 crystal ()_ Metal Deficiency Defect There are many solids which are difficult to prepare in the stoichiometric composition and contain less ‘amount of the metal as compared to the stoichiometric proportion. A typical example of this type is FeO which is mostly found with a composition of Fe, ..O. It may actually range from Fe, 0 to Fe, 40. In crystals of FeO some Fe cations are missing and the loss of positive charge is made up by the presence of required number of Fe" ions. ' On increasing temperature coordination number decreases. On increasing pressure; coordination number increases. Fin a crystal complete lattice of ion along a line are dissapeared, such defect is called line defect. Schotthy defects and Frenkel defects are point defects. - Structure of diamond : Sols which follows structure of diamonds known as diamond cubic. Diamond has cep structure where carbon atroms are present at comers and face centre with four more atom present at alternate tetrahedral voids or 50% THY so number of effective atoms: [Bx p-o—5)o(4x2)> z 2 The carbon atoms present in THV touches its four surrounding atoms so coordination nuraber is equal to four. ‘The carbon atoms at fcc lattice do not touches atom at all. Distance between two adjacent carbon atoms (21} 8 fey PE 3 #034, $09 PE=34 (a) Illustrations Ilustration 16, In the Schottky defect (1) cations are missing from the lattice sites and occupy the interstitial sites (2) equal number of cations and anions are missing (3) anions are missing and electrons are present in their place (4) equal number of extra cations and electrons are present in the interstitial sites Solution Ans. (2) ore Basa IMlustration 17. Assertion :~ Schottky type defects is chown by crystals with high co-ordination number. Reason = In Schottky defect equal number of cations and anions are missing from their lattice sites. Ma QB @c @D Solution Ans. (2) Ilustration 18. Schotthy defect lowers the density of ionic crystals while Frenkel defect does not, Discuss. Solution. In Schotthy defect, cerlain cation and anions are missing irom the crystal lattice. Therefore, the density of the crystal decreases. However, in Frenkel defect the fons do not leave the lattice but they simply change their positions from lattice points to the interstitial spaces. As a result, the density of the crystal remains unchanged. i i 3 i 3 i i 23Feed Bae 1, The edge length of face centred cubic unit cell having rock salt structure is 508 pm. the radius of the cation is 110 pm, the radius of the anion is (1) 144 pm (2) 288 pm (3) 618 pm (4) 398 pm 2. ina solid ‘AB’ having ihe NaCi struaure, ‘A’ atoms occupy the every cep and B atoms are in OHV, If all the face-centred atoms along one of the axes are removed, then the resultant stoichiometry ofthe solid is~ (1) AB, @AB GAB, AB, 3. How many unit cells are present in a cube shaped ideal crystal of NaCl of mass 1.00 g? [Atomic mass : Na = 23, Cl = 35.5] (0) 5.14 x10 (2)1.28 x 10% (3) 1.71 x10 (@) 2.57 x10 4, Asolid AB has the NaCl structure, If radius of the cation A’ is 120 pm, the maximum value of the radius of the anion Bis (1) 290 pm (2) 350 pm (3) 250 pm ¢4) 400 pm 5. Ifthe distnace between Nav and Cl-ions in sodium chloride crystal is x pm, then length of the edge of the unit call is . (1) 2x pm 2) 4x pm (3) x/2 pm (4) x/4 pm 6. HOP crystal in made of A ions and B ions are arranged in 2/3" of octahedral voids. The simplest formula of unit cell is AB, QAB, BAB, MAB, 7. AFCC crystal of O (oxide) ions has M™ ions in 50% of octahedral voids, then the value of n is (2 (B33 34 ayn 8. If the edge length of a KCi unit cell is 488 pm, what is the length of KCI hond if it exystallises in the foc structure ? 41) 122 pm (2) 244 pm (3) 488 pm (4) 974 pm 9. Ina solid lattice, the cation has left a lattice site and is located at interstitial position, the lattice defect is {Aj interstitial defect (2) vacancy detect G3) Frenkel defect, (4) Schotthy defect